CN102839301B - Rare earth coblat-based alloy, alloy powder and manufacturing method of alloy and alloy powder - Google Patents
Rare earth coblat-based alloy, alloy powder and manufacturing method of alloy and alloy powder Download PDFInfo
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- CN102839301B CN102839301B CN201210341933.8A CN201210341933A CN102839301B CN 102839301 B CN102839301 B CN 102839301B CN 201210341933 A CN201210341933 A CN 201210341933A CN 102839301 B CN102839301 B CN 102839301B
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- 239000000956 alloy Substances 0.000 title claims abstract description 118
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 82
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 77
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 77
- 239000000843 powder Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 95
- 239000010941 cobalt Substances 0.000 claims abstract description 95
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 95
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 22
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 21
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 12
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005204 segregation Methods 0.000 claims abstract description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 59
- 239000001257 hydrogen Substances 0.000 claims description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 32
- 238000005275 alloying Methods 0.000 claims description 25
- 239000008188 pellet Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 13
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 9
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000531 Co alloy Inorganic materials 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052773 Promethium Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
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- 235000009165 saligot Nutrition 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a rare earth cobalt-based alloy, alloy powder and a manufacturing method of the alloy and the alloy powder. Particularly, the rare earth cobalt-based alloy material which consists of samarium, cobalt, iron, copper, zirconium and at least one of other rare earth elements (lanthanum, cerium, praseodymium, neodymium, europium, gadolinium and a combination of the lanthanum, cerium, praseodymium, neodymium, europium and gadolinium) is manufactured, and adopts a microstructure that RCo7 phase grains are wrapped with RCo5 phase grains, wherein an RCo5 chemical compound is in a crystalline hexagonal structure, an RCo7 chemical compound is in a crystalline and hexagonal structure (R comprises an SM element and at least one of other light rare earth elements), and other light rare earth elements are distributed in the RCo5 phase in a segregation manner. The invention further discloses the manufacturing method of the rare earth cobalt-based alloy and the alloy powder, which is moderate in condition, low in equipment requirement, high in efficiency, and suitable for industrial production.
Description
Technical field
The present invention relates to the preparing technical field of rare earth cobalt base alloy, particularly, the invention provides a kind of novel rare earth cobalt base alloy and powder preparation method thereof.
Background technology
SmCo (SmCo) permanent magnet alloy is a kind of permanent magnet material with higher Curie temperature, higher HCJ (Hcj) and low HCJ temperature factor, is generally considered the permanent magnet material that a class is hopeful to realize high temperature application most.At present, samarium cobalt permanent magnet Ti Shi western countries are at one of object of Material Field primary study, it is mainly used in the important military industry field such as space flight, aviation, navigation, meanwhile, high performance 2:17 type SmCo magnet is expected to meet the use of the equipment such as hybrid vehicle and wind-power electricity generation.But up to the present, industrial 2:17 type SmCo sintered magnet magnetic energy product is less than 1/2nd of theoretical magnetic energy product.
For improving the magnetic property of 2:17 type SmCo magnet, researchist both domestic and external has carried out diverse ways trial, from chemical composition and thermal treatment process two aspects of magnet, carry out a large amount of research, produced part Study achievement and patent (United States Patent (USP) NO.4172717, NO.4213803, NO.4221613, NO.4375996).But the preparation of its magnetic still adopts the method for traditional Mechanical Crushing and airflow milling or ball milling, preparation technology's relative complex, and the particle monocrystalline of magnetic can not realize good consistence, thus its magnetic property has been produced to adverse influence.
In the production of rare earth permanent-magnetic material, the effect of hydrogen obtains research extensively and profoundly.As everyone knows, many rare earths. intermetallic compound has the characteristic of inhaling hydrogen, dehydrogenation under differing temps; Hydrogen also has the characteristic that causes its disproportionation to be decomposed.Rare earth. the feature along crystalline substance fracture and transgranular fracture that transition metal alloy produces at suction hydrogen, certain embodiments interalloy itself causes alloy broken, thereby obtains the magnetic of certain particle size, and Here it is utilizes the hydrogen of the broken alloy pig of hydrogen to break (HD) technique.
