CN116765419A - W-V-Mo-Re-HfO 2 -Y 2 O 3 Chemical preparation method of nano powder and fine crystal block material thereof - Google Patents
W-V-Mo-Re-HfO 2 -Y 2 O 3 Chemical preparation method of nano powder and fine crystal block material thereof Download PDFInfo
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- 239000011858 nanopowder Substances 0.000 title claims abstract description 23
- 238000005285 chemical preparation method Methods 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- -1 rare earth salt Chemical class 0.000 claims description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000013590 bulk material Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000002362 hafnium Chemical class 0.000 claims description 3
- 150000003746 yttrium Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000005551 mechanical alloying Methods 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 102100028292 Aladin Human genes 0.000 description 24
- 101710065039 Aladin Proteins 0.000 description 24
- 239000000956 alloy Substances 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 15
- 230000006872 improvement Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001272 pressureless sintering Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical group S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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
- B22F9/24—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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/03—Press-moulding apparatus therefor
-
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses W-V-Mo-Re-HfO 2 ‑Y 2 O 3 The chemical preparation method of the nano powder and the fine crystal block material thereof, wherein the preparation method comprises the following steps: s1 precursor preparation, S2 step-by-step hydrogen pyrolysis reduction and S3 powder sintering solidification, and the superfine W-V-Mo-Re-HfO prepared by the method 2 ‑Y 2 O 3 The precursor of the micro-alloyed rare earth oxide nano powder is prepared by chemical reaction, and the elements realize the mixing of molecular grades; compared with W-V-Mo-Re-HfO obtained by mechanical alloying 2 ‑Y 2 O 3 Powder, powder element prepared by the schemeThe distribution of the elements is more uniform, the grain size is finer, and no other impurities are introduced.
Description
Technical Field
The invention relates to the technical field of plasma materials, in particular to a W-V-Mo-Re-HfO 2 -Y 2 O 3 A chemical preparation method of nano powder and a fine crystal block material thereof.
Background
The nuclear energy produced by the nuclear fusion reactor has the characteristics of reproducibility, small pollution and the like, and is an important way for solving the problem of energy exhaustion and resource shortage. One of the most critical problems is the development of fusion stacks for plasma-facing materials. The first wall is required to bear high heat load, high ion flux and neutron irradiation, and tungsten (W) and tungsten-based alloy have remarkable high-temperature performance and are considered as the most promising plasma-facing materials in fusion reaction devices. However, the low temperature brittleness, high ductile-brittle transition temperature, low recrystallization temperature, irradiation embrittlement, etc. have limited the application of tungsten-based alloys. In recent years, researchers have conducted intensive studies on reducing brittleness of tungsten-based alloys. Oxide particle dispersion strengthening is an effective way to improve service brittleness, increase recrystallization temperature, decrease ductile-brittle transition temperature, and enhance irradiation capability, such as HfO 2 、ThO 2 、Y 2 O 3 、La 2 O 3 、CeO 2 、ZrO 2 And Al 2 O 3 Etc. to the W matrix to enhance high temperature performance. Oxide particles (Y) 2 O 3 ) Has high melting point (2410 ℃) and stable physicochemical properties, and W-Y 2 O 3 The alloy has excellent mechanical property, thermal shock damage resistance and radiation damage resistance, so the nano oxide (Y) is doped in the W matrix 2 O 3 ) Particles are considered to be one of the most promising candidate materials for the plasma-facing fusion reactor (PFM) in the future. And recent studies have found that oxide particles (HfO 2 ) Can accelerate W-Y at lower temperature 2 O 3 Sintering densification of the alloy proceeds, thus, in W-Y 2 O 3 On the basis of (a) continuing to add oxide particles (HfO 2 ) Make it not toCoaction with oxide particles on W matrix (Y 2 O 3 The dispersion distribution of the particles improves the strength of the alloy, hfO 2 The dispersed distribution of particles accelerates sintering densification); on the other hand, the W matrix is subjected to multi-component microalloying, V, mo and Re are good radiation-resistant materials, and can form solid solution with W, and the overall performance of the W-based alloy is greatly improved by combining the theories of delayed diffusion effect, lattice distortion effect and the like and the dispersion strengthening of oxide particles. Research results show that the smaller the oxide particles are, the better the dispersibility is, which is beneficial to improving the uniformity and density of microstructure in the sintering process; meanwhile, the refinement of the W crystal grains can not only reduce the ductile-brittle transition temperature of W, but also improve the high-temperature mechanical property and the thermal shock resistance of the material.
