CN107900373A - Ultra-fine W Cu composite powders and preparation method thereof - Google Patents
Ultra-fine W Cu composite powders and preparation method thereof Download PDFInfo
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- CN107900373A CN107900373A CN201711288859.7A CN201711288859A CN107900373A CN 107900373 A CN107900373 A CN 107900373A CN 201711288859 A CN201711288859 A CN 201711288859A CN 107900373 A CN107900373 A CN 107900373A
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- 239000000843 powder Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 35
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 230000009467 reduction Effects 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 24
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 98
- 229910052802 copper Inorganic materials 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 15
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 description 26
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052927 chalcanthite Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance 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
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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—
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a kind of ultra-fine W Cu composite powders and preparation method thereof, this method includes：(1) mantoquita, zinc salt and sodium tungstate solution are mixed, to obtain mixed solution；(2) mixed solution is sent and is stirred, reacts into autoclave, so as to liquid after being reacted；(3) liquid after the reaction is filtered and cleaning treatment, to obtain copper tungstate Zinc Tungstate composite powder presoma and filtered fluid；(4) processing is dried in the copper tungstate Zinc Tungstate composite powder presoma, so as to composite powder presoma after being dried；(5) composite powder presoma after the drying is subjected to reduction treatment in a hydrogen atmosphere, to obtain ultra-fine W Cu composite powders.The ultra-fine W Cu composite powders that purity is high, crystallite dimension is small and W Cu component ratios are controllable can be made using this method, while the technique is simple, it can be achieved that mass production, has a good application prospect.
Description
Technical field
The invention belongs to composite metal powder preparation field, specifically, the present invention relates to ultra-fine W-Cu composite powders and
Its preparation method.
Background technology
Tungsten has the performances such as high-melting-point, high density, resistance fusion welding, electrical erosion resistance, elevated temperature strength be good, the thermal conductivity and electricity of copper
Conductance is high, ductility is good, easy to process, and part prepared by the two alloying can have the performance of tungsten and copper concurrently, be widely used in
Military project material and electronic material.But since tungsten, copper powders are mutually insoluble, contact angle is big, the two can be only formed pseudo-alloy, adopts
The W-Cu composite material consistency prepared with traditional powder metallurgy and infiltration method is poor, has been difficult to meet wanting for modern material
Ask.The existing method for preparing ultra-fine W-Cu composite powders both at home and abroad, otherwise the long contaminating metal element of Ball-milling Time, and gained powder
End is easy to agglomerating caking, and wall sticking phenomenon is serious；The precursor powder prepared is had a great influence by reaction temperature and reaction time,
Reduction control is more difficult；Complex technical process, it is difficult to which mass generates.
Therefore, the existing technology for preparing ultra-fine W-Cu composite powders is further improved.
The content of the invention
It is contemplated that solve at least some of the technical problems in related technologies.For this reason, the present invention
One purpose is to propose a kind of ultra-fine W-Cu composite powders and preparation method thereof.Purity height, crystal grain can be made using this method
The ultra-fine W-Cu composite powders that size is small and W-Cu component ratios are controllable, while the technique is simple, it can be achieved that producing in enormous quantities, tool
There is good application prospect.
The technical solution of the applicant is that inventor has found to complete based on following：At present, ultra-fine W-Cu is prepared both at home and abroad
The method of composite powder mainly has mechanical alloying method, high temperature reduction method, atomization drying method and sol-gel process, chemical precipitation
Method etc..Mechanical alloying method is to stir evenly two kinds of elemental metalpowders of W, Cu, in high energy ball mill carry out ball milling make W,
Cu powder is uniformly mixed, and forms nanocrystalline W-Cu solid solution, and it is larger that the major defect of this method will reach grain size
The Ball-milling Time that powder needs is very long, this just inevitably brings impurity metallic elements, and gained powder is easy to agglomerating caking,
Wall sticking phenomenon is serious.Atomization drying method is that ammonium metatungstate and copper nitrate are made into mixed solution, the W- obtained after atomization drying
Cu presomas are roasted, then product is reduced under hydrogen, that is, obtain W-Cu composite powders, using made from atomization drying method
W-Cu composite powder particles are tiny and uniform, are not easily introduced impurity, but the precursor powder reduction control prepared is relatively difficult, by
Reaction temperature and reaction time have a great influence.Sol-gel process is to be readily able to metallic compound (inorganic salts or the metal alcohol of hydrolysis
Salt) react in certain solvent with water or other materials, gel is formed, is made after the processing such as drying/calcining and reduction
W-Cu composite powders, W-Cu composite powders purity made from this method is high, and particle diameter distribution is uniform, but technical process is complex, difficult
Generated with mass.Present inventor by trying to explore to the preparation process of existing ultra-fine W-Cu composite powders,
The defects of aiming to solve the problem that in the prior art, is desirably to obtain with that purity is high, crystallite dimension is small and W-Cu component ratios are controllable is super
Thin W-Cu composite powders.
