CN107900373B - Superfine W-Cu composite powder and preparation method thereof - Google Patents
Superfine W-Cu composite powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 106
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003751 zinc Chemical class 0.000 claims abstract description 20
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001879 copper Chemical class 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims description 22
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 description 6
- 238000011946 reduction process Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 229910052927 chalcanthite Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B22F1/0007—
Abstract
The invention discloses superfine W-Cu composite powder and a preparation method thereof, wherein the method comprises the following steps: (1) mixing copper salt, zinc salt and sodium tungstate solution to obtain mixed solution; (2) sending the mixed solution into a high-pressure reaction kettle for stirring and reacting so as to obtain reacted liquid; (3) filtering and cleaning the reacted liquid to obtain a copper tungstate-zinc tungstate composite powder precursor and a filtrate; (4) drying the copper tungstate-zinc tungstate composite powder precursor to obtain a dried composite powder precursor; (5) and reducing the dried composite powder precursor in a hydrogen atmosphere to obtain the superfine W-Cu composite powder. The method can be used for preparing the superfine W-Cu composite powder with high purity, small grain size and controllable W-Cu component proportion, and meanwhile, the process is simple, can realize mass production and has good application prospect.
Description
Technical Field
The invention belongs to the field of metal composite powder preparation, and particularly relates to superfine W-Cu composite powder and a preparation method thereof.
Background
Tungsten has the properties of high melting point, high density, fusion welding resistance, electric corrosion resistance, high-temperature strength and the like, copper has high thermal conductivity and electric conductivity, good ductility and easy processing, and parts prepared by alloying the tungsten and the copper can have the properties of tungsten and copper and can be widely applied to military materials and electronic materials. However, tungsten powder and copper powder are not mutually dissolved, the contact angle is large, the tungsten powder and the copper powder can only form pseudo alloy, and the W-Cu composite material prepared by the traditional powder metallurgy and infiltration method has poor compactness and is difficult to meet the requirements of modern materials. The existing method for preparing superfine W-Cu composite powder at home and abroad has the disadvantages that the ball milling time is long, the powder contains impurity metal elements, the obtained powder is easy to agglomerate and agglomerate, and the wall sticking phenomenon is serious; or the prepared precursor powder is greatly influenced by the reaction temperature and the reaction time, and the reduction control is difficult; or the process is complex and difficult to generate in batch.
Therefore, the existing technology for preparing ultra-fine W-Cu composite powder is in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide an ultra-fine W-Cu composite powder and a method for preparing the same. The method can be used for preparing the superfine W-Cu composite powder with high purity, small grain size and controllable W-Cu component proportion, and meanwhile, the process is simple, can realize mass production and has good application prospect.
The technical solution of the applicant is completed by the inventors based on the following findings: at present, the method for preparing the superfine W-Cu composite powder at home and abroad mainly comprises a mechanical alloying method, a high-temperature reduction method, an atomization drying method, a sol-gel method, a chemical precipitation method and the like. The mechanical alloying method is to stir W, Cu two kinds of metal element powder evenly, ball milling is carried out in a high-energy ball mill to lead W, Cu powder to be mixed evenly and form W-Cu solid solution of nano crystal, the main disadvantage of the method is that the ball milling time required for reaching powder with larger grain size is very long, which inevitably brings impurity metal elements, the obtained powder is easy to agglomerate and agglomerate, and the wall sticking phenomenon is serious. The spray drying method is characterized in that ammonium metatungstate and copper nitrate are prepared into a mixed solution, a W-Cu precursor obtained after spray drying is roasted, a product is reduced under hydrogen to obtain W-Cu composite powder, the W-Cu composite powder prepared by the spray drying method is fine and uniform in particle and not easy to introduce impurities, but the reduction control of the prepared precursor powder is difficult and is greatly influenced by reaction temperature and reaction time. The sol-gel method is to react easily hydrolyzed metal compound (inorganic salt or metal alkoxide) with water or other substances in a certain solvent to form gel, and then prepare W-Cu composite powder after drying/calcining, reducing and the like. The inventor of the application actively explores the existing preparation process of the superfine W-Cu composite powder, aims to overcome the defects in the prior art and aims to obtain the superfine W-Cu composite powder with high purity, small grain size and controllable W-Cu component proportion.
