CN103111623A - 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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- CN103111623A CN103111623A CN2013100864983A CN201310086498A CN103111623A CN 103111623 A CN103111623 A CN 103111623A CN 2013100864983 A CN2013100864983 A CN 2013100864983A CN 201310086498 A CN201310086498 A CN 201310086498A CN 103111623 A CN103111623 A CN 103111623A
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- 239000000843 powder Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000005275 alloying Methods 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 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007789 sealing 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
- 238000005303 weighing Methods 0.000 claims description 2
- 229910001257 Nb alloy Inorganic materials 0.000 abstract description 17
- 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
- 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
- 238000004519 manufacturing process Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 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
- 239000003870 refractory metal Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000257226 Muscidae Species 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
- 238000006253 efflorescence 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 206010037844 rash Diseases 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
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Technical field
The invention belongs to the dusty material field, relate to a kind of preparation method of Nb-W-Mo-Zr alloy powder, relate in particular to a kind of preparation method of nanocrystalline Nb-W-Mo-Zr alloy powder.
Background technology
Niobium-base alloy is the lightest refractory metal of density, have the characteristics such as fusing point is high, corrosion resistance strong, thermal neutron intercepting and capturing face is little, can be used to make the critical component of 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.
At present the niobium based high-temperature alloy mainly adopts the traditional handicraft manufacturing of ingot casting-pressure processing-machining, exists complex process, stock utilization is low, cost is high, material structure is thick and segregation, is difficult to prepare the deficiency such as Irregular Shaped Parts.And powder metallurgical technique just in time can overcome above-mentioned deficiency, can be used for low-cost in enormous quantities preparation even tissue, complex-shaped near-net-shape parts.Due to the fusing point high (2460 ℃) of niobium, active large (easily and the reactions such as 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.At present the niobium alloy powder preparation method of higher degree mainly contains hydrogenation-go hydrogenization method, ion rotary electrode method, electron beam atomization, electron beam rapid solidification and room temperature mechanical alloying.
Hydrogenation-dehydrogenation method is that the differences of mechanical properties of utilizing niobium to inhale after hydrogen, dehydrogenation prepares powder, mainly comprises hydrogenation, powder process and three steps of dehydrogenation.At first be the hydrogenation of niobium alloy, after element powders is smelted into the niobium alloy ingot casting, is divided into fritter high-temperature heating under hydrogen atmosphere and oozes hydrogen, then be cooled to room temperature.Next is powder process, utilizes fragmentation, efflorescence equipment that the block hydrogenated niobium that diameter is not more than 2.5cm is carried out fragmentation, classification under inert gas shielding, prepares the niobium alloy powder of hydrogenation.Be dehydrogenation at last, under cryogenic conditions, with niobium alloy powder Repeat-heating dehydrogenation in vacuum drying oven 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 can utilize its excellent superconductivity to prepare superconductor.
The operation principle of PREP method is that the niobium alloy ingot casting is processed into bar-shaped consutrode, the electrode bar end face of High Rotation Speed is melted by plasma arc, the drop that is melted on bar end face flies out under the effect of centrifugal force, is rapidly solidificated into tiny spherical powder particle in cooling medium (vacuum, helium or argon gas).
Electron beam atomization technique is the unique industrialization means of high-purity refractory metal that obtain at present, is also economy, the effective method that obtains High-purity Niobium.Its principle is, under vacuum condition, the niobium ingot via the VAR melting in the EB chamber moves under electron gun, and high-power electron beam makes its continuous fusing, and drip melt is on atwirl water-cooled copper dish, and molten drop is cast aside by rotating disc.Drop is because capillary effect is spherical in shape, with the collision of chamber wall in be cooled to rapidly alloy powder.Except vacuum condition, niobium alloy powder also can prepare under helium or argon gas atmosphere.
The electron beam rapid solidification method is that the electron beam centrifugal atomization apparatus is improved a little, and the atomized flow of alloy liquid droplet is 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 of the method preparation, have in the zone, interdendritic than EBA, cooldown rate that the PREP powder is larger, the alloy liquid droplet state of these pine-tree structures before rapid solidification be forming core just.
The standby niobium alloy powder gap field trash of plasma rotating electrode method and electron beam atomization legal system is less, and purity is higher, but production cost is high, has seriously restricted commercially producing of powder metallurgy niobium alloy.
Room-temperature ball-milling is as the term suggests namely at room temperature carry out the method for ball milling.The method is that element powders and the abrading-ball that proportioning is good is placed in the ball grinder that is 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, more than usually needing 40h.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing superfine nano-crystalline niobium-base alloy powder.The niobium-base alloy powder of the method preparation is evenly tiny, has nanocrystalline structure.
The preparation technology that the low temperature ball milling prepares nanocrystalline niobium alloy powder is as shown in Figure 1:
The first step is at first in alloying component ratio weighing element powders;
Second step is placed in element powders and abrading-ball the ball grinder that is equipped with air bleeding valve;
In the 3rd step, with the ball grinder sealing, repeat to vacuumize, be filled with high-purity argon gas 3-5 time;
The 4th Walk is placed in ball grinder and carries out ball milling on the low temperature ball mill that fills liquid nitrogen, and rotational speed of ball-mill is controlled in the scope of 300-500 r/min, and Ball-milling Time is 5-10h;
Wu Walk, the complete rear taking-up ball grinder of ball milling takes out alloy powder, seal.
Different from room-temperature ball-milling, the low temperature ball milling is as for carrying out in liquid nitrogen environment with ball grinder.Under the low temperature environment of liquid nitrogen, powder more easily obtains highdensity dislocation, accelerates the alloying process, thereby can greatly 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 particle diameter of preparation is evenly tiny, has nanocrystalline structure, can realize the activated sintering in powder metallurgy process, reduces sintering temperature.