Due to the special suction hydrogen behavior of 2:17 type SmCo alloy, make HD technique fail to be applied in the suitability for industrialized production of this material always.As: the people's such as A.Kianvash research shows Sm (Co, Cu, Fe, Zr)
8.92commercial alloy, at 30MPa, could effectively be inhaled hydrogen and be broken into the magnetic that mean sizes is 400 μ m under 200 ° of C.The research of Evans etc. shows that 2:17 type SmCo compound is extremely low at 150 ° of following hydrogen-absorption speeds of C, under 150 ° of C and 200 ° of C, P.C.T (pressure, composition, humid test) the detection data of (P=1.3MPa) suction hydrogen show that H/M (being the ratio of hydrogen atom and atoms metal) reaches respectively 0.20 and 0.16, and the hydride composition of formation is Sm
2co
17h
～5, its structure does not change, and remains water chestnut side Th
2zn
17type structure, just lattice parameter changes.
The people's such as the Zheng Liuwei of domestic Iron and Steel Research Geueral Inst, Li Jiankui research also shows that 2:17 type SmCo magnet is under 100 ° of C, 1.0Mpa hydrogen pressure, the most easily there is hydrogen abstraction reaction in magnet, about 10 hours, it is maximum that hydrogen－sucking amount reaches, after 20 hours, magnet efflorescence degree is best.Yet the hydrogen－sucking amount of this technique is still very low, at all cannot be for the preparation of industrialization 2:17 type SmCo magnet.
The technique of 2:17 type SmCo magnetic is realized in this area in the urgent need to developing low-cost, simple and effective preparation, to further improve the magnetic property of 2:17 type SmCo magnet.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide cost low, mild condition, the preparation method of the Rare-Earth Cobalt base alloy powder that equipment requirements is low, the magnetic of preparing by the method can better meet rare earth cobalt-based sintered magnet and the requirement of rare earth cobalt-based bonded magnet to magnetic.
A first aspect of the present invention, a kind of Rare-Earth Cobalt base alloy material is provided, described material comprises following component or substantially following component, consists of: samarium, cobalt, iron, copper, zirconium and at least one other light rare earths, wherein said other light rare earthss comprise: lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, or its combination
Wherein, by the gross weight of alloy material, the total rare earth that comprises samarium and other light rare earthss accounts for 23～27wt% and other light rare earthss account for 2～15wt%, and cobalt accounts for 45～55wt%, and iron accounts for 10～20wt%, and copper accounts for 3～9wt%, and zirconium accounts for 1～3wt%.
In a preference, described alloy material is that two kinds of compounds form complex body, and described two kinds of compounds are: the 1) RCo of crystalloid hexagonal structure
7type compound, in formula, R represents Sm element and other light rare earthss; 2) crystalloid has the RCo of hexagonal structure
5based compound, wherein R comprises Sm element and at least one other light rare earths.
In another preference, described alloy material has RCo
5wrap up mutually RCo
7the microtexture of grain formation born of the same parents' shape, preferably, RCo
7grain size is 5 ~ 50 μ m, RCo
5phase size is 5 ~ 30 μ m
In another preference, other light rare earths segregations in described material are distributed in RCo
5in based compound.
In another preference, at RCo
5content Y1 and the RCo of other light rare earthss in based compound (comprising: lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, or its combination)
7the ratio (Y1/Y2)>=2 of the content Y2 of other light rare earthss in based compound, preferably>=3, more preferably>=4.
In another preference, described alloy material is ingot casting or particle.
A second aspect of the present invention, provides a kind of rare earth cobalt-based alloying pellet, and the material of described particle is the Rare-Earth Cobalt base alloy material described in first aspect present invention, and the particle diameter of described particle is 1-50mm.
In another preference, the particle diameter of described particle is 5～10mm.
In another preference, described particle, by the ingot casting of the Rare-Earth Cobalt base alloy material as described in first aspect present invention, is made by fragmentation.Preferably, crumbling method is Mechanical Crushing.