To this end, in one aspect of the present invention, the present invention provides a method of preparing an ultra-fine W-Cu composite powder, according to an embodiment of the present invention, the method including:
(1) mixing copper salt, zinc salt and sodium tungstate solution to obtain mixed solution;
(2) sending the mixed solution into a high-pressure reaction kettle for stirring and reacting so as to obtain reacted liquid;
(3) filtering and cleaning the reacted liquid to obtain a copper tungstate-zinc tungstate composite powder precursor and a filtrate;
(4) drying the copper tungstate-zinc tungstate composite powder precursor to obtain a dried composite powder precursor;
(5) and reducing the dried composite powder precursor in a hydrogen atmosphere to obtain the superfine W-Cu composite powder.
According to the method for preparing the superfine W-Cu composite powder, disclosed by the embodiment of the invention, copper salt, zinc salt and sodium tungstate are reacted to obtain a copper tungstate-zinc tungstate composite powder precursor, then the precursor is placed in a hydrogen atmosphere for reduction reaction by utilizing the characteristic that the tungstate can be reduced by hydrogen, and the reduction temperature is controlled to be between the volatilization temperatures of elemental zinc and elemental copper, so that the elemental zinc generated by reduction can be gasified and smoothly discharged, and the superfine W-Cu composite powder is obtained. And because the crystal grain size of the precursor is fine and evenly distributed, the precursor is not easy to have abnormal growth of the crystal grain in the hydrogen reduction process, and the obtained superfine W-Cu composite powder can be kept at the submicron crystal grain size. Therefore, the method can be used for preparing the superfine W-Cu composite powder with high purity, small grain size and controllable W-Cu component proportion, and meanwhile, the process is simple, can realize mass production and has good application prospect.
In addition, the method of preparing the ultra-fine W — Cu composite powder according to the above-described embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, in step (1), the copper salt is mixed with the zinc salt, the sodium tungstate solution as Cu2+And Zn2+The sum of the number of moles of Na2WO4The mole number is 1-2: 1, mixing. This is advantageous in improving the grade of the ultrafine W-Cu composite powder.
In some embodiments of the present invention, in step (2), the stirring speed is 200-500 r/min. This can further improve the grade of the ultrafine W-Cu composite powder.
In some embodiments of the invention, in step (2), the pressure in the autoclave is from 0.3 to 1.5 MPa. This can further improve the grade of the ultrafine W-Cu composite powder.
In some embodiments of the present invention, in the step (2), the reaction temperature is 100-180 ℃ and the reaction time is 1-5 h. This can further improve the grade of the ultrafine W-Cu composite powder.
In some embodiments of the present invention, in step (5), the temperature of the reduction treatment is 700-1000 ℃ and the time is 1-3 h. This can further improve the grade of the ultrafine W-Cu composite powder.
In yet another aspect of the present invention, an ultra-fine W-Cu composite powder is provided. According to an embodiment of the present invention, the composite powder is prepared by the above-described method for preparing an ultra-fine W-Cu composite powder. Thus, an ultrafine W-Cu composite powder having a high purity, a small crystal grain size and a controllable W-Cu component ratio can be obtained.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing an ultra-fine W-Cu composite powder according to one embodiment of the present invention;
FIG. 2 is an SEM photograph of a dried copper tungstate-zinc tungstate composite powder precursor, according to one embodiment of the invention;
FIG. 3 is an XRD spectrum of a dried copper tungstate-zinc tungstate composite powder precursor, according to one embodiment of the invention;
FIG. 4 is an SEM photograph of an ultra-fine W-20 wt.% Cu composite powder according to one embodiment of the present invention;
fig. 5 is an XRD pattern of an ultra-fine W-20 wt.% Cu composite powder according to one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the present invention, the present invention provides a method of preparing an ultra-fine W-Cu composite powder, according to an embodiment of the present invention, with reference to fig. 1, the method including:
s100: mixing copper salt and sodium tungstate solution
In this step, a copper salt, a zinc salt and a sodium tungstate solution are mixed to obtain a mixed solution. It should be noted that the specific type of the copper salt and the zinc salt is not particularly limited, and those skilled in the art can select them according to actual needs, for example, the copper salt may be CuSO4·5H2O, the zinc salt can be Zn (NO)3)2·6H2And O. Specifically, the added zinc salt reacts with sodium tungstate to generate zinc tungstate precipitate, a reduction product of the zinc tungstate in a hydrogen atmosphere is tungsten powder, zinc is gasified and volatilized in the reduction process and discharged, and the content of W in the W-Cu composite powder can be increased by increasing the addition of the zinc salt.
