CN113894289A - Preparation method of nano tungsten-rhenium powder with low oxygen content - Google Patents
Preparation method of nano tungsten-rhenium powder with low oxygen content Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 68
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 29
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract 6
- 239000000126 substance Substances 0.000 claims abstract 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 9
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 abstract description 7
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910003449 rhenium oxide Inorganic materials 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910000691 Re alloy Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
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Abstract
The existing tungsten-rhenium powder reduction process has the problem that rhenium is not reduced completely, a large amount of gas can be decomposed from unreduced residual rhenium oxide in the alloy sintering process, and the gas which is not discharged in time is heated and expanded in the alloy, so that bulging and even cracking are caused. The invention discloses a preparation method of nano tungsten-rhenium powder with low oxygen content, which comprises the steps of preparing a tungsten-rhenium precursor by a wet chemical method, heating the tungsten-rhenium precursor to 400-plus-one temperature of 500 ℃ in a hydrogen environment, preserving heat for 60-180min, heating to 600-plus-one temperature of 700 ℃, preserving heat for 60-180min, heating to 1000-plus-one temperature of 1200 ℃, preserving heat for 60-180min, then cooling to 500 ℃, and cooling to room temperature to obtain W-Re composite powder. The method for preparing the tungsten-rhenium precursor by adopting a wet chemical method comprises the following specific steps: mixing tungstate aqueous solution and rhenate aqueous solution, heating to 90-110 ℃, adding oxalic acid aqueous solution, heating until the solution is completely evaporated, washing and drying.
Description
Technical Field
The invention relates to the technical field of tungsten-based alloy powder, in particular to a preparation method of nano tungsten-rhenium powder with low oxygen content.
Background
As the market for rotary anode targets has expanded, the demand for domestic rotary anode targets has also increased. The rotary anode target generates X rays under the bombardment of high-energy electron beams, the temperature of a working environment is up to 2300 ℃, and the metal material can generate an air bleeding phenomenon when the rotary anode target operates at high temperature for a long time, so that the phenomena of flashover, breakdown and other failures of the ray tube are caused. Therefore, in terms of material selection of the rotary anode target, in order to prevent severe damage phenomena such as swelling, cracking, melting and the like, a material having the functions of generating X-rays, high atomic number, high temperature resistance, good thermal shock resistance, low vapor pressure, rapid heat dissipation and the like should be selected, and the tungsten-rhenium alloy target is most widely applied at present.
Tungsten is the metal with the highest melting point (3422 ℃) among metals, has high atomic number and low high-temperature steam pressure, and has excellent mechanical properties at high temperature. But due to poor ductility at room temperature, formability is low, severely limiting the formability of tungsten and its resistance to mechanical loads. Rhenium is the second highest melting metal (about 3177 c) and has excellent tensile strength, creep limit, proof strength, and thermal shock resistance. The addition of rhenium can improve the ductility of tungsten, greatly reduce the DBTT (ductile-brittle transition temperature) of tungsten and effectively improve the brittleness and the melting loss resistance of tungsten. The X-ray tube works intermittently, when the X-ray tube works cold and hot, the target surface material is easy to crack, tungsten has notch sensitivity and is easy to cause the crack to expand and deepen, once the crack expands and deepens, the base material can be exposed under the bombardment of electron beams to generate other wavelength rays, and the efficiency and the dosage of the X-ray tube are reduced, so that rhenium is doped in the tungsten, the high temperature resistance of the target surface is improved, the occurrence of the crack is reduced, the efficiency of the rotary anode target is effectively improved, and the service life of the rotary anode target is effectively prolonged.