For this reason, in one aspect of the invention, the present invention proposes a kind of method for preparing ultra-fine W-Cu composite powders, root
According to the embodiment of the present invention, this method includes：
(1) mantoquita, zinc salt and sodium tungstate solution are mixed, to obtain mixed solution；
(2) mixed solution is sent and is stirred, reacts into autoclave, so as to liquid after being reacted；
(3) liquid after the reaction is filtered and cleaning treatment, to obtain copper tungstate-Zinc Tungstate composite powder forerunner
Body and filtered fluid；
(4) processing is dried in the copper tungstate-Zinc Tungstate composite powder presoma, so as to composite powder after being dried
Last presoma；
(5) composite powder presoma after the drying is subjected to reduction treatment in a hydrogen atmosphere, to obtain ultra-fine W-
Cu composite powders.
The method for preparing ultra-fine W-Cu composite powders according to embodiments of the present invention is by by mantoquita and zinc salt and sodium tungstate
Reaction, obtains copper tungstate-Zinc Tungstate composite powder presoma, then can be by the characteristic of hydrogen reducing, by forerunner using tungstates
Body, which is placed under hydrogen atmosphere, carries out reduction reaction, and controls reduction temperature between simple substance zinc and elemental copper volatilization temperature,
Easy to which the simple substance zinc that reduce generation can gasify and smoothly discharge, ultra-fine W-Cu composite powders are thus obtained.And because of presoma
Crystallite dimension it is tiny and be evenly distributed, so presoma is not susceptible to abnormal grain growth phenomenon in hydrogen reduction,
So as to which the ultra-fine W-Cu composite powders obtained can be maintained at submicron order crystallite dimension.Thus, it can be made pure using this method
The ultra-fine W-Cu composite powders that degree is high, crystallite dimension is small and W-Cu component ratios are controllable, while the technique is simple, it can be achieved that large quantities of
Amount production, has a good application prospect.
In addition, the method according to the above embodiment of the present invention for preparing ultra-fine W-Cu composite powders can also be with following attached
The technical characteristic added：
In some embodiments of the invention, it is in step (1), the mantoquita and the zinc salt, the sodium tungstate is molten
Liquid according to Cu2+And Zn2+The sum of molal quantity and Na2WO4Molal quantity is 1~2：1 is mixed.Thus, be conducive to improve ultra-fine
The grade of W-Cu composite powders.
In some embodiments of the invention, in step (2), the mixing speed is 200-500r/min.Thus, may be used
Further improve the grade of ultra-fine W-Cu composite powders.
In some embodiments of the invention, in step (2), the pressure in the autoclave is 0.3-
1.5MPa.Thus, it can further improve the grade of ultra-fine W-Cu composite powders.
In some embodiments of the invention, in step (2), the reaction temperature is 100-180 degrees Celsius, during reaction
Between be 1-5h.Thus, it can further improve the grade of ultra-fine W-Cu composite powders.
In some embodiments of the invention, in step (5), the temperature of the reduction treatment is Celsius for 700-1000
Degree, time 1-3h.Thus, it can further improve the grade of ultra-fine W-Cu composite powders.
In another aspect of the invention, the present invention proposes a kind of ultra-fine W-Cu composite powders.It is real according to the present invention
Example is applied, which be prepared using the above-mentioned method for preparing ultra-fine W-Cu composite powders.Thus, it can obtain purity
The ultra-fine W-Cu composite powders high, crystallite dimension is small and W-Cu component ratios are controllable.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment
Substantially and it is readily appreciated that, wherein：
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing ultra-fine W-Cu composite powders；
Fig. 2 is the SEM photographs of copper tungstate-Zinc Tungstate composite powder presoma after drying according to an embodiment of the invention
Piece；
Fig. 3 is the XRD diagram of copper tungstate-Zinc Tungstate composite powder presoma after drying according to an embodiment of the invention
Spectrum；
Fig. 4 is the SEM photograph of ultra-fine W-20wt.%Cu composite powders according to an embodiment of the invention；
Fig. 5 is the XRD spectrum of ultra-fine W-20wt.%Cu composite powders according to an embodiment of the invention.
Embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or has the function of same or like element.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of method for preparing ultra-fine W-Cu composite powders, according to this
The embodiment of invention, with reference to figure 1, this method includes：
S100：Mantoquita and sodium tungstate solution are mixed
In the step, mantoquita, zinc salt and sodium tungstate solution are mixed, to obtain mixed solution.Need what is illustrated
It is that the particular type of mantoquita and zinc salt is not particularly restricted, those skilled in the art can be selected according to actual needs
Select, for example, mantoquita can be CuSO4·5H2O, zinc salt can be Zn (NO3)2·6H2O.Specifically, the zinc salt and wolframic acid that add
Sodium reaction generation Zinc Tungstate precipitation, the reduzate of Zinc Tungstate in a hydrogen atmosphere is tungsten powder, wherein zinc gas in reduction process
Change volatilization discharge, the content of W in W-Cu composite powders can be improved by improving the addition of zinc salt.
According to still a further embodiment, can be by mantoquita and zinc salt, sodium tungstate solution according to Cu2+And Zn2+Mole
The sum of number and Na2WO4Molal quantity is 1~2：1 is mixed.Specifically, can be according in the ultra-fine W-Cu composite powders of final products
The value of W/Cu determines the relative amounts of mantoquita and zinc salt, is achieved in the control to W and Cu component ratios.Specifically, such as by n
(Cu2+)+n(Zn2+)/n(Na2WO4)=1/1, when zinc salt addition is zero, i.e. n (Zn2+)=0, n (Cu2+)/n(Na2WO4)=1/
When 1, gained presoma component is copper tungstate one-component, is through reducing obtained ultra-fine W-Cu composite powders Cu contents
25.82%, this is the attainable maximum level of Cu components in made ultra-fine W-Cu composite powders.Keeping n (Cu2+)+n(Zn2 +)/n(Na2WO4)=1/1, and in the case of improving zinc salt addition, the Cu contents in the ultra-fine W-Cu composite powders of gained are less than
25.82%.Such as need that W-20wt.%Cu is made, then the relative amounts of mantoquita and zinc salt are n (Cu2+)/n(Zn2+)=0.723/
0.277。
S200：Mixed solution is sent and is stirred, reacts into autoclave
In the step, mixed solution is sent and is stirred, reacts into autoclave, so as to liquid after being reacted.Tool
Body, mixed solution contains mantoquita, zinc salt and sodium tungstate, then in autoclave, in the copper ion and zinc salt in mantoquita
Zinc ion is reacted with sodium tungstate, respectively obtains copper tungstate and Zinc Tungstate precipitation, and the related chemistry reaction equation being related to is as follows：
Cu2++WO4 2-=CuWO4↓
Zn2++WO4 2-=ZnWO4↓
According to one embodiment of present invention, mixing speed is not particularly restricted, and those skilled in the art can root
Made choice according to actual needs, a specific embodiment according to the present invention, mixing speed can be 200-500r/min.Invention
People has found that the stir speed (S.S.) is substantially better than the rate of deposition that other conditions improve liquid after reaction.
According to still a further embodiment, the pressure in autoclave is not particularly restricted, the skill of this area
Art personnel can make choice according to actual needs, a specific embodiment according to the present invention, the pressure in autoclave
Can be 0.3-1.5MPa.
According to still another embodiment of the invention, the condition of reaction is not particularly restricted, and those skilled in the art can
To be made choice according to actual needs, a specific embodiment according to the present invention, reaction temperature can be that 100-180 is Celsius
Degree, the reaction time can be 1-5h.Inventor has found, if reaction temperature is excessive, has WO3Generation, will if reaction temperature is too low
Rate of deposition is caused to decline.Thus, it can ensure tungsten precipitation under the conditions of being somebody's turn to do completely and product production is more uniform.
S300：Liquid after reaction is filtered and cleaning treatment
In the step, after reaction liquid at the same time containing copper tungstate precipitation and Zinc Tungstate precipitation, by liquid after reaction carry out filtering and
Cleaning treatment, obtains copper tungstate-Zinc Tungstate composite powder presoma and filtered fluid.Inventor has found, is obtained by hydro-thermal reaction
Composite powder presoma crystallite dimension it is tiny and be evenly distributed.