Therefore, the preparation of micro-alloyed rare earth oxide nano powder with finer grains and more uniform oxide distribution is a reasonable way for improving the performance of tungsten-based alloys. However, during the subsequent sintering process, the oxide particles tend to segregate at the grain boundaries, thereby becoming stress concentration regions, weakening the adhesion at the interface between the substrates, leading to grain-oriented fracture and low toughness, and thus reducing the mechanical properties of the alloy.
Therefore, the preparation of the multi-element doped superfine tungsten-based composite powder and the preparation of the high-performance fine-grain block material with uniform tissues is a great technical problem.
Disclosure of Invention
To solve the technical problems in the prior art, the invention provides a superfine (20 nm) W-V-Mo-Re-HfO 2 -Y 2 O 3 A chemical preparation method of nano powder and a fine crystal block material thereof.
The invention is realized by adopting the following technical scheme: W-V-Mo-Re-HfO 2 -Y 2 O 3 The chemical preparation method of the nano powder comprises the following steps:
s1, dissolving vanadate, molybdate, rhenate and soluble rare earth salt in water to form a mixed solution, and adding triethanolamine after fully stirring; continuously stirring, and adding tungstate when the mixed solution is heated to a certain temperature; fully mixing the solution system, heating to a certain temperature, and adding oxalic acid; heating and stirring until the solution is completely evaporated to obtain a precursor;
s2, grinding the precursor into fine powder, placing the fine powder into a burning boat, placing the burning boat containing the fine powder into a reduction furnace, and carrying out three-step reduction in a hydrogen atmosphere;
s3, loading the reduction product obtained in the S2 into a steel mold, compacting the powder, and then sintering in two steps under the hydrogen atmosphere to obtain the W-V-Mo-Re-HfO 2 -Y 2 O 3 Nano powder.
As a further improvement of the above scheme, in S1, the vanadate is ammonium metavanadate; the molybdate is ammonium molybdate tetrahydrate; the rhenate is ammonium perrhenate; the tungstate is ammonium metatungstate.
As a further improvement of the above scheme, in S1, the soluble hafnium salt is a chloride or sulfate of hafnium.
As a further improvement of the above scheme, in S1, the soluble yttrium salt is yttrium nitrate, oxalate, carbonate, chloride or sulfate.
As a further improvement of the scheme, in the step S1, the ratio of the mass percentage of the V element in the precursor to the mass percentage of the W element in the precursor is 0.2-5:100.
as a further improvement of the scheme, in S1, the ratio of the mass percentage of Mo element in the precursor to the mass percentage of W element in the precursor is 0.2-5:100.
as a further improvement of the scheme, in S1, the ratio of the mass percent of Re element in the precursor to the mass percent of W element in the precursor is 0.2-5:100.
as a further improvement of the above scheme, in S1, the ratio of the mass percentage of the rare earth oxide particles in the precursor to the mass percentage of the W element in the precursor is 0.2-5:100.
as a further improvement of the scheme, in S1, the mass ratio of the triethanolamine to the soluble rare earth salt is 120-200:100.
as a further improvement of the scheme, in S1, adding tungstate at 60-100 ℃;100-140 deg.c, oxalic acid is added.
As a further improvement of the above scheme, in S2, the specific operation of the three-step reduction is as follows: preserving the temperature for 20-40 minutes at 380-420 ℃; then heating to 550-650 ℃, and preserving heat for 50-70 minutes; heating to 800-900 deg.c and maintaining for 100-240 min.
As a further improvement of the scheme, in S3, the two-step sintering method specifically comprises the following steps: preserving heat for 2h in a hydrogen atmosphere at 1200 ℃ and performing presintering; and (3) preserving the temperature for 3 hours in a hydrogen atmosphere at 2150 ℃ and carrying out final sintering.
In the step S3, presintering is adopted, so that the relative density rho of the green body is more than 70-80%, and the size of the pore is reduced to a thermodynamically unstable value to prepare for final sintering. The two-step pressureless sintering method can inhibit the growth of crystal grains and realize densification, so that not only is the grain size of a pressureless sintering sample refined, but also the microstructure is uniform, and the sintering performance is better.