In another preference, described particle is used as the raw material of the broken technique of hydrogen.
In another preference, described particle is with the method preparation shown in fifth aspect present invention.
A third aspect of the present invention, a kind of Rare-Earth Cobalt base alloy powder is provided, described powder breaks technique with the Rare-Earth Cobalt base alloy material described in first aspect present invention or the rare earth cobalt-based alloying pellet described in second aspect present invention by hydrogen and makes, and the particle diameter of this powder is 50～600 μ m.
In another preference, the particle diameter of described powder is 100～500 μ m.
A fourth aspect of the present invention, provides a kind of preparation method of Rare-Earth Cobalt base alloy powder, and described method comprises the steps:
(i) under hydrogen exists, the rare earth cobalt-based alloying pellet described in second aspect present invention is inhaled to hydrogen and process, obtain the alloying pellet of inhaling after hydrogen;
(ii) alloying pellet after the suction hydrogen of preparation in step (i) is carried out to dehydrogenation processing, thereby obtain Rare-Earth Cobalt base alloy powder.
In another preference, in step (i), temperature is 20～150 ℃.
In another preference, in step (i), hydrogen gas pressure is 200～350KPa.
In another preference, in step (i), the treatment time is 0.5～3 hour.
In another preference, in step (i), at 20～150 ℃, the particle described in second aspect present invention is placed 0.5～3 hour in the hydrogen atmosphere of 200～350KPa.
In another preference, in step (ii), will inhale alloying pellet after hydrogen at the temperature of 20～150 ° of C, vacuum heat-preserving 5～8 hours, rear cool to room temperature, alloy is fractured into the powder of particle diameter 200～500 μ m left and right.
In a fifth aspect of the present invention, a kind of preparation method of rare earth cobalt-based alloying pellet is provided, comprise the following steps:
(1) by samarium, cobalt, iron, copper, zirconium and at least one other light rare earths (preferably, this light rare earths comprises: lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, or its combination) according to mass percent, prepare burden, wherein, by the gross weight of alloy material, the total rare earth that comprises samarium and other light rare earthss accounts for 23～27wt% and other light rare earthss account for 2～15wt%, cobalt accounts for 45～55wt%, iron accounts for 10～20wt%, and copper accounts for 3～9wt%, and zirconium accounts for 1～3wt%;
(2) batching described in step (1) is made to alloy cast ingot; With
(3) alloy cast ingot obtaining in step (2) is broken into particle;
In another preference, the alloy cast ingot described in step (2) adopts induction melting method to make.
In another preference, the crumbling method described in step (3) is Mechanical Crushing.
In another preference, the particle described in step (3) is that size is 1-50mm, more preferably 5～10mm.
A sixth aspect of the present invention, provides a kind of goods, and described goods contain the Rare-Earth Cobalt base alloy powder that third aspect present invention provides, or the Rare-Earth Cobalt base alloy powder being provided by third aspect present invention is made.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction result of the Rare-Earth Cobalt base alloy powder of embodiment 1 and embodiment 2 preparations;
Fig. 2 is the X-ray diffraction result of the 2:17 type samarium Co-based alloy of comparative example's 1 preparation;
Fig. 3 is the micro-structure diagram of the rare earth cobalt base alloy of embodiment 1 preparation;
Fig. 4 is the micro-structure diagram of the rare earth cobalt base alloy of embodiment 2 preparations;
Fig. 5 is the micro-structure diagram of the 2:17 type samarium Co-based alloy of comparative example's 1 preparation.
Fig. 6 is out of phase EDS elemental composition detected result in the rare earth cobalt base alloy of embodiment 1, embodiment 2 and comparative example 1 preparation.
Embodiment
The inventor, by long-term and deep research, is surprised to find that the Co-base alloy material that has added or contained other light rare earthss, and it is very outstanding that it inhales hydrogen effect, is therefore especially suitable for use as the raw material that the broken technique of hydrogen is prepared rare earth permanent-magnetic material powder.On this basis, contriver has completed the present invention.
