CN100582267C - Method for preparing grain-refining W-Ni-Fe alloy containing rare earth - Google Patents
Method for preparing grain-refining W-Ni-Fe alloy containing rare earth Download PDFInfo
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- CN100582267C CN100582267C CN200810030663A CN200810030663A CN100582267C CN 100582267 C CN100582267 C CN 100582267C CN 200810030663 A CN200810030663 A CN 200810030663A CN 200810030663 A CN200810030663 A CN 200810030663A CN 100582267 C CN100582267 C CN 100582267C
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Abstract
The invention relates to a method of preparing high-performance fine-grained W-Ni-Fe alloy containing a trace of rare earth. The invention uses ultra-fine / nano-W-Ni-Fe composite powder containing a trace of rare earth Y, La and Ce, which is prepared through conducting the sol, sponging drying and thermal recovery to soluble tungsten salt, soluble nickel salt, crystals of soluble malysite and a trace of soluble rare-earth salt. In the composite powder, W accounts for 88 to 97wt percent; and rare earth oxides account for 0.02 to 0.8wt percent, and rests are Ni and Fe. The composite powder can be shaped by pressing and can be pre-burnt in the reducing atmosphere; and then the composite powder can be sintered by solid phases and liquid phases to be prepared into high-performance fine-grained W-Ni-Fe alloy containing a trace of rare earth. The tensile-strength of the alloy prepared by the invention is ranged from 1000 to 1300 MPa, and the elongation is ranged from 15 to 30 percent, and the grain size is ranged from 1 to 10 micrometers. With good powder formability, and the invention has excellent dynamic mechanical property and forms ability of partial adiabatic shear bands.
Description
Technical field:
A kind of preparation method who contains the high-performance grain-refining W-Ni-Fe alloy of trace rare-earth, relate to nano material and field of powder metallurgy, particularly adopt nanotechnology, rear-earth-doped, solid state sintering and liquid phase sintering preparation to contain the method for trace rare-earth high-performance grain-refining W-Ni-Fe alloy.
Background technology:
The W-Ni-Fe high-density alloy has characteristics such as density height, intensity height, ductility height, is mainly used in many aspects such as aviation device, radiation shielding, military project weapon material for a long time.The production method of tradition W-Ni-Fe alloy is that W powder, Ni powder, Fe powder and other alloying element powder mixing, compacting, liquid phase sintering are reached near complete fine and close, adopts the liquid phase sintering tungsten grain to grow up rapidly, can reach 40-60 μ m usually, and alloy mechanical property is lower.
Tungsten grain refinement and interpolation trace element can improve alloy mechanical property greatly in the W-Ni-Fe alloy, and the tungsten grain degree directly depends on the starting powder granularity.Adopt prepared by mechanical alloy ultra-fine/nanocrystalline composite powder is the maximum a kind of method of research in the hope of improving alloy mechanical property and thinning microstructure structure, and obtains very big achievement.The inventor herein adopts the nanocrystalline W-Ni-Fe composite powder of prepared by mechanical alloy alloy density after solid state sintering and liquid phase sintering can reach 99% at calendar year 2001 national defence patent " prepare with powder metallurgy technology thin brilliant high-performance high-density alloy (patent No.: 01101064.9) " report, tensile strength can reach 1100-1300MPa, unit elongation is more than 20%, and grain-size is at 1-5 μ m.And people such as external S Park report also that at article " Dynamic deformation behavior of an oxide-dispersed tungstenheavy alloy fabricated by mechanical alloying " high-density alloy that contains rare earth oxide of employing prepared by mechanical alloy has good dynamic properties.But, since in the ma process powder repeatedly ball milling produce cold welding and tear, cause the pattern of powder to produce sheet, be unfavorable for being shaped.And be easy to generate ball milling and be mingled with, and trace rare earth oxides mixes inhomogeneous.At this problem of mechanical alloying powder, patent " method for preparing nano level tungsten base composite powder with colloidal sol-spraying drying-thermal reduction; ZL03143136.4 " report in 2003, adopt the prepared nanometer tungsten base composite powder of colloidal sol-spraying drying-thermal reduction to have fine size, distributed components, the characteristics that purity is high, the powder Fisher particle size is less than 1.0 μ m, specific surface granularity after the dispersion and powder morphology are analyzed granularity less than 100nm, the tungsten grain degree of powder is 20-50nm, powder is spherical in shape, and formability is fine, powder does not have other and is mingled with, and oxygen level is lower than 0.2%, and this powder has good sintering activity.But adopting the alloyed tungsten crystal grain after this powder liquid phase sintering is about 25 μ m, approaches traditional W-Ni-Fe alloy, and alloy property is also close with conventional alloy property.