S400：Processing is dried in copper tungstate-Zinc Tungstate composite powder presoma
In the step, processing is dried in the above-mentioned copper tungstate-Zinc Tungstate composite powder presoma that obtains, to be done
Composite powder presoma after dry.Thus, the moisture in copper tungstate-Zinc Tungstate composite powder presoma is advantageously reduced, after raising
The reduction efficiency of composite powder presoma after continuous drying, and reduce reduction energy consumption.A specific embodiment according to the present invention, will
After the drying that copper tungstate-Zinc Tungstate composite powder presoma is dried to obtain composite powder presoma SEM photograph as shown in Fig. 2,
Its XRD spectrum is as shown in Figure 3.
S500：Composite powder presoma carries out reduction treatment after in a hydrogen atmosphere will be dry
In the step, composite powder presoma after drying obtained above is subjected to reduction treatment in a hydrogen atmosphere, with
Just ultra-fine W-Cu composite powders are obtained.Specifically, composite powder presoma contains copper tungstate and Zinc Tungstate at the same time after dry, wherein
Copper tungstate and Zinc Tungstate react with hydrogen respectively, by the temperature for controlling reduction treatment so that react the zinc gasification of gained
Volatilization discharge, and copper leaves in solid-state, and because composite powder presoma crystallite dimension is tiny after drying and is evenly distributed, so its
Abnormal grain growth phenomenon is not susceptible in above-mentioned reduction process, the ultra-fine W-Cu that can obtain submicron order crystallite dimension is compound
Powder.The related chemistry reaction equation being related to is：
CuWO4(s)+4H2(g)=Cu (s)+W (s)+4H2O↑
ZnWO4(s)+4H2(g)=Zn (g) ↑+W (s)+4H2O↑
According to one embodiment of present invention, the condition of reduction treatment is not particularly restricted, and those skilled in the art can
To be made choice according to actual needs, a specific embodiment according to the present invention, the temperature of reduction treatment can be 700-
1000 degrees Celsius, the time can be 1-3h.Inventor has found that, if reduction temperature is excessive, overlong time, can make production die size
It is larger, and if reduction temperature is too low, the time is too short, be unfavorable for zinc gasification volatilization.Thus, use the reduction treatment condition can be with
Ensure that the ultra-fine W-Cu composite powders of gained have higher grade and value.
The method for preparing ultra-fine W-Cu composite powders according to embodiments of the present invention is by by mantoquita and zinc salt and sodium tungstate
Reaction, obtains copper tungstate-Zinc Tungstate composite powder presoma, then can be by the characteristic of hydrogen reducing, by forerunner using tungstates
Body, which is placed under hydrogen atmosphere, carries out reduction reaction, and controls reduction temperature between simple substance zinc and elemental copper volatilization temperature,
Easy to which the simple substance zinc that reduce generation can gasify and smoothly discharge, ultra-fine W-Cu composite powders are thus obtained.And because of presoma
Crystallite dimension it is tiny and be evenly distributed, so presoma is not susceptible to abnormal grain growth phenomenon in hydrogen reduction,
So as to which the ultra-fine W-Cu composite powders obtained can be maintained at submicron order crystallite dimension.Thus, it can be made pure using this method
The ultra-fine W-Cu composite powders that degree is high, crystallite dimension is small and W-Cu component ratios are controllable, while the technique is simple, it can be achieved that large quantities of
Amount production, has a good application prospect.
As described above, the method for preparing ultra-fine W-Cu composite powders according to embodiments of the present invention can have selected from following
At least one advantage：
1) present invention process flow is simple, and impurity is not easily introduced in reaction process, and the W-Cu that can prepare high-purity is answered
Close powder.
2) copper tungstate-Zinc Tungstate composite powder presoma crystallite dimension that the present invention is obtained by hydro-thermal reaction is tiny and divides
Cloth is uniform, therefore presoma is not susceptible to abnormal grain growth phenomenon, the W-Cu composite powders of acquisition in hydrogen reduction
It can keep the crystallite dimension of submicron order.