According to a further embodiment of the invention, the copper salt may be mixed with the zinc salt, sodium tungstate solution as Cu2+And Zn2+The sum of the number of moles of Na2WO4The mole number is 1-2: 1, mixing. Specifically, the relative addition of copper salt and zinc salt can be determined according to the W/Cu value in the final product superfine W-Cu composite powder, thereby realizing the control of the proportion of W and Cu components. In particular, e.g. from n (Cu)2+)+n(Zn2+)/n(Na2WO4) When zinc salt is added in an amount of zero, i.e. n (Zn), 1/12+)＝0，n(Cu2+)/n(Na2WO4) When the precursor component is 1/1, the obtained precursor component is a single component of copper tungstate, and the Cu content of the superfine W-Cu composite powder obtained by reduction is 25.82%, which is the maximum content of the Cu component in the superfine W-Cu composite powder. In the presence of a holding n (Cu)2+)+n(Zn2 +)/n(Na2WO4) When the amount of zinc salt added was increased to 1/1, the Cu content in the resulting ultrafine W — Cu composite powder was less than 25.82%. If W-20 wt.% Cu is to be produced, the relative amounts of copper and zinc salts are added to n (Cu)2+)/n(Zn2+)＝0.723/0.277。
S200: the mixed solution is sent to a high-pressure reaction kettle for stirring and reaction
In the step, the mixed solution is sent to a high-pressure reaction kettle to be stirred and reacted, so as to obtain a reacted solution. Specifically, the mixed solution contains copper salt, zinc salt and sodium tungstate, copper ions in the copper salt and zinc ions in the zinc salt react with the sodium tungstate in the high-pressure reaction kettle to respectively obtain copper tungstate and zinc tungstate precipitates, and related chemical reaction formulas are as follows:
Cu2++WO4 2-＝CuWO4↓
Zn2++WO4 2-＝ZnWO4↓
according to an embodiment of the present invention, the stirring speed is not particularly limited, and one skilled in the art can select the stirring speed according to actual needs, and according to an embodiment of the present invention, the stirring speed may be 200-500 r/min. The inventor finds that the stirring speed is obviously better than other conditions to improve the precipitation rate of the liquid after reaction.
According to still another embodiment of the present invention, the pressure in the autoclave is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the pressure in the autoclave may be 0.3 to 1.5 MPa.
According to another embodiment of the present invention, the reaction conditions are not particularly limited, and can be selected by one skilled in the art according to actual needs, and according to one embodiment of the present invention, the reaction temperature can be 100-180 ℃ and the reaction time can be 1-5 h. The inventors have found that if the reaction temperature is too high, there will be WO3If the reaction temperature is too low, the precipitation rate will be reduced. Thus, under this condition, it is ensured that the tungsten precipitation is complete and the product growth is more uniform.
S300: filtering and cleaning the reacted liquid
In the step, the reacted liquid contains copper tungstate precipitate and zinc tungstate precipitate, and the reacted liquid is filtered and cleaned to obtain a copper tungstate-zinc tungstate composite powder precursor and a filtrate. The inventors found that the composite powder precursor obtained by hydrothermal reaction had fine crystal grain size and uniform distribution.
S400: drying the copper tungstate-zinc tungstate composite powder precursor
In the step, the obtained copper tungstate-zinc tungstate composite powder precursor is dried to obtain a dried composite powder precursor. Therefore, the method is beneficial to reducing the moisture in the copper tungstate-zinc tungstate composite powder precursor, improving the reduction efficiency of the composite powder precursor after subsequent drying, and reducing the reduction energy consumption. According to an embodiment of the present invention, an SEM photograph of a dried composite powder precursor obtained by drying a copper tungstate-zinc tungstate composite powder precursor is shown in fig. 2, and an XRD spectrum is shown in fig. 3.