Concrete, the inventor has developed a kind of novel Rare-Earth Cobalt base alloy material, this alloy material has the component that comprises samarium, cobalt, iron, copper, zirconium and at least one other light rare earths, and rare earth accounts for 23～27wt% (wherein containing other light rare earthss of 2～15%), cobalt accounts for 45～55wt%, iron accounts for 10～20wt%, and copper accounts for 3～9wt%, and zirconium accounts for 1～3wt%.Test result shows, this alloy material has following constitutional features:
1. described in, material is the complex body being comprised of two kinds of compounds, and two kinds of described compounds are: 1) a kind of RCo of crystalloid hexagonal structure
7type compound, wherein R comprises Sm element and at least one other light rare earths; 2) a kind of crystalloid has the RCo of hexagonal structure
5based compound, wherein R at least comprises Sm element and a kind of other light rare earthss.
2. described in, material has RCo
5wrap up mutually RCo
7the microtexture of grain formation born of the same parents' shape, preferably, RCo
7grain size is 5 ~ 50 μ m, RCo
5phase size is 5 ~ 30 μ m.
3. other light rare earths segregations described in material are distributed in RCo
5in based compound.
Owing to having said structure feature, described Rare-Earth Cobalt base alloy material can easily carry out broken (HD) technique of hydrogen under comparatively gentle condition.
Term
As used herein, term " rare earth element " refers to lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and 17 kinds of elements of yttrium (Y).
Term " light rare earths " refers to lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, or its combination.Especially, in this article, " other light rare earthss " refers to not comprise the combination of the light rare earths of samarium element, i.e. lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, or its combination.
Term " substantially by ... form " represent to contain other compositions (as impurity) trace or trace.
Rare-Earth Cobalt base alloy material and preparation thereof
Rare-Earth Cobalt base alloy material of the present invention comprises following component or substantially following component, consists of: samarium, cobalt, iron, copper, zirconium and at least one other light rare earths.
Can be used for rare earth element of the present invention and be not particularly limited, comprise samarium and at least one other light rare earths.
In the present invention, representational light rare earths example comprises (but being not limited to): lanthanum, cerium, praseodymium, neodymium, europium, gadolinium, or its combination.
Preferably, light rare earths comprises praseodymium, neodymium and composition thereof.
The preparation method of Rare-Earth Cobalt base alloy material is as follows:
Samarium, cobalt, iron, copper, zirconium and at least one other light rare earths are prepared burden according to mass percent, its middle-weight rare earths accounted for for 23～27% (wherein containing other light rare earthss of 2～15%), and cobalt accounts for 45～55%, and iron accounts for 10～20%, copper accounts for 3～9%, and zirconium accounts for 1～3%.Above-mentioned batching is mixed and made into alloy.
In the present invention, alloy is prepared by various ordinary methods (preferably induction melting method).
Rare earth cobalt-based alloying pellet and preparation thereof
Rare earth cobalt-based alloying pellet of the present invention comprises following component or substantially following component, consists of: samarium, cobalt, iron, copper, zirconium and at least one other light rare earths, the component concentration of various elements is as above-mentioned Rare-Earth Cobalt base alloy material.
The microstructure characteristic of rare earth cobalt-based alloying pellet of the present invention is as follows: the complex body that 1. it is comprised of two kinds of compounds, these two kinds of compounds are: 1) a kind of RCo of crystalloid hexagonal structure
7type compound, wherein R comprises Sm element and at least one other light rare earths; 2) a kind of crystalloid has the RCo of hexagonal structure
5based compound, wherein R at least comprises Sm element and a kind of other light rare earthss, RCo
5wrap up mutually RCo
7the microtexture of grain formation born of the same parents' shape, preferably, RCo
7grain size is 5 ~ 50 μ m, RCo
5phase size is 5 ~ 30 μ m.2. other light rare earths segregations in this alloy are distributed in RCo
5in based compound.
