CN103111623B - Method for preparing nanocrystalline Nb-W-Mo-Zr alloy powder - Google Patents
Method for preparing nanocrystalline Nb-W-Mo-Zr alloy powder Download PDFInfo
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- CN103111623B CN103111623B CN201310086498.3A CN201310086498A CN103111623B CN 103111623 B CN103111623 B CN 103111623B CN 201310086498 A CN201310086498 A CN 201310086498A CN 103111623 B CN103111623 B CN 103111623B
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- 239000000843 powder Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000005275 alloying Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000000740 bleeding effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910001257 Nb alloy Inorganic materials 0.000 abstract description 17
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 239000000956 alloy Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000004663 powder metallurgy Methods 0.000 abstract description 3
- 238000000875 high-speed ball milling Methods 0.000 abstract 1
- 238000010894 electron beam technology Methods 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 6
- 229910052758 niobium Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007712 rapid solidification Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021398 atomic carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009690 centrifugal atomisation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
Abstract
The invention belongs to the field of powder material, and relates to a method for preparing nanocrystalline Nb-W-Mo-Zr alloy powder. The method performs high-speed ball milling in low-temperature environment of liquid nitrogen, powder easily obtains high-density dislocation, the alloying process is accelerated, thus the ball milling time can be greatly shortened, and the alloy powder with finer particle size than grain and powder is obtained. The average particle size of the Nb-5wt%W-2wt%Mo-1wt%Zr alloy powder prepared by the technology is 500nm, the average grain size is 9nm, and the alloying degree is 100%. The method provided by the invention has the advantages that the particle size of the prepared niobium alloy powder is uniform and fine, the alloy powder has a nanocrystalline structure, activated sintering in the powder metallurgy process can be realized, and the sintering temperature is lowered.
Description
Technical field
The invention belongs to field of powder material, relate to a kind of preparation method of Nb-W-Mo-Zr alloy powder, particularly relate to a kind of preparation method of nanocrystalline Nb-W-Mo-Zr alloy powder.
Background technology
Niobium-base alloy is the refractory metal that density is the lightest, there is the features such as fusing point is high, corrosion resistance strong, thermal neutron intercepting and capturing face is little, can be used to the critical component manufacturing rocket engine, aircraft jet pipe, satellite and nuclear reactor, be widely used in the fields such as Aero-Space, atomic energy, medical treatment and nuclear industry, be considered to the most promising high-temperature structural material of future generation.
Current niobium based high-temperature alloy mainly adopts the traditional handicraft manufacture of ingot casting-pressure processing-machining, there is complex process, stock utilization is low, cost is high, material structure is thick and segregation, be difficult to prepare the deficiencies such as Irregular Shaped Parts.And powder metallurgical technique just in time can overcome above-mentioned deficiency, can be used for low cost prepares even tissue, complex-shaped near-net-shape parts in enormous quantities.Due to the fusing point of niobium high (2460 DEG C), active large reactions such as (easily and) alloying element, clearance-type atomic carbon, oxygen, nitrogen, the preparation of niobium alloy powder is a large technical bottleneck of its powder metallurgical production technique always.The niobium alloy powder preparation method of current higher degree mainly contains hydrogenation-remove hydrogenization method, ion rotary electrode method, electron beam atomization, electron beam rapid solidification and room temperature mechanical alloying.
Hydrogenation-dehydrogenation method utilizes niobium to inhale hydrogen, differences of mechanical properties after dehydrogenation to prepare powder, mainly comprises hydrogenation, powder process and dehydrogenation three steps.First be the hydrogenation of niobium alloy, after element powders being smelted into niobium alloy ingot casting, be divided into fritter in a hydrogen atmosphere high-temperature heating ooze hydrogen, be then cooled to room temperature.Next is powder process, utilizes broken, that diameter is not more than 2.5cm by powered equipment block hydrogenated niobium to carry out fragmentation, classification under inert gas shielding, prepares the niobium alloy powder of hydrogenation.Be finally dehydrogenation, under cryogenic, by the Repeat-heating dehydrogenation in a vacuum furnace of the niobium alloy powder of hydrogenation, obtain the in irregular shape niobium alloy powder identical with original niobium alloy ingot casting microstructure.The standby niobium powder of hydrogenation-dehydrogenation legal system is unsuitable for preparing powdered metal parts, but the superconductivity of its excellence can be utilized to prepare superconductor.