S500: reducing the dried composite powder precursor in hydrogen atmosphere
In the step, the dried composite powder precursor is subjected to reduction treatment in a hydrogen atmosphere to obtain the superfine W-Cu composite powder. Specifically, the dried composite powder precursor contains copper tungstate and zinc tungstate, wherein the copper tungstate and the zinc tungstate react with hydrogen respectively, the zinc obtained by the reaction is gasified, volatilized and discharged by controlling the temperature of reduction treatment, the copper is left in a solid state, and the grain size of the dried composite powder precursor is small and uniformly distributed, so that abnormal grain growth is not easy to occur in the reduction process, and the superfine W-Cu composite powder with the submicron grain size can be obtained. The related chemical reaction formula is as follows:
CuWO4(s)+4H2(g)＝Cu(s)+W(s)+4H2O↑
ZnWO4(s)+4H2(g)＝Zn(g)↑+W(s)+4H2O↑
according to an embodiment of the present invention, the conditions of the reduction treatment are not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to an embodiment of the present invention, the temperature of the reduction treatment may be 700-. The inventor finds that if the reduction temperature is too high, the time is too long, the grain size of the product is larger, and if the reduction temperature is too low, the time is too short, and the gasification and volatilization of zinc are not facilitated. Therefore, the reduction treatment condition can ensure that the obtained superfine W-Cu composite powder has higher grade and value.
According to the method for preparing the superfine W-Cu composite powder, disclosed by the embodiment of the invention, copper salt, zinc salt and sodium tungstate are reacted to obtain a copper tungstate-zinc tungstate composite powder precursor, then the precursor is placed in a hydrogen atmosphere for reduction reaction by utilizing the characteristic that the tungstate can be reduced by hydrogen, and the reduction temperature is controlled to be between the volatilization temperatures of elemental zinc and elemental copper, so that the elemental zinc generated by reduction can be gasified and smoothly discharged, and the superfine W-Cu composite powder is obtained. And because the crystal grain size of the precursor is fine and evenly distributed, the precursor is not easy to have abnormal growth of the crystal grain in the hydrogen reduction process, and the obtained superfine W-Cu composite powder can be kept at the submicron crystal grain size. Therefore, the method can be used for preparing the superfine W-Cu composite powder with high purity, small grain size and controllable W-Cu component proportion, and meanwhile, the process is simple, can realize mass production and has good application prospect.
As described above, the method of preparing an ultra-fine W-Cu composite powder according to an embodiment of the present invention may have at least one advantage selected from the following:
1) the method has simple process flow, is not easy to introduce impurities in the reaction process, and can prepare high-purity W-Cu composite powder.
2) The crystal grain size of the precursor of the copper tungstate-zinc tungstate composite powder obtained by the hydrothermal reaction is fine and is uniformly distributed, so that the abnormal growth of the crystal grain of the precursor is not easy to occur in the hydrogen reduction process, and the obtained W-Cu composite powder can keep the submicron-grade crystal grain size.
In yet another aspect of the present invention, an ultra-fine W-Cu composite powder is provided. According to an embodiment of the present invention, the composite powder is prepared by the above-described method for preparing an ultra-fine W-Cu composite powder. Thus, an ultrafine W-Cu composite powder having a high purity, a small crystal grain size and a controllable W-Cu component ratio can be obtained. It should be noted that the features and advantages described above with respect to the method of preparing the ultra-fine W-Cu composite powder are also applicable to the ultra-fine W-Cu composite powder, and will not be described herein again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Taking Na2WO4·2H2O 99.59g，CuSO4·5H2O 54.16g，Zn(NO3)2·6H2Adding 300mL of deionized water into 24.72g of O to prepare a mixed solution, placing the mixed solution in a high-pressure reaction kettle for reaction at the reaction temperature of 170 ℃ for 4h at the stirring speed of 400r/min, filtering, cleaning and drying a sample after the reaction to obtain a dried copper tungstate-zinc tungstate composite powder precursor. The precursor is placed in an atmosphere furnace to be reduced in hydrogen atmosphere at the reduction temperature of 900 ℃ for 2h to obtainThe SEM photograph of the superfine W-20 wt.% Cu composite powder is shown in figure 4, and the XRD pattern is shown in figure 5.
Example 2
Taking Na2WO4·2H2O 99.59g，CuSO4·5H2O 24.12g，Zn(NO3)2·6H2Adding 300mL of deionized water into 61.07g of the mixed solution to prepare a mixed solution, placing the mixed solution in a high-pressure reaction kettle for reaction at the reaction temperature of 180 ℃ for 3h at the stirring speed of 400r/min, filtering, cleaning and drying a sample after the reaction to obtain a dried copper tungstate-zinc tungstate composite powder precursor. And (3) placing the precursor in an atmosphere furnace to reduce in a hydrogen atmosphere at 1000 ℃ for 1h to obtain the superfine W-10 wt.% Cu composite powder.