This heterogeneous microstructure and other light rare earthss are at RCo
5segregation mutually distributes, and makes above-mentioned alloying pellet possess good hydrogen sucking function, thereby can be used for the broken technique of hydrogen, produces the Rare-Earth Cobalt base alloy powder with outstanding magnet magnetic property.
The preparation method of rare earth cobalt-based alloying pellet is as follows:
Step 1, batching: samarium, cobalt, iron, copper, zirconium and at least one other light rare earths are prepared burden according to mass percent, its middle-weight rare earths accounted for for 23～27% (wherein containing other light rare earthss of 2～15%), and cobalt accounts for 45～55%, and iron accounts for 10～20%, copper accounts for 3～9%, and zirconium accounts for 1～3%;
Step 2, adopt induction melting method to make alloy cast ingot batching in step 1;
Step 3, the alloy cast ingot Mechanical Crushing obtaining in step 2 is become to fritter particle, size 5～10mm;
The preparation of Rare-Earth Cobalt base alloy powder
With rare earth cobalt-based alloying pellet of the present invention, by conventional suction hydrogen-dehydrogenation, process (hydrogen breaks technique), just can make the Rare-Earth Cobalt base alloy powder that particle diameter is very little.
The preparation method of Rare-Earth Cobalt base alloy powder is as follows:
Step 1, at 20～150 ℃, the particle obtaining in step 3 is placed 1.5～3 hours in the hydrogen atmosphere of 200～350KPa.
Step 2, by the alloying pellet of completing steps 4 at the temperature of 100～150 ° of C, vacuum heat-preserving 5～8 hours, rear cool to room temperature, alloy is fractured into the powder of particle diameter 200～500 about μ m.
A kind of method steps of preferably preparing Rare-Earth Cobalt base alloy powder by the broken technique of hydrogen of the present invention is as follows:
By samarium, cobalt, iron, copper, zirconium and at least one other light rare earths batching, rare earth accounted for for 23～27% (wherein containing other light rare earthss of 2～15%), and cobalt accounts for 45～55%, and iron accounts for 10～20%, and copper accounts for 3～9%, and zirconium accounts for 1～3%.Described batching made to alloy cast ingot and be broken into fritter particle, at 20～150 ℃, the fritter particle making being placed 1.5～3 hours in the hydrogen atmosphere of 200～350KPa.By the alloying pellet that completes above-mentioned steps at the temperature of 100～150 ° of C, vacuum heat-preserving 5～8 hours, rear cool to room temperature, alloy is fractured into the powder of particle diameter 200～500 about μ m.
Application
Powdered alloy of the present invention is applicable to the bonding and sintered magnet that preparation has magnetic property.
Compared with prior art, major advantage of the present invention comprises:
(1) heterogeneous microstructure of Rare-Earth Cobalt base alloy material provided by the invention, and light rare earths is at RCo
5segregation mutually distributes the hydrogen－sucking amount of alloy is increased considerably, thereby can realize effective suction hydrogen fragmentation of alloy.
(2) Rare-Earth Cobalt base alloy powder preparation method provided by the present invention at ambient temperature, places 1.5～3 hours in the hydrogen atmosphere of 200～350KPa, realizes effective suction hydrogen of alloy; Compare with the suction hydrogen technique of existing 2:17 type SmCo alloy, inhaling hydrogen temperature, hydrogen pressure and all having realized on the suction hydrogen time significantly and having optimized, low for equipment requirements, with low cost, be more suitable for suitability for industrialized production.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Embodiment 1
The preparation of Rare-Earth Cobalt base alloy powder
Raw material: samarium, cobalt, iron, copper, zirconium, praseodymium.
Above-mentioned raw materials is prepared burden with mass percent, alloying constituent: samarium 20.5%, praseodymium 5%, cobalt 50.7%, iron 15.5%, copper 6.0%, zirconium 2.3%.