In another aspect of the invention, the present invention proposes a kind of ultra-fine W-Cu composite powders.It is real according to the present invention
Example is applied, which be prepared using the above-mentioned method for preparing ultra-fine W-Cu composite powders.Thus, it can obtain purity
The ultra-fine W-Cu composite powders high, crystallite dimension is small and W-Cu component ratios are controllable.It is it should be noted that above-mentioned super for preparing
The described feature and advantage of method of thin W-Cu composite powders are equally applicable to the ultra-fine W-Cu composite powders, no longer superfluous herein
State.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
Take Na2WO4·2H2O 99.59g, CuSO4·5H2O 54.16g, Zn (NO3)2·6H2O 24.72g, addition go from
Sub- water 300mL is made into mixed solution, is placed in autoclave and is reacted, and reaction temperature is 170 DEG C, and reaction time 4h, is stirred
Speed 400r/min is mixed, by the sample filtering after reaction, cleaning, drying, after being dried before copper tungstate-Zinc Tungstate composite powder
Drive body.Presoma is placed in atmosphere furnace and is reduced in a hydrogen atmosphere, reduction temperature is 900 DEG C, and recovery time 2h, obtains ultra-fine
W-20wt.%Cu composite powders, its SEM photograph is as shown in figure 4, XRD spectrum is as shown in Figure 5.
Embodiment 2
Take Na2WO4·2H2O 99.59g, CuSO4·5H2O 24.12g, Zn (NO3)2·6H2O 61.07g, addition go from
Sub- water 300mL is made into mixed solution, is placed in autoclave and is reacted, and reaction temperature is 180 DEG C, and reaction time 3h, is stirred
Speed 400r/min is mixed, by the sample filtering after reaction, cleaning, drying, after being dried before copper tungstate-Zinc Tungstate composite powder
Drive body.Presoma is placed in atmosphere furnace and is reduced in a hydrogen atmosphere, reduction temperature is 1000 DEG C, and recovery time 1h, is surpassed
Thin W-10wt.%Cu composite powders.
Comparative example
Take Na2WO4·2H2O 99.59g, CuSO4·5H2O 75.38g, add deionized water 300mL and are made into mixed solution,
It is placed in autoclave and is reacted, reaction temperature is 160 DEG C, reaction time 5h, mixing speed 400r/min, after reaction
Sample filtering, cleaning, drying, copper tungstate powder precursor after being dried.Presoma is placed in atmosphere furnace in hydrogen gas
Reduced under atmosphere, reduction temperature is 800 DEG C, recovery time 3h, obtains ultra-fine W-25.82wt.%Cu composite powders.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms is not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
Combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this area
Art personnel can be tied the different embodiments or example described in this specification and different embodiments or exemplary feature
Close and combine.
Although the embodiment of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (7)
- A kind of 1. method for preparing ultra-fine W-Cu composite powders, it is characterised in that including：(1) mantoquita, zinc salt and sodium tungstate solution are mixed, to obtain mixed solution；(2) mixed solution is sent and is stirred, reacts into autoclave, so as to liquid after being reacted；(3) liquid after the reaction is filtered and cleaning treatment, so as to obtain copper tungstate-Zinc Tungstate composite powder presoma and Filtered fluid；(4) processing is dried in the copper tungstate-Zinc Tungstate composite powder presoma, before composite powder after being dried Drive body；(5) composite powder presoma after the drying is subjected to reduction treatment in a hydrogen atmosphere, is answered to obtain ultra-fine W-Cu Close powder.
- 2. according to the method described in claim 1, it is characterized in that, in step (1), by the mantoquita and the zinc salt, institute State sodium tungstate solution according to Cu2+And Zn2+The sum of molal quantity and Na2WO4Molal quantity is 1~2：1 is mixed.
- 3. according to the method described in claim 1, it is characterized in that, in step (2), the mixing speed is 200-500r/ min。
- 4. the method according to claim 1 or 3, it is characterised in that in step (2), the pressure in the autoclave Power is 0.3-1.5MPa.
- 5. according to the method described in claim 4, it is characterized in that, in step (2), the reaction temperature is taken the photograph for 100-180 Family name's degree, reaction time 1-5h.
- 6. according to the method described in claim 1, it is characterized in that, in step (5), the temperature of the reduction treatment is 700- 1000 degrees Celsius, time 1-3h.
- 7. a kind of ultra-fine W-Cu composite powders, it is characterised in that the composite powder is using any one of claim 1-6 What the method for preparing ultra-fine W-Cu composite powders was prepared.
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