In the traditional tungsten-rhenium powder preparation process, tungsten powder and rhenium powder are mixed and then subjected to mechanical ball milling, so that the problem of rhenium reduction does not need to be solved, but long-time grinding is needed to achieve the degree of tungsten-rhenium solid solution and powder nanoscale, and impurities are introduced due to the abrasion of grinding equipment and media in the grinding process. In the prior art, tungsten powder and ammonium rhenate solution are mixed and then reduced, but microscopic observation of the obtained tungsten-rhenium powder shows that a large amount of rhenium particles are bonded into clusters and attached to the surfaces of the tungsten particles, the components are not uniformly distributed, and the particle size has a bimodal structure.
In the prior tungsten-rhenium powder reduction process, the problem of incomplete rhenium reduction often exists, a large amount of gas can be decomposed from unreduced residual rhenium oxide in the alloy sintering process, and the gas which is not discharged in time is heated and expanded in the alloy, so that the alloy bulges and even cracks.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for preparing nano tungsten-rhenium powder with low oxygen content.
A preparation method of nano tungsten-rhenium powder with low oxygen content comprises the following steps:
step 1: tungsten-rhenium precursor
A certain amount of ammonium metatungstate (AMT, Aladdin, purity is more than or equal to 99.95 percent) and ammonium rhenate (NH)4ReO4Purity not less than 99.9%), oxalic acid (C)2H2O4·2H2O, analytically pure) are respectively dissolved in deionized water, stirred until the solution is clear and free of precipitate, the ammonium metatungstate solution and the ammonium rhenate solution are mixed and stirred and then placed in a magnetic stirrer for heating, a rotor is adjusted to a proper rotating speed, oxalic acid solution is added when the temperature is heated to 90-110 ℃, and then the temperature is kept within the range of 120-140 ℃ until the solution is completely evaporated. And taking out the powder, washing the powder with alcohol, standing the powder for precipitation, putting the powder into a vacuum drying box, setting the temperature of the vacuum drying box at 140 ℃, and drying the powder for 12 hours to obtain a precursor.
In step 1, the addition amounts of ammonium rhenate and oxalic acid are respectively 5.26-42.86% and 33.89-56.68% of the mass of ammonium metatungstate.
Step 2: reduction of
Putting the tungsten-rhenium powder into a burning boat, putting the burning boat into a high-temperature tube furnace, keeping the burning boat at the middle position of a tube body, vacuumizing the tube furnace, introducing hydrogen (the purity of the hydrogen is more than or equal to 99.999 percent, and the flow rate of the hydrogen is 0.45-0.55L/min), ensuring that no other gas except the hydrogen exists in a furnace chamber of the tube furnace, then heating to 400-fold-fluid 500 ℃ at 8-12 ℃/min, preserving the heat for 60-180min, heating to 600-fold-fluid 700 ℃ at 8-12 ℃/min, preserving the heat for 60-180min, heating to 1000-fold-fluid 1200 ℃ at 8-12 ℃/min, preserving the heat for 60-180min, cooling to 480-fold-fluid 520 ℃ at 4-6 ℃/min after the heat preservation is finished, and finally cooling to room temperature.
The obtained W-Re composite powder has uniform component distribution, the powder granularity is 160-300nm, the reduction is more thorough, and the oxygen content is lower
The invention has the beneficial effects that:
according to the invention, the ammonium rhenate and the ammonium metatungstate are required to be thoroughly dissolved to obtain an ammonium rhenate solution and an ammonium metatungstate solution, and then the ammonium rhenate solution and the ammonium metatungstate solution are mixed and heated under the condition of ensuring that no undissolved particles exist, so that the ammonium rhenate and the metatungstate can be uniformly mixed, and the components of the obtained precursor powder are uniformly distributed.
Since the rhenium oxide begins to be reduced at about 400 c and a small amount of residual suboxide is substantially completely reduced to metallic Re at a reduction temperature of 800 c, the reduction temperature of conventional reduction processes tends to be below 1000 c, but this results in incomplete reduction and the occurrence of unreduced residual rhenium oxide which decomposes into a large amount of gas by heating during the subsequent sintering of the alloy, causing the alloy to bulge and even crack, severely affecting the properties of the alloy.