In induction melting furnace, above-mentioned batching is smelted into respectively to alloy cast ingot, method by Mechanical Crushing is broken into alloy the particle of 5～10mm left and right, particle is put into and inhaled hydrogen stove, by mechanical pump, vacuum tightness in stove is extracted into below 2Pa, at ambient temperature, high-purity hydrogen is filled with in stove, and the pressure that makes hydrogen keeps inhaling for 1.5 hours hydrogen after reaching 270KPa, inhale after hydrogen finishes hydrogen in stove is emitted, by mechanical pump, body of heater vacuum tightness is extracted into the following rear furnace body of 5Pa and starts Heating Dehydrogenation, when temperature rises to 150 ° of C, after keeping temperature to vacuum tightness to be reduced to below 2Pa, stop heating, and body of heater is cooled to room temperature.
Result:
Made the powder of particle diameter 200～500 μ m.
The X-ray diffraction of powdered sample the results are shown in accompanying drawing 1.Result shows, the powder after fragmentation is by RCo substantially
5phase and RCo
7form mutually.
The micro-structure diagram of alloy material is shown in accompanying drawing 3.Result shows, alloy material is mainly that adularescent wraps up the heterogeneous microstructure that black forms mutually mutually, comprehensive XRD and EDS detected result, and known white is RCo mutually
5mutually and black is RCo mutually
7phase.
The EDS elemental composition detected result of alloy material is shown in accompanying drawing 6.Result shows, RCo
5elementary composition by samarium, cobalt, iron, copper, zirconium and praseodymium, RCo
7elementary composition by samarium, cobalt, iron, copper, zirconium and praseodymium; RCo
5the content of mutually middle praseodymium element (4.45%) is apparently higher than RCo
7the content of mutually middle praseodymium element (0.98%), this shows that the praseodymium element adding is that segregation is distributed in RCo
5mutually.
Embodiment 2
The preparation of Rare-Earth Cobalt base alloy powder
Raw material: samarium, cobalt, iron, copper, zirconium, neodymium.
Above-mentioned raw materials is prepared burden with mass percent, alloying constituent: samarium 20.5%, neodymium 5%, cobalt 50.7%, iron 15.5%, copper 6.0%, zirconium 2.3%.
In induction melting furnace, above-mentioned batching is smelted into respectively to alloy cast ingot, method by Mechanical Crushing is broken into alloy the particle of 5～10mm left and right, particle is put into and inhaled hydrogen stove, by mechanical pump, vacuum tightness in stove is extracted into below 2Pa, at ambient temperature, high-purity hydrogen is filled with in stove, and the pressure that makes hydrogen keeps inhaling for 1.5 hours hydrogen after reaching 270KPa, inhale after hydrogen finishes hydrogen in stove is emitted, by mechanical pump, body of heater vacuum tightness is extracted into the following rear furnace body of 5Pa and starts Heating Dehydrogenation, when temperature rises to 150 ° of C, after keeping temperature to vacuum tightness to be reduced to 2Pa, stop heating, and body of heater is cooled to room temperature.
The X-ray diffraction of sample the results are shown in accompanying drawing 1, and micro-structure diagram is shown in accompanying drawing 3, and EDS elemental composition detected result is shown in accompanying drawing 6.
Result:
Made the powder of particle diameter 200～500 μ m.
The X-ray diffraction of powdered sample the results are shown in accompanying drawing 1.Result shows, after dehydrogenation, powdered alloy is substantially by RCo
5phase and RCo
7form mutually.
The micro-structure diagram of alloy material is shown in accompanying drawing 4.Result shows, alloy material is mainly that adularescent wraps up the heterogeneous microstructure that black forms mutually mutually, comprehensive XRD and EDS detected result, and known white is RCo mutually
5mutually and black is RCo mutually
7phase.
The EDS elemental composition detected result of alloy material is shown in accompanying drawing 5.Result shows, RCo
5by samarium, cobalt, iron, copper, zirconium and neodymium element, formed RCo
7by samarium, cobalt, iron, copper, zirconium and neodymium element, formed; RCo
5the content of mutually middle neodymium element (4.28%) is apparently higher than RCo
7the content of mutually middle neodymium element (1.02%), this shows that the neodymium element adding is that segregation is distributed in RCo
5mutually.