The operation principle of PREP method is that niobium alloy ingot casting is processed into bar-shaped consutrode, the electrode bar end face of High Rotation Speed is plasma arc melting, the drop that bar end face is melted flies out under the influence of centrifugal force, in cooling medium (vacuum, helium or argon gas), be rapidly solidificated into tiny spherical powder particle.
Electron beam atomization technique is the unique industrialization means obtaining high-purity refractory metal at present, is also the economy, the effective method that obtain High-purity Niobium.Its principle is, under vacuum, the niobium ingot via VAR melting in EB room moves under electron gun, and high-power electron beam makes it constantly melt, and drip melt is on atwirl water-cooled copper dish, and molten drop is cast aside by rotating disc.Drop due to capillary effect spherical in shape, with the collision of chamber wall in be cooled to alloy powder rapidly.Except vacuum condition, niobium alloy powder also can be prepared under helium or argon gas atmosphere.
Electron beam rapid solidification method is improved a little electron beam centrifugal atomization apparatus, the atomized flow of alloy liquid droplet directly struck on a water-cooled copper plate, obtains the preparation method of the sheet alloy powder of rapid solidification.Adopt the sheet niobium alloy powder prepared of the method, there is in interdendritic regions the cooldown rate larger than EBA, PREP powder, the alloy liquid droplet state of these pine-tree structures before rapid solidification just forming core.
Plasma rotating electrode process and the standby niobium alloy powder gap field trash of electron beam atomization legal system less, purity is higher, but production cost is high, seriously constrains commercially producing of powder metallurgy niobium alloy.
Namely room-temperature ball-milling as the term suggests at room temperature carry out the method for ball milling.The method is that the good element powders of proportioning and abrading-ball are placed in the ball grinder being full of inert gas, and ball grinder carries out high-energy ball milling under room temperature environment, and powder forms alloy powder under high-speed impact.But when utilizing the method to produce niobium alloy powder, Ball-milling Time is longer, usually needs more than 40h.
Summary of the invention
The object of this invention is to provide a kind of method preparing superfine nano-crystalline niobium-base alloy powder.Niobium-base alloy powder prepared by the method is evenly tiny, has nanocrystalline structure.
Low temperature ball milling prepares the preparation technology of nanocrystalline niobium alloy powder as shown in Figure 1:
The first step, first weighs element powders in alloying component ratio;
Second step, is placed in the ball grinder being equipped with air bleeding valve by element powders and abrading-ball;
3rd step, seals ball grinder, repeats to vacuumize, be filled with high-purity argon gas 3-5 time;
4th Walk, is placed in ball grinder on the low temperature ball mill filling liquid nitrogen and carries out ball milling, and rotational speed of ball-mill controls in the scope of 300-500 r/min, and Ball-milling Time is 5-10h;
Wu Walk, takes out ball grinder after ball milling, is taken out by alloy powder, seals.
Different from room-temperature ball-milling, low temperature ball milling is carried out as in liquid nitrogen environment by ball grinder.Under the low temperature environment of liquid nitrogen, powder more easily obtains highdensity dislocation, accelerates alloying process, thus greatly can shorten Ball-milling Time, obtains crystal grain and the more tiny alloy powder of powder size.
Advantage of the present invention is that the niobium alloy powder uniform particle sizes of preparation is tiny, has nanocrystalline structure, can realize the activated sintering in powder metallurgy process, reduces sintering temperature.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention
Detailed description of the invention
embodiment 1: prepare nanocrystalline Nb-5wt%W-2 wt%Mo-1wt%Zr alloy powder with low temperature ball-milling technology
The first step, employing purity > 99.8%, granularity are the Nb powder of-325 mesh; Purity > 99.9%, granularity are the W powder of 3 ~ 5 μm; Purity > 99.9%, granularity is the Mo powder of 1 ~ 2 μm; Purity > 99.5%, granularity are the Zr powder of 4 ~ 8 μm is raw material.
Second step, preparing 4 parts of quality according to the composition proportion of Nb-5wt%W-2wt%Mo-1wt%Zr is the pre-alloyed powder of 100g.