Summary of the invention:
In order to overcome above deficiency, the present invention proposes a kind of by soluble tungsten salt, soluble nickel salt, soluble ferric iron salt, soluble rare-earth salt crystal, through colloidal sol-spraying drying-thermal reduction, ultra-fine/the method for nanometer W-Ni-Fe composite powder that preparation contains trace rare-earth, W:88～97wt% in the composite powder, the rare earth oxide content of Y, La or Ce is 0.02～0.8wt%, and all the other compositions are that Ni and Fe, wherein Ni: Fe is 1: 1～4: 1.With the composite powder press forming, the pre-burning in reducing atmosphere of W-Ni-Fe shaping base contains the trace rare-earth grain-refining W-Ni-Fe alloy after be prepared into high-performance after solid state sintering and the liquid phase sintering, alloy mechanical property is good, tensile strength is 1000～1300MPa, unit elongation is 15～30%, and grain-size is tiny, and grain fineness number is 1～10 μ m, and this alloy has good dynamic properties and form local Adiabatic Shear band ability, and powder forming is good.Concrete scheme of the present invention is as follows:
(1) select soluble tungsten salt, soluble nickel salt, soluble ferric iron salt crystal to be configured to colloidal sol, soluble tungsten salt is ammonium metawolframate or ammonium tungstate, soluble nickel salt is nickelous chloride, single nickel salt, nickelous nitrate or nickelous oxalate, soluble ferric iron salt is iron(ic) chloride, ferric sulfate, iron nitrate or ironic oxalate, join with lanthanum nitrate, Yttrium trinitrate or cerous nitrate soluble ree salt form and to form colloid in the mixing solutions, W:88～97wt% in the colloidal sol wherein, all the other compositions are Ni and Fe, add the oxide compound of rare earth elements such as Y, the La of 0.02～0.8wt% or Ce with the soluble ree salt form; The colloidal sol of configuration is made tungsten ferronickel composite oxides precursor powder after spray-dried, precursor powder is prepared the ultra-fine/nanometer W-Ni-Fe composite powder that contains trace rare-earth element then 300～600 ℃ of calcinings after 350～600 ℃ of insulations 1～3 hour and 700～900 ℃ of insulation 0.5～3h reduction under reducing atmosphere;
(2) with composite powder press forming under 100～400MPa pressure;
(3) the shaping base prepares presintered compact in 700～1000 ℃ of insulation 1～3h pre-burning under protective atmosphere;
(4) presintered compact carries out solid state sintering at 1100～1300 ℃ of insulation 1～3h under protective atmosphere;
(5) be to carry out the intensified-sintered one-tenth of liquid phase W-Ni-Fe alloy in 5～30 minutes with the sintered blank behind the solid state sintering 1380～1500 ℃ of soaking times, protective atmosphere is H
2, N
2+ H
2, Ar, N
2Or vacuum atmosphere.
Advantage of the present invention and positively effect are embodied in:
(1) in the W-Ni-Fe composite powder, add rare earth element, effectively suppressed powder the growing up of tungsten grain in sintering process, refinement alloy structure, improved the mechanical property of alloy.
(2) with traditional liquid phase sintering W-Ni-Fe alloy phase ratio, the alloyed tungsten grain-size of the present invention's preparation reduces by 6～10 times; Have typical liquid phase sintering and organize spherical tungsten grain structure, grain-size is 1～10 μ m.