Comparative example 1
Raw material: samarium, cobalt, iron, copper, zirconium.
Above-mentioned raw materials is prepared burden with mass percent, alloying constituent: samarium 25.5%, cobalt 50.7%, iron 15.5%, copper 6.0%, zirconium 2.3%.
In induction melting furnace, above-mentioned batching is smelted into alloy cast ingot, method by Mechanical Crushing is broken into alloy the particle of 5～10mm left and right, particle is put into and inhaled hydrogen stove, by mechanical pump, vacuum tightness in stove is extracted into below 2Pa, at ambient temperature, high-purity hydrogen is filled with in stove, and the pressure that makes hydrogen keeps inhaling for 1.5 hours hydrogen after reaching 270KPa, inhale after hydrogen finishes hydrogen in stove is emitted, by mechanical pump, body of heater vacuum tightness is extracted into the following rear furnace body of 5Pa and starts Heating Dehydrogenation, when temperature rises to 150 ° of C, after keeping temperature to vacuum tightness to be reduced to 2Pa, stop heating, and body of heater is cooled to room temperature.
The X-ray diffraction of sample the results are shown in accompanying drawing 2, and micro-structure diagram is shown in accompanying drawing 4, and EDS elemental composition detected result is shown in accompanying drawing 6.
Result:
Alloying pellet size is unchanged.
After dehydrogenation, the X-ray diffraction of sample the results are shown in accompanying drawing 2.Result shows, after dehydrogenation, sample is only containing Sm
2co
17phase.
Alloy microstructure figure is shown in accompanying drawing 5.Result shows, alloy material is mainly the heterogeneous microstructure consisting of black phase and micro-crystal boundary, comprehensive XRD and EDS detected result, and known black is Sm mutually
2co
17phase.
The EDS elemental composition detected result of alloy material is shown in accompanying drawing 6.Result shows, Sm
2co
17samarium, cobalt, iron, copper, zr element, consist of, its quality percentage composition is respectively: samarium 25.02%, cobalt 51.12%, iron 15.86%, copper 5.85%, zirconium 2.15%.
The result of embodiment 1,2 and comparative example 1 alloy fragmentation under identical processing condition is as follows:
After hydrogen in embodiment 1,2 and comparative example 1 is broken, product cut size compares, and known alloy material provided by the invention can carry out the broken technique of hydrogen under comparatively gentle condition, thereby makes Rare-Earth Cobalt base alloy powder.
Embodiment 3
The preparation of Rare-Earth Cobalt base alloy powder
Repeat embodiment 1, difference is, with 2.5% neodymium+2.5% praseodymium, replaces 5% praseodymium.
As a result, made the powder of particle diameter 150～500 μ m.
Embodiment 4
Goods containing Rare-Earth Cobalt base alloy powder
Rare-Earth Cobalt base alloy powder in the present invention, by after evenly mixing with caking agent, can be magnetized and is pressed into block bonded magnet.
Also powdered alloy of the present invention can be prepared into the powdered alloy that particle diameter is more tiny through ball milling or airflow milling technique, then be prepared into the sintered magnet with magnetic property through orientation, die mould, sintering and aging technique.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (12)
1. a Rare-Earth Cobalt base alloy material, it is characterized in that, described material comprises following component or substantially following component, consists of: samarium, cobalt, iron, copper, zirconium and at least one other light rare earths, and wherein said other light rare earthss comprise: lanthanum, cerium, praseodymium, neodymium, europium, or its combination
Wherein, by the gross weight of alloy material, the total rare earth that comprises samarium and other light rare earthss accounts for 23～27wt% and other light rare earthss account for 2～15wt%, cobalt accounts for 45～55wt%, iron accounts for 10～20wt%, and copper accounts for 3～9wt%, and zirconium accounts for 1～3wt%;
And described alloy material is that two kinds of compounds form complex body, and described two kinds of compounds are: the 1) RCo of crystalloid hexagonal structure
7type compound, in formula, R represents Sm element and other light rare earthss; 2) crystalloid has the RCo of hexagonal structure
5based compound, wherein R comprises Sm element and at least one other light rare earths.