3rd step, the powder configured being placed in respectively 4 materials is the stainless ball grinder of heat treatment, and in each tank, put into each 20 of the sintered carbide ball that diameter is 10mm, 8mm, 6mm, is sealed by ball grinder, repeats to vacuumize, fill high-purity argon gas 4 times.
Tetra-Walk, is placed in ball grinder and fills on the low temperature ball mill of liquid nitrogen, ball milling 7 h, and rotational speed of ball-mill is 350r/min.
5th step, after ball milling completes, takes out powder, seals in argon shield glove box.
The particle mean size of the Nb-5wt%W-2wt%Mo-1wt%Zr alloy powder adopting this technique to prepare is 500nm, and average grain size is 9nm, and alloying level is 100%.
Claims (1)
1. a preparation method for nanocrystalline Nb-W-Mo-Zr alloy powder, is characterized in that the method comprises the following steps:
The first step, first weighs element powders in alloying component ratio, and employing purity > 99.8%, granularity are the Nb powder of-325mesh; Purity > 99.9%, granularity are the W powder of 3 ~ 5 μm; Purity > 99.9%, granularity is the Mo powder of 1 ~ 2 μm; Purity > 99.5%, granularity are the Zr powder of 4 ~ 8 μm is raw material;
Second step, is placed in the ball grinder being equipped with air bleeding valve by element powders and abrading-ball, and to prepare 4 parts of quality according to the composition proportion of Nb-5wt%W-2wt%Mo-1wt%Zr be the pre-alloyed powder of 100g;
3rd step, the powder configured being placed in respectively 4 materials is the stainless ball grinder of heat treatment, and in each tank, put into each 20 of the sintered carbide ball that diameter is 10mm, 8mm, 6mm, ball grinder is sealed, repeats to vacuumize, be filled with high-purity argon gas 3-5 time;
Tetra-Walk, is placed in ball grinder and fills on the low temperature ball mill of liquid nitrogen, and rotational speed of ball-mill controls in the scope of 300-500r/min, and Ball-milling Time is 5-10h;
Wu Walk, after ball milling completes, takes out powder, seals in argon shield glove box.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103658677B (en) * | 2013-12-30 | 2016-06-08 | 北京科技大学 | The preparation method of a kind of nano powder of tungsten carbide |
| CN109317660A (en) * | 2018-09-27 | 2019-02-12 | 南京工业大学 | A kind of method of the low temperature ball milling in-situ solidifying technology preparation isometric nano-crystal Kufil of two-phase |
| CN110355375B (en) * | 2019-08-26 | 2020-12-18 | 西北有色金属研究院 | Preparation method of nano carbide in-crystal strengthened medium-high strength niobium alloy powder |
| CN112475302B (en) * | 2020-11-16 | 2023-02-24 | 安徽省瑞峻粉末金属材料有限公司 | Preparation method of superfine nanocrystalline VN alloy powder |
Citations (3)
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| CN1623215A (en) * | 2002-01-24 | 2005-06-01 | H.C.施塔克公司 | Capacitor-grade lead wires with increased tensile strength and hardness |
| KR20050111457A (en) * | 2004-05-21 | 2005-11-25 | 박종덕 | The fe-based nano-alloy powders and the method there of |
| CN101549405A (en) * | 2009-05-19 | 2009-10-07 | 燕山大学 | High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material |
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| US20050092400A1 (en) * | 2002-03-04 | 2005-05-05 | Leibniz-Institut Fur Festkorper-Und | Copper-niobium alloy and method for the production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623215A (en) * | 2002-01-24 | 2005-06-01 | H.C.施塔克公司 | Capacitor-grade lead wires with increased tensile strength and hardness |
| KR20050111457A (en) * | 2004-05-21 | 2005-11-25 | 박종덕 | The fe-based nano-alloy powders and the method there of |
| CN101549405A (en) * | 2009-05-19 | 2009-10-07 | 燕山大学 | High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material |
Non-Patent Citations (1)
| Title |
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| Fabrication and characterization of nanocrystalline Nb–W–Mo–Zr alloy powder by ball milling;D.Z. Zhang等;《Journal of Refractory Metals and Hard Materials》;20120531(第32期);45–50页 * |
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