(3) with traditional liquid phase sintering W-Ni-Fe alloy phase ratio, the alloy tensile strength of the present invention's preparation exceeds more than 200～400MPa, reaches 1000～1300MPa, and unit elongation is 15～30%.
(4) the thin brilliant armour piercing shot bullet core material of armour-piercing self-sharpening is efficiently injured in the very suitable preparation of the present invention.
Embodiment
Embodiment 1:
(1) takes by weighing 160.0g ammonium metawolframate, 44.7g nickelous nitrate, 28.0g iron nitrate, 0.2g Yttrium trinitrate and be dissolved in 766gH
2O is configured to the 20wt% mixing solutions; Solution is carried out spraying drying, and spraying drying, inlet temperature are 300 ℃, 190 ℃ of air outlet temperatures, and feed rate is 20ml/min, obtains tungsten ferronickel oxide precursor powder.Precursor powder is calcined in air, and calcining temperature is 600 ℃, and calcination time is 90min, obtains tungsten ferronickel oxide composite end.With tungsten ferronickel oxide composite end at H
2Respectively through the two step reducing process of 400 ℃ of insulation 1.5h, 700 ℃ of insulation 2h, obtain containing 0.04wt%Y under the atmosphere
2O
3Ultra-fine/nano composite powder of 90W-7Ni-3Fe.
(2) will contain 0.04wt%Y
2O
3Ultra-fine/nano composite powder of 90W-7Ni-3Fe be pressed into tension specimen in the 200MPa mold pressing.
(3) the tension specimen pressed compact is incubated the 1h pre-burning at 800 ℃ in hydrogen sintering furnace.
(4) sample after the pre-burning is carried out solid state sintering at 1200 ℃ of insulation 2h.
(5) sample behind the solid state sintering is carried out liquid phase sintering at 1380 ℃ of insulation 30min, obtain spherical tungsten grain and the mutually equally distributed fine and close alloy of bonding, the tungsten grain size is at 1～10m, and tensile strength is more than 1150MPa, and unit elongation is more than 25%.
Embodiment 2:
(1) takes by weighing 173.6g ammonium metawolframate, 32.8g nickelous nitrate, 20.5g iron nitrate, 0.4g lanthanum nitrate and be dissolved in 773gH
2O is configured to the 20wt% mixing solutions; Solution is carried out spray dried, dry, and spraying drying, inlet temperature are 300 ℃, 190 ℃ of air outlet temperatures, and feed rate is 20ml/min, obtains tungsten ferronickel oxide precursor powder.Precursor powder is calcined in air, and calcining temperature is 600 ℃, and calcination time is 90min, obtains tungsten ferronickel oxide composite end.With tungsten ferronickel oxide composite end at H
2Respectively through the two step reducing process of 480 ℃ of insulation 1h, 800 ℃ of insulation 1h, obtain containing 0.1wt%La under the atmosphere
2O
3Ultra-fine/nano composite powder of 93W-4.9Ni-2.1Fe.
(2) will contain 0.1wt%La
2O
3Ultra-fine/nano composite powder of 93W-4.9Ni-2.1Fe be pressed into tension specimen in the 300MPa mold pressing.
(3) the tension specimen pressed compact is incubated the 1h pre-burning at 900 ℃ in hydrogen sintering furnace.
(4) sample after the pre-burning is carried out solid state sintering at 1250 ℃ of insulation 1.5h.
(5) it is intensified-sintered the sample behind the solid state sintering to be carried out instantaneous liquid phase at 1400 ℃ of insulation 20min, obtains the spherical tungsten grain and the mutually equally distributed fine and close alloy that bonds, and the tungsten grain size is at 1～10m, and tensile strength is more than 1050MPa, and unit elongation is more than 15%.