The invention also provides the W-V-Mo-Re-HfO prepared by adopting any one of the methods 2 -Y 2 O 3 Fine crystal bulk material of nano powder.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to an ultrafine W-V-Mo-Re-HfO prepared by chemical reaction 2 -Y 2 O 3 The precursor of the micro-alloyed rare earth oxide nano powder is prepared by chemical reaction, and the elements realize the mixing of molecular grades; compared with W-V-Mo-Re-HfO obtained by mechanical alloying 2 -Y 2 O 3 The powder prepared by the scheme has more uniform distribution of the powder elements, finer grain size and no introduction of other impurities. Compared with the conventional two-step reduction method, the scheme adds the step of heat preservation for 20-40 minutes at 380-420 ℃; the method aims to increase a reduction buffer stage at a lower temperature, fully discharge gas generated by powder before the reduction process starts, fully contact hydrogen with the powder, fully absorb the hydrogen from the surface to the inside of the tungsten oxide, reduce the reduction time at a high temperature, thoroughly reduce the precursor and obtain finer powder particle size (20 nm). Burning outThe alloy material after junction has uniform structure, oxide particles are dispersed and distributed, the density reaches 98.4 percent, the average grain size is 5.7 mu m, and the micro Vickers hardness at room temperature is 439HV 0.2 The tensile breaking strength at 200 ℃ is 612MPa, which is superior to pure W and W-Y 2 O 3 。
Drawings
FIG. 1 is a schematic flow chart of a preparation method according to an embodiment of the present invention;
FIG. 2 is a graph showing the difference in the total mass fraction of solid solution elements in W-V-Mo-Re-HfO 2 -Y 2 O 3 XRD patterns of the reduced powder showed that a significant W peak was present and no other impurity peaks were present, indicating that W-V-Mo-Re-HfO 2 -Y 2 O 3 The precursor is thoroughly reduced, and when the total mass fraction of V, mo and Re is increased to 5%, peaks of V and oxides thereof, mo and oxides thereof, re and oxides thereof are not found to exist;
FIG. 3 is a three-step reduction process of W-V-Mo-Re-HfO 2 -Y 2 O 3 The morphology graph of the powder can be seen that the particle size of the reduced powder is about 20nm, and the size is superior to W-V-Mo-Re-HfO obtained by mechanical alloying and a two-step reduction method 2 -Y 2 O 3 Powder (200 nm);
FIG. 4 is a W-V-Mo-Re-HfO 2 -Y 2 O 3 The gold phase diagram of the alloy block shows that the alloy crystal grains are fine, and the oxide particles are in dispersion distribution;
FIG. 5 is a W-V-Mo-Re-HfO 2 -Y 2 O 3 The fracture morphology diagram of the alloy block can be seen from the diagram that the section is void-free and clean, and the segregation of oxide particles is avoided.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, wherein it is to be understood that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
Example 1
Referring to FIGS. 1-5, the invention provides a W-V-Mo-Re-HfO 2 -Y 2 O 3 The chemical preparation method of the composite powder comprises the following steps:
step 1: precursor preparation
Ammonium metavanadate (NH) 4 VO 3 Aladin with purity not less than 99.9%), ammonium molybdate tetrahydrate (H) 24 Mo 7 N 6 O 24 ·4H 2 O, aladin, purity not less than 99.9%), ammonium perrhenate (NH) 4 ReO 4 Aladin with purity not less than 99.0%), hafnium chloride (HfCl) 4 Aladin with purity not less than 99.9%), yttrium nitrate hexahydrate (Y (NO) 3 ) 3 ·6H 2 O, aladin with purity more than or equal to 99.5 percent) and triethanolamine (C) 16 H 22 N 4 O 3 Dissolving Aladin with purity more than or equal to 99.0% in deionized water, heating and stirring to obtain mixed solution, dissolving ammonium metatungstate (AMT, aladin with purity more than or equal to 99.95%) in deionized water, stirring, pouring into the mixed solution, and adding oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O, aladin with purity more than or equal to 99.5 percent, and the precipitate obtained after the mixed solution is stirred and evaporated to dryness is W-V-Mo-Re-HfO 2 -Y 2 O 3 A precursor.