The invention sets up three stages of reduction temperatures, wherein the first stage (400-500 ℃) and the second stage (600-700 ℃) ensure that the rhenium oxide and the tungsten oxide can be basically reduced, and the third stage (1000-1200 ℃) can ensure that the residual rhenium oxide can be completely reduced, and the particles can not grow up and coarsen due to overhigh reduction temperature and volatilization pressure when the oxides are reduced.
Drawings
FIG. 1 is a scanning electron microscope photograph of the W-Re composite powder obtained in example 2.
FIG. 2 is an X-ray diffraction pattern of the W-Re composite powder obtained in example 2.
FIG. 3 is a ZETA potential particle size of the W-Re composite powder obtained in example 2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A preparation method of nano tungsten-rhenium powder with low oxygen content comprises the following steps:
step 1: tungsten-rhenium precursor
Ammonium metatungstate (AMT, Aladdin, purity is not less than 99.95%), ammonium rhenate (NH)4ReO4Purity not less than 99.9%), oxalic acid (C)2H2O4·2H2O, analytically pure) are respectively dissolved in deionized water and stirred until the solution is clear and has no precipitate; mixing and stirring the ammonium metatungstate solution and the ammonium rhenate solution, then putting the mixture into a magnetic stirrer for heating, adjusting a rotor to a proper rotating speed, adding the oxalic acid solution when heating to 100 ℃, and keeping the temperature at 130 ℃ until the solution is completely evaporated. And taking out the powder, washing the powder with alcohol, standing the powder for precipitation, putting the powder into an oven, setting the temperature of the oven at 130 ℃, and drying the powder for 12 hours to obtain a precursor.
Wherein the addition amount of ammonium rhenate is 11.98% of the mass of ammonium metatungstate, and the addition amount of oxalic acid is 37.44% of the mass of ammonium metatungstate.
Step 2: reduction of
The precursor is flatly laid in a burning boat, the burning boat is placed in a high-temperature tube furnace, the burning boat is kept in the middle of a tube body, the high-temperature tube furnace is vacuumized, hydrogen is introduced (the purity of the hydrogen is more than or equal to 99.999%, and the flow rate of the hydrogen is 0.5L/min), the fact that no other gas except the hydrogen exists in the furnace chamber of the tube furnace is guaranteed, the temperature is increased to 400 ℃ at the rate of 10 ℃/min, the temperature is kept for 120min, the temperature is increased to 600 ℃ at the rate of 10 ℃/min, the temperature is kept for 60min, the temperature is increased to 1000 ℃ at the rate of 10 ℃/min, the temperature is kept for 60min, the temperature is reduced to 500 ℃ at the rate of 5 ℃/min after the temperature is kept, and finally the temperature is reduced to room temperature.
The microstructure of the W-Re composite powder obtained in the example is porous coralline, the average grain diameter is 180.10nm, the oxygen content is 7200ppm, the XRD spectrum only shows the diffraction peak of W, but the peak is obviously widened compared with pure W, and the peak position is obviously shifted overall, thereby indicating that the Re is basically dissolved into the W matrix while the W-Re composite powder is nanocrystallized.
Example 2
A preparation method of nano tungsten-rhenium powder with low oxygen content comprises the following steps:
step 1: tungsten-rhenium precursor
Ammonium metatungstate (AMT, Aladdin, purity is more than or equal to 99.95%), ammonium rhenate (NH)4ReO4Purity not less than 99.9 percent) and oxalic acid (C)2H2O4·2H2O, analytically pure) are respectively dissolved in deionized water and stirred until the solution is clear and has no precipitate; mixing and stirring the ammonium metatungstate solution and the ammonium rhenate solution, then putting the mixture into a magnetic stirrer for heating, adjusting a rotor to a proper rotating speed, adding the oxalic acid solution when heating to 100 ℃, and keeping the temperature at 130 ℃ until the solution is completely evaporated. And taking out the powder, washing the powder with alcohol, standing the powder for precipitation, putting the powder into an oven, setting the temperature of the oven at 130 ℃, and drying the powder for 12 hours to obtain a precursor.