Comparative example
Taking Na2WO4·2H2O 99.59g，CuSO4·5H2Adding 75.38g of O, adding 300mL of deionized water to prepare a mixed solution, placing the mixed solution in a high-pressure reaction kettle for reaction at the reaction temperature of 160 ℃ for 5h at the stirring speed of 400r/min, filtering, cleaning and drying a sample after the reaction to obtain a dried copper tungstate powder precursor. And (3) placing the precursor in an atmosphere furnace to reduce in a hydrogen atmosphere at the reduction temperature of 800 ℃ for 3h to obtain the superfine W-25.82 wt.% Cu composite powder.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (5)
1. A method of preparing an ultra-fine W-Cu composite powder, comprising:
(1) mixing copper salt, zinc salt and sodium tungstate solution to obtain mixed solution;
(2) sending the mixed solution into a high-pressure reaction kettle for stirring and reacting so as to obtain reacted liquid;
(3) filtering and cleaning the reacted liquid to obtain a copper tungstate-zinc tungstate composite powder precursor and a filtrate;
(4) drying the copper tungstate-zinc tungstate composite powder precursor to obtain a dried composite powder precursor;
(5) reducing the dried composite powder precursor in hydrogen atmosphere to obtain superfine W-Cu composite powder,
wherein, in the step (1), the copper salt, the zinc salt and the sodium tungstate solution are mixed according to Cu2+ and Zn2+ mole number of the sum with Na2WO4The mole number is 1-2: 1, and increasing the content of W in the W-Cu composite powder by increasing the addition amount of the zinc salt.
2. The method as claimed in claim 1, wherein in step (2), the stirring speed is 200-500 r/min.
3. The method according to claim 1 or 2, wherein in the step (2), the pressure in the autoclave is 0.3 to 1.5 MPa.
4. The method as claimed in claim 3, wherein in step (2), the reaction temperature is 100-180 ℃ and the reaction time is 1-5 h.
5. The method as claimed in claim 1, wherein in step (5), the temperature of the reduction treatment is 700-1000 ℃ for 1-3 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103223494A (en) * | 2013-03-27 | 2013-07-31 | 河南科技大学 | Preparation method of tungsten copper oxide composite powder through hydro-thermal synthesis |
| CN103537686A (en) * | 2013-10-16 | 2014-01-29 | 河南科技大学 | Preparation method of WCu composite powder with tungsten coating copper |
| CN104942303A (en) * | 2015-07-01 | 2015-09-30 | 崇义章源钨业股份有限公司 | Method for preparing tungsten powder |
| CN106077695A (en) * | 2016-08-11 | 2016-11-09 | 河南科技大学 | A kind of preparation method of high-copper tungsten copper nano composite powder |
-
2017
- 2017-12-07 CN CN201711288859.7A patent/CN107900373B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103223494A (en) * | 2013-03-27 | 2013-07-31 | 河南科技大学 | Preparation method of tungsten copper oxide composite powder through hydro-thermal synthesis |
| CN103537686A (en) * | 2013-10-16 | 2014-01-29 | 河南科技大学 | Preparation method of WCu composite powder with tungsten coating copper |
| CN104942303A (en) * | 2015-07-01 | 2015-09-30 | 崇义章源钨业股份有限公司 | Method for preparing tungsten powder |
| CN106077695A (en) * | 2016-08-11 | 2016-11-09 | 河南科技大学 | A kind of preparation method of high-copper tungsten copper nano composite powder |
Non-Patent Citations (2)
| Title |
|---|
| Nano-composite Powder of Tungsten Coated Copper Produced by Thermo-chemistry Co-reduction;Li Junqiang等;《Rare Metal Materials and Engineering》;20121231;第41卷(第12期);2091-2094 * |
| Synthesis and densification of W-30 wt%Cu composite powders using ammonium meta tungstate and copper nitrate as precursors;Ardestani, M.等;《INTERNATIONAL JOURNAL OF REFRACTORY METALS & HARD》;20090731;第27卷(第4期);796-800 * |
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