Wherein the mass fraction of the V element is 0.2wt% of the W element, the mass fraction of the Mo element is 0.2wt% of the W element, the mass fraction of the Re element is 0.2wt% of the W element, and the HfO is as follows 2 The mass fraction of the element is 0.2wt% of the W element, Y 2 O 3 The mass fraction of the catalyst was 0.2wt% of W element, the amount of triethanolamine added was 0.5ml, and the amount of oxalic acid added was 39.0% of the sum of the mass of ammonium metatungstate, ammonium metavanadate, ammonium molybdate and ammonium perrhenate.
Step 2: stepwise hydrogen pyrolysis reduction
Fully grinding the blocky precursor obtained in the step 1 in a mortar to obtain fine powder, sieving the fine powder by a 100-mesh screen, and then placing a sintering boat containing the fine powder into a hydrogen (the purity of the hydrogen is more than or equal to 99.999%) reducing furnace for three-step reduction: firstly, the temperature is raised to 380-420 ℃, and the temperature is kept for 20-40 minutes, so that residual organic matters are fully decomposed and volatilized; then heating to 550-650 ℃, and preserving heat for 50-70 minutes; heating to 800-900 deg.c, maintaining for 100-240 min, and cooling to room temperature.
Step 3: powder sintering and curing
And (3) filling the powder obtained in the step (2) into a stainless steel die, pressing the powder into a blank by using a manual powder tablet press, maintaining the pressure at about 25MPa, and demoulding after maintaining the pressure for 3 minutes to obtain a tungsten-based composite material green body. Presintering in a tube furnace, wherein the sintering process is that the hydrogen atmosphere is kept at 1200 ℃ for 60min, and then high-temperature sintering is carried out for 3h at 2150 ℃ in the hydrogen atmosphere, and finally the W-V-Mo-Re-HfO is obtained 2 -Y 2 O 3 And (3) a composite block.
W-V-Mo-Re-HfO obtained in this example 2 -Y 2 O 3 The density of the alloy is up to 98.6%, the average grain size is 5.5 mu m, and the micro Vickers hardness at room temperature is 442HV 0.2 Tensile break strength at 200 ℃ is 618MPa, which is superior to pure W and W-Y 2 O 3 (tensile break strength at 200 ℃ C. Was 512MPa and 534MPa, respectively).
Example 2
The invention provides a W-V-Mo-Re-HfO 2 -Y 2 O 3 The chemical preparation method of the composite powder comprises the following steps:
step 1: precursor preparation
Ammonium metavanadate (NH) 4 VO 3 Aladin with purity not less than 99.9%), ammonium molybdate tetrahydrate (H) 24 Mo 7 N 6 O 24 ·4H 2 O, aladin, purity not less than 99.9%), ammonium perrhenate (NH) 4 ReO 4 Aladin with purity not less than 99.0%), hafnium chloride (HfCl) 4 Aladin with purity not less than 99.9%), yttrium nitrate hexahydrate (Y (NO) 3 ) 3 6H2O, aladin, purity not less than 99.5%) and triethanolamine (C) 16 H 22 N 4 O 3 Dissolving Aladin with purity more than or equal to 99.0% in deionized water, heating and stirring to obtain mixed solution, dissolving ammonium metatungstate (AMT, aladin with purity more than or equal to 99.95%) in deionized water, stirring, pouring into the mixed solution, and adding oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O, aladin with purity more than or equal to 99.5 percent) and the mixed solution is stirred and evaporated to dryness to obtain precipitateIs W-V-Mo-Re-HfO 2 -Y 2 O 3 A precursor.
Wherein the mass fraction of the V element is 4.6wt% of the W element, the mass fraction of the Mo element is 0.2wt% of the W element, the mass fraction of the Re element is 0.2wt% of the W element, and the HfO is as follows 2 The mass fraction of the element is 0.2wt% of the W element, Y 2 O 3 The mass fraction of the catalyst was 0.2wt% of W element, the amount of triethanolamine added was 0.5ml, and the amount of oxalic acid added was 39.0% of the sum of the mass of ammonium metatungstate, ammonium metavanadate, ammonium molybdate and ammonium perrhenate.