Wherein the addition amount of ammonium rhenate is 11.98% of the mass of ammonium metatungstate, and the addition amount of oxalic acid is 37.44% of the mass of ammonium metatungstate.
Step 2: reduction of
The precursor is flatly laid in a burning boat, the burning boat is placed in a high-temperature tube furnace, the burning boat is kept in the middle of a tube body, the high-temperature tube furnace is vacuumized, hydrogen is introduced (the purity of the hydrogen is more than or equal to 99.999%, and the flow rate of the hydrogen is 0.5L/min), the fact that no other gas except the hydrogen exists in the furnace chamber of the tube furnace is guaranteed, the temperature is increased to 450 ℃ at the speed of 10 ℃/min, the temperature is kept for 120min, the temperature is increased to 600 ℃ at the speed of 10 ℃/min, the temperature is kept for 60min, the temperature is increased to 1000 ℃ at the speed of 10 ℃/min, the temperature is kept for 60min, the temperature is reduced to 500 ℃ at the speed of 5 ℃/min after the temperature is kept, and finally the temperature is reduced to the room temperature.
The W-Re composite powder obtained in this example was subjected to scanning by an electron microscope, as shown in FIG. 1. As can be seen from fig. 1: the W-Re composite powder obtained in this example had a porous coral-like structure.
The W-Re composite powder obtained in this example was subjected to X-ray diffraction, as shown in FIG. 2. As can be seen from fig. 2: in the W-Re composite powder obtained in this example, Re element was substantially dissolved in the W matrix.
The W-Re composite powder obtained in this example was subjected to ZETA potential particle size characterization as shown in FIG. 3. As can be seen from fig. 3: the particle size of the W-Re composite powder obtained in the embodiment is nano, the particle size distribution is unimodal, and the particle sizes are similar.
In conclusion, the microstructure of the W-Re composite powder obtained in this example was porous coral-like, the average particle size was 201.50nm, the oxygen content was 4518ppm, and the XRD pattern showed only the diffraction peak of W, but the peak was significantly broadened and the peak position was significantly shifted as a whole, indicating that Re was substantially dissolved in the W matrix while the W-Re composite powder was nanosized.
Example 3
A preparation method of nano tungsten-rhenium powder with low oxygen content comprises the following steps:
step 1: tungsten-rhenium precursor
Ammonium metatungstate (AMT, Aladdin, purity is not less than 99.95%), ammonium rhenate (NH)4ReO4Purity not less than 99.9%), oxalic acid (C)2H2O4·2H2O, analytically pure) are respectively dissolved in deionized water and stirred until the solution is clear and has no precipitate; mixing and stirring the ammonium metatungstate solution and the ammonium rhenate solution, then putting the mixture into a magnetic stirrer for heating, adjusting a rotor to a proper rotating speed, adding the oxalic acid solution when heating to 100 ℃, and keeping the temperature at 130 ℃ until the solution is completely evaporated. And taking out the powder, washing the powder with alcohol, standing the powder for precipitation, putting the powder into an oven, setting the temperature of the oven at 130 ℃, and drying the powder for 12 hours to obtain precursor powder.
Wherein the addition amount of ammonium rhenate is 11.98% of the mass of ammonium metatungstate, and the addition amount of oxalic acid is 37.44% of the mass of ammonium metatungstate.
Step 2: reduction of
The precursor is flatly laid in a burning boat, the burning boat is placed in a high-temperature tube furnace, the burning boat is kept in the middle of a tube body, the high-temperature tube furnace is vacuumized, hydrogen is introduced (the purity of the hydrogen is more than or equal to 99.999%, and the flow rate of the hydrogen is 0.5L/min), the fact that no other gas except the hydrogen exists in the furnace chamber of the tube furnace is guaranteed, the temperature is increased to 500 ℃ at the rate of 10 ℃/min, the temperature is kept for 120min, the temperature is increased to 600 ℃ at the rate of 10 ℃/min, the temperature is kept for 60min, the temperature is increased to 1000 ℃ at the rate of 10 ℃/min, the temperature is kept for 60min, the temperature is reduced to 500 ℃ at the rate of 5 ℃/min after the temperature is kept, and finally the temperature is reduced to the room temperature.