Description of drawings
Fig. 1 is process chart of the present invention
The specific embodiment
Embodiment 1: prepare nanocrystalline Nb-5wt%W-2 wt%Mo-1wt%Zr alloy powder with the low temperature ball-milling technology
The first step, adopting purity＞99.8%, granularity is the Nb powder of-325 mesh; Purity＞99.9%, granularity are the W powder of 3 ~ 5 μ m; Purity＞99.9%, granularity are the Mo powder of 1 ~ 2 μ m; Purity＞99.5%, granularity are that the Zr powder of 4 ~ 8 μ m is raw material.
Second step is according to 4 parts of pre-alloyed powders that quality is 100g of composition proportion preparation of Nb-5wt%W-2wt%Mo-1wt%Zr.
In the 3rd step, it is the stainless ball grinder of heat treatment that the powder that configures is placed in respectively 4 materials, and puts into each 20 of the sintered carbide balls that diameter is 10mm, 8mm, 6mm in each tank, with ball grinder sealing, repeats to vacuumize, fills high-purity argon gas 4 times.
Si Walk is placed in ball grinder on the low temperature ball mill that fills liquid nitrogen, and ball milling 7 h, rotational speed of ball-mill are 350r/min.
In the 5th step, after ball milling is completed, in the argon shield glove box, powder is taken out, seals.
Adopting the particle mean size of the Nb-5wt%W-2wt%Mo-1wt%Zr alloy powder of this technique preparation is 500nm, and average grain size is 9nm, and alloying level is 100%.
Claims (2)
1. the preparation method of a nanocrystalline Nb-W-Mo-Zr alloy powder is characterized in that the method comprises the following steps:
The first step is at first in alloying component ratio weighing element powders;
Second step is placed in element powders and abrading-ball the ball grinder that is equipped with air bleeding valve;
In the 3rd step, with the ball grinder sealing, repeat to vacuumize, be filled with high-purity argon gas 3-5 time;
The 4th Walk is placed in ball grinder and carries out ball milling on the low temperature ball mill that fills liquid nitrogen, and rotational speed of ball-mill is controlled in the scope of 300-500 r/min, and Ball-milling Time is 5-10h;
Wu Walk, the complete rear taking-up ball grinder of ball milling takes out alloy powder, seal.
2. the preparation method of nanocrystalline Nb-W-Mo-Zr alloy powder as claimed in claim 1 is characterized in that the method is specially:
The first step, adopting purity＞99.8%, granularity is the Nb powder of-325 mesh; Purity＞99.9%, granularity are the W powder of 3 ~ 5 μ m; Purity＞99.9%, granularity are the Mo powder of 1 ~ 2 μ m; Purity＞99.5%, granularity are that the Zr powder of 4 ~ 8 μ m is raw material;
Second step is according to 4 parts of pre-alloyed powders that quality is 100g of composition proportion preparation of Nb-5wt%W-2wt%Mo-1wt%Zr;
In the 3rd step, it is the stainless ball grinder of heat treatment that the powder that configures is placed in respectively 4 materials, and puts into each 20 of the sintered carbide balls that diameter is 10mm, 8mm, 6mm in each tank, with ball grinder sealing, repeats to vacuumize, fills high-purity argon gas 4 times;
Si Walk is placed in ball grinder on the low temperature ball mill that fills liquid nitrogen, and ball milling 7 h, rotational speed of ball-mill are 350r/min;
In the 5th step, after ball milling is completed, in the argon shield glove box, powder is taken out, seals.
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| CN201310086498.3A CN103111623B (en) | 2013-03-19 | 2013-03-19 | Method for preparing nanocrystalline Nb-W-Mo-Zr alloy powder |
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| CN201310086498.3A CN103111623B (en) | 2013-03-19 | 2013-03-19 | Method for preparing nanocrystalline Nb-W-Mo-Zr alloy powder |
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| CN103111623B CN103111623B (en) | 2015-06-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103658677A (en) * | 2013-12-30 | 2014-03-26 | 北京科技大学 | Nanometer tungsten carbide powder preparing method |
| 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 |
| CN110355375A (en) * | 2019-08-26 | 2019-10-22 | 西北有色金属研究院 | The preparation method of high-strength niobium alloy powder in the transgranular enhanced type of nano-carbide |
| CN112475302A (en) * | 2020-11-16 | 2021-03-12 | 安徽省瑞峻粉末金属材料有限公司 | Preparation method of superfine nanocrystalline VN alloy powder |
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| 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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- 2013-03-19 CN CN201310086498.3A patent/CN103111623B/en not_active Expired - Fee Related
Patent Citations (4)
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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 |
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Non-Patent Citations (1)
| Title |
|---|
| D.Z. ZHANG等: "Fabrication and characterization of nanocrystalline Nb–W–Mo–Zr alloy powder by ball milling", 《JOURNAL OF REFRACTORY METALS AND HARD MATERIALS》, no. 32, 31 May 2012 (2012-05-31), pages 45 - 50 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103658677A (en) * | 2013-12-30 | 2014-03-26 | 北京科技大学 | Nanometer tungsten carbide powder preparing method |
| 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 |
| CN110355375A (en) * | 2019-08-26 | 2019-10-22 | 西北有色金属研究院 | The preparation method of high-strength niobium alloy powder in the transgranular enhanced type of nano-carbide |
| CN112475302A (en) * | 2020-11-16 | 2021-03-12 | 安徽省瑞峻粉末金属材料有限公司 | Preparation method of superfine nanocrystalline VN 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 |
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