Step 2: stepwise hydrogen pyrolysis reduction
Fully grinding the blocky precursor obtained in the step 1 in a mortar to obtain fine powder, sieving the fine powder by a 100-mesh screen, and then placing a sintering boat containing the fine powder into a hydrogen (the purity of the hydrogen is more than or equal to 99.999%) reducing furnace for three-step reduction: firstly, the temperature is raised to 380-420 ℃, and the temperature is kept for 20-40 minutes, so that residual organic matters are fully decomposed and volatilized; then heating to 550-650 ℃, and preserving heat for 50-70 minutes; heating to 800-900 deg.c, maintaining for 100-240 min, and cooling to room temperature.
Step 3: powder sintering and curing
And (3) filling the powder obtained in the step (2) into a stainless steel die, pressing the powder into a blank by using a manual powder tablet press, maintaining the pressure at about 25MPa, and demoulding after maintaining the pressure for 3 minutes to obtain a tungsten-based composite material green body. Presintering in a tube furnace, wherein the sintering process is that the hydrogen atmosphere is kept at 1200 ℃ for 60min, and then high-temperature sintering is carried out for 3h at 2150 ℃ in the hydrogen atmosphere, and finally the W-V-Mo-Re-HfO is obtained 2 -Y 2 O 3 And (3) a composite block.
W-V-Mo-Re-HfO obtained in this example 2 -Y 2 O 3 The density of the alloy is up to 98.1%, the average grain size is 5.9 mu m, and the room temperature micro Vickers hardness is 435HV 0.2 The tensile breaking strength at 200 ℃ is 605MPa, which is superior to pure W and W-Y 2 O 3 (tensile break strength at 200 ℃ C. Was 512MPa and 534MPa, respectively).
Example 3
The invention provides a W-V-Mo-Re-HfO 2 -Y 2 O 3 Composite powder meltingThe preparation method comprises the following steps:
step 1: precursor preparation
Ammonium metavanadate (NH) 4 VO 3 Aladin with purity not less than 99.9%), ammonium molybdate tetrahydrate (H) 24 Mo 7 N 6 O 24 ·4H 2 O, aladin, purity not less than 99.9%), ammonium perrhenate (NH) 4 ReO 4 Aladin with purity not less than 99.0%), hafnium chloride (HfCl) 4 Aladin with purity not less than 99.9%), yttrium nitrate hexahydrate (Y (NO) 3 ) 3 ·6H 2 O, aladin with purity more than or equal to 99.5 percent) and triethanolamine (C) 16 H 22 N 4 O 3 Dissolving Aladin with purity more than or equal to 99.0% in deionized water, heating and stirring to obtain mixed solution, dissolving ammonium metatungstate (AMT, aladin with purity more than or equal to 99.95%) in deionized water, stirring, pouring into the mixed solution, and adding oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O, aladin with purity more than or equal to 99.5 percent, and the precipitate obtained after the mixed solution is stirred and evaporated to dryness is W-V-Mo-Re-HfO 2 -Y 2 O 3 A precursor.
Wherein the mass fraction of the V element is 0.2wt% of the W element, the mass fraction of the Mo element is 0.2wt% of the W element, the mass fraction of the Re element is 4.6wt% of the W element, and the HfO is the same as that of the W element 2 The mass fraction of the element is 0.2wt% of the W element, Y 2 O 3 The mass fraction of the catalyst was 0.2wt% of W element, the amount of triethanolamine added was 0.5ml, and the amount of oxalic acid added was 39.0% of the sum of the mass of ammonium metatungstate, ammonium metavanadate, ammonium molybdate and ammonium perrhenate.
Step 2: stepwise hydrogen pyrolysis reduction
Fully grinding the blocky precursor obtained in the step 1 in a mortar to obtain fine powder, sieving the fine powder by a 100-mesh screen, and then placing a sintering boat containing the fine powder into a hydrogen (the purity of the hydrogen is more than or equal to 99.999%) reducing furnace for three-step reduction: firstly, the temperature is raised to 380-420 ℃, and the temperature is kept for 20-40 minutes, so that residual organic matters are fully decomposed and volatilized; then heating to 550-650 ℃, and preserving heat for 50-70 minutes; heating to 800-900 deg.c, maintaining for 100-240 min, and cooling to room temperature.