Claims (1)
1. preparation method who contains the grain-refining W-Ni-Fe alloy of rare earth, with solid state sintering, liquid phase sintering, trace rare-earth Y, La or Ce mix with colloidal sol-spraying drying-thermal reduction preparation contain trace rare-earth ultra-fine/nanometer W-Ni-Fe composite powder prepares the W-Ni-Fe alloy through two-step sintering, it is characterized in that may further comprise the steps:
(1) mixes through the ultra-fine/nanometer W-Ni-Fe composite powder of colloidal sol-spraying drying-thermal reduction preparation by soluble tungsten salt, soluble nickel salt, soluble ferric iron salt crystal and trace rare-earth Y, La or Ce, W:88～97wt% in the composite powder, the rare earth oxide content that contains Y, La or Ce is 0.02～0.8wt%, all the other compositions are that Ni and Fe, wherein Ni: Fe is 1: 1～4: 1; Described soluble tungsten salt is ammonium metawolframate or ammonium tungstate, soluble nickel salt is nickelous chloride, single nickel salt, nickelous nitrate or nickelous oxalate, soluble ferric iron salt is iron(ic) chloride, ferric sulfate, iron nitrate or ironic oxalate, joins with lanthanum nitrate, Yttrium trinitrate or cerous nitrate soluble ree salt form and forms colloid in the mixing solutions;
(2) with the composite powder press forming, pressing pressure is 100～400Mpa;
(3) the shaping base is prepared into presintered compact after pre-burning under protective atmosphere, and calcined temperature is 700～1000 ℃, and soaking time is 1～3 hour;
(4) with presintered compact solid state sintering under protective atmosphere, sintering temperature is 1100～1300 ℃, and soaking time is 1～3 hour; Liquid phase sintering becomes the W-Ni-Fe alloy, and the liquid phase sintering temperature is 1380～1500 ℃, and soaking time is 5～30 minutes, and described protective atmosphere is H
2, N
2+ H
2, Ar, N
2Or vacuum atmosphere.
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| CN100582267C true CN100582267C (en) | 2010-01-20 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013084748A1 (en) * | 2011-12-07 | 2013-06-13 | 株式会社アライドマテリアル | Sintered tungsten alloy |
| CN102787249B (en) * | 2012-09-07 | 2014-05-14 | 洛阳高新四丰电子材料有限公司 | Sintering process for preparing high-density tungsten ferro-nickel alloy |
| CN102974823B (en) * | 2012-12-12 | 2015-05-20 | 广汉川冶新材料有限责任公司 | Sintering method of high gravity alloy |
| WO2016061721A1 (en) * | 2014-10-20 | 2016-04-28 | 中南大学 | Method for preparing rare-earth oxide dispersion strengthened fine-grained tungsten material |
| CN104630532B (en) * | 2015-02-10 | 2016-12-07 | 中南大学 | A kind of preparation method of carbide and rare earth oxide complex intensifying carefully brilliant tungsten material |
| CN106591613B (en) * | 2016-11-10 | 2018-02-13 | 洛阳科威钨钼有限公司 | The method that tungsten-molybdenum alloy is prepared using beneficial element doping |
| CN106834856B (en) * | 2017-01-16 | 2018-11-16 | 西安华山金属制品有限公司 | A kind of W-Ni-Fe-Y-ZrB2Heterogeneous alloy material and preparation method thereof |
| CN107629624B (en) * | 2017-09-15 | 2019-11-26 | 广州中国科学院工业技术研究院 | Rare earth metal ferroalloy wave absorbing agent and preparation method thereof, application |
| CN108723380A (en) * | 2018-06-07 | 2018-11-02 | 江西离子型稀土工程技术研究有限公司 | A kind of preparation method of rare earth-iron base pre-alloyed powder |
| CN109158612B (en) * | 2018-09-21 | 2021-12-17 | 河南科技大学 | Preparation method of tungsten alloy precursor composite powder, tungsten alloy and preparation method thereof |
| CN113913665A (en) * | 2021-09-30 | 2022-01-11 | 中国科学院重庆绿色智能技术研究院 | Nano lanthanum oxide reinforced tungsten-based composite material and preparation method thereof |
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