The microstructure of the W-Re composite powder obtained in the embodiment is porous coralline, the average grain diameter is 166.33nm, the oxygen content is 3982ppm, the XRD spectrum only shows the diffraction peak of W, but the W-Re composite powder has obvious peak broadening compared with pure W, and the peak position has obvious shift on the whole, which shows that the Re is basically dissolved into the W matrix while the W-Re composite powder is nanocrystallized.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A preparation method of nano tungsten-rhenium powder with low oxygen content is characterized in that a wet chemical method is adopted to prepare a tungsten-rhenium precursor, the tungsten-rhenium precursor is heated to 400-plus-500 ℃ in a hydrogen environment and is kept warm for 60-180min, the tungsten-rhenium precursor is heated to 600-plus-700 ℃ and is kept warm for 60-180min, then the tungsten-rhenium precursor is heated to 1000-plus-1200 ℃ and is kept warm for 60-180min, and then the tungsten-rhenium precursor is cooled to 500 ℃ and is cooled to room temperature to obtain W-Re composite powder.
2. The method for preparing nano tungsten-rhenium powder with low oxygen content as claimed in claim 1, wherein the particle size of the W-Re composite powder is 160-300nm, and the oxygen content is less than or equal to 7200 ppm.
3. The method for preparing nano tungsten-rhenium powder with low oxygen content according to claim 1, characterized in that the wet chemical method is adopted to prepare the tungsten-rhenium precursor by the following specific steps: mixing the tungstate aqueous solution and the rhenate aqueous solution, heating to 90-110 ℃, adding the oxalic acid aqueous solution, heating until the solution is completely evaporated, washing and drying to obtain the precursor.
4. The method for preparing nano tungsten-rhenium powder with low oxygen content according to claim 3, wherein the tungstate is ammonium metatungstate, ammonium paratungstate or ammonium tungstate, and the rhenate is ammonium rhenate.
5. The method for preparing nano tungsten-rhenium powder with low oxygen content according to claim 3, wherein the tungstate is ammonium metatungstate, and the rhenate is ammonium rhenate; the mass ratio of ammonium rhenate to ammonium metatungstate is 5.26-42.86: 100, the mass ratio of oxalic acid to ammonium metatungstate is 33.89-56.68: 100.
6. the method for preparing nano W-Re powder with low oxygen content as claimed in claim 3, wherein the heating is carried out at a temperature of 120-140 ℃ to complete evaporation of the solution.
7. The method of claim 1, wherein the tungsten-rhenium precursor is placed in a burning boat, the burning boat is placed in a high temperature tube furnace, the burning boat is kept in the middle of the tube, the tube furnace is evacuated, and then hydrogen is introduced to make the chamber of the tube furnace pure hydrogen.
8. The method for preparing nano tungsten-rhenium powder with low oxygen content according to claim 7, wherein the flow rate of hydrogen is 0.45-0.55L/min.
9. The method for preparing nano W-Re powder with low oxygen content as claimed in claim 7, wherein the W-Re precursor is heated to 400-500 ℃ at a rate of 8-12 ℃/min, the temperature is maintained for 60-180min, then heated to 600-700 ℃ at a rate of 8-12 ℃/min, the temperature is maintained for 60-180min, then heated to 1000-1200 ℃ at a rate of 8-12 ℃/min, the temperature is maintained for 60-180min, and then cooled to 480-500 ℃ at a rate of 4-6 ℃/min, and finally cooled to room temperature to obtain the W-Re composite powder.
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