Step 3: powder sintering and curing
And (3) filling the powder obtained in the step (2) into a stainless steel die, pressing the powder into a blank by using a manual powder tablet press, maintaining the pressure at about 25MPa, and demoulding after maintaining the pressure for 3 minutes to obtain a tungsten-based composite material green body. Presintering in a tube furnace, wherein the sintering process is that the hydrogen atmosphere is kept at 1200 ℃ for 60min, and then high-temperature sintering is carried out for 3h at 2150 ℃ in the hydrogen atmosphere, and finally the W-V-Mo-Re-HfO is obtained 2 -Y 2 O 3 And (3) a composite block.
W-V-Mo-Re-HfO obtained in this example 2 -Y 2 O 3 The density of the alloy is up to 98.9%, the average grain size is 5.3 mu m, and the room temperature micro Vickers hardness is 447HV 0.2 Tensile break strength at 200deg.C is 625MPa, which is superior to pure W and W-Y 2 O 3 (tensile break strength at 200 ℃ C. Was 512MPa and 534MPa, respectively).
Example 4
This example provides a W-V-Mo-Re-HfO prepared by the method of any one of the above examples 2 -Y 2 O 3 The fine-grain bulk material of the nano powder has even alloy material structure, dispersed and distributed oxide particles, the density of the fine-grain bulk material reaches 98.4 percent, the average grain size is 5.7 mu m, and the micro Vickers hardness at room temperature is 439HV 0.2 The tensile breaking strength at 200 ℃ is 612MPa, which is superior to pure W and W-Y 2 O 3 。
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (10)
1.W-V-Mo-Re-HfO 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized by comprising the following steps:
s1, preparing a precursor, namely dissolving vanadate, molybdate, rhenate and soluble rare earth salt in water to form a mixed solution, and adding triethanolamine after fully stirring; continuously stirring, and adding tungstate after the mixed solution is heated; adding oxalic acid after fully mixing and heating the solution system; heating and stirring until the solution is completely evaporated to obtain a precursor;
s2, carrying out hydrogen pyrolysis reduction step by step, grinding the precursor into powder, placing the powder into a sintering boat, placing the sintering boat containing the powder into a reduction furnace, and carrying out three-step reduction in a hydrogen atmosphere;
s3, sintering and solidifying the powder, loading the reduced product obtained in the S2 into a die, compacting the powder, and then sintering in two steps under the hydrogen atmosphere to obtain the W-V-Mo-Re-HfO 2 -Y 2 O 3 Nano powder.
2. The W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, vanadate is ammonium metavanadate;
the molybdate is ammonium molybdate tetrahydrate;
the rhenate is ammonium perrhenate;
the tungstate is ammonium metatungstate;
the soluble rare earth salt is any one of soluble hafnium salt and soluble yttrium salt;
wherein the soluble hafnium salt is any one of chloride or sulfate of hafnium; the soluble yttrium salt is any one of nitrate, oxalate, carbonate, chloride or sulfate of yttrium.
3. The W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, the ratio of the mass percent of the V element in the precursor to the mass percent of the W element in the precursor is 0.2-5:100.
4. the W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, the ratio of the mass percent of Mo element in the precursor to the mass percent of W element in the precursor is 0.2-5:100.
5. the W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, the ratio of the mass percent of Re element in the precursor to the mass percent of W element in the precursor is 0.2-5:100.
6. the W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, the ratio of the mass percent of rare earth oxide particles in the precursor to the mass percent of W element in the precursor is 0.2-5:100.
7. the W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S1, the mass ratio of triethanolamine to soluble rare earth salt is 120-200:100.
8. the W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S2, the specific operation steps of three-step reduction are as follows: firstly, keeping the temperature of a boat containing fine powder at 380-420 ℃ for 20-40 minutes; then heating to 550-650 ℃, and preserving heat for 50-70 minutes; heating to 800-900 deg.c and maintaining for 100-240 min.
9. The W-V-Mo-Re-HfO of claim 1 2 -Y 2 O 3 The chemical preparation method of the nano powder is characterized in that in S3, the two-step sintering method comprises the following specific operation steps: the powder compacted in the mould is firstly preserved for 120 minutes in the hydrogen atmosphere of 1200 ℃ and is presintered; the final sintering was then carried out by incubating for 180 minutes under a hydrogen atmosphere at 2150 ℃.
10. W-V-Mo-Re-HfO prepared by the process as claimed in any one of claims 1 to 9 2 -Y 2 O 3 Fine crystal bulk material of nano powder.
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