2. Rare-Earth Cobalt base alloy material as claimed in claim 1, is characterized in that, at RCo
5content Y1 and the RCo of other light rare earthss in based compound
7the ratio (Y1/Y2)>=2 of the content Y2 of other light rare earthss in based compound, wherein, described light rare earths comprises: lanthanum, cerium, praseodymium, neodymium, europium, or its combination.
3. Rare-Earth Cobalt base alloy material as claimed in claim 1, is characterized in that, described alloy material has RCo
5wrap up mutually RCo
7the microtexture of grain formation born of the same parents' shape, preferably, RCo
7grain size is 5～50 μ m, RCo
5phase size is 5～30 μ m.
4. Rare-Earth Cobalt base alloy material as claimed in claim 1, is characterized in that, other light rare earths segregations in described material are distributed in RCo
5in based compound.
5. the Rare-Earth Cobalt base alloy material as described in any one in claim 1-4, is characterized in that, described alloy material is ingot casting or particle.
6. a rare earth cobalt-based alloying pellet, is characterized in that, the material of described particle is Rare-Earth Cobalt base alloy material claimed in claim 1, and the particle diameter of described particle is 1-50mm.
7. a Rare-Earth Cobalt base alloy powder, is characterized in that, described powder breaks technique with Rare-Earth Cobalt base alloy material claimed in claim 1 or rare earth cobalt-based alloying pellet claimed in claim 6 by hydrogen and makes, and the particle diameter of this powder is 50～600 μ m.
8. Rare-Earth Cobalt base alloy powder as claimed in claim 7, is characterized in that, the particle diameter of described powder is 100～500 μ m.
9. a preparation method for Rare-Earth Cobalt base alloy powder, is characterized in that, described method comprises the steps:
(i) under hydrogen exists, rare earth cobalt-based alloying pellet claimed in claim 6 is inhaled to hydrogen and process, obtain the alloying pellet of inhaling after hydrogen;
(ii) alloying pellet after the suction hydrogen of preparation in step (i) is carried out to dehydrogenation processing, thereby obtain Rare-Earth Cobalt base alloy powder.
10. the preparation method of rare earth cobalt-based alloying pellet as claimed in claim 6, is characterized in that, comprises the following steps:
(1) by samarium, cobalt, iron, copper, zirconium and at least one other light rare earths, according to mass percent, prepare burden, wherein, by the gross weight of alloy material, the total rare earth that comprises samarium and other light rare earthss accounts for 23～27wt% and other light rare earthss account for 2～15wt%, and cobalt accounts for 45～55wt%, and iron accounts for 10～20wt%, copper accounts for 3～9wt%, and zirconium accounts for 1～3wt%;
(2) batching described in step (1) is made to alloy cast ingot; With
(3) alloy cast ingot obtaining in step (2) is broken into particle.
11. preparation methods as claimed in claim 10, is characterized in that, described light rare earths comprises: lanthanum, cerium, praseodymium, neodymium, europium, or its combination.
12. 1 kinds of goods, is characterized in that, described goods contain Rare-Earth Cobalt base alloy powder claimed in claim 7, or are made by Rare-Earth Cobalt base alloy powder claimed in claim 7.
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| CN103537684B (en) * | 2013-11-07 | 2015-04-15 | 湖南航天工业总公司 | Production method for samarium cobalt alloy powder |
| CN108147365A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of Hydrogen Separation and the method for purifying |
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| CN101882494A (en) * | 2010-05-17 | 2010-11-10 | 中国科学院宁波材料技术与工程研究所 | Samarium-cobalt sintered magnet material and preparation method thereof |
| CN102071339A (en) * | 2011-01-24 | 2011-05-25 | 宁波科星材料科技有限公司 | Samarium-cobalt permanent magnet material and preparation method thereof |
| CN102420037A (en) * | 2010-09-24 | 2012-04-18 | 株式会社东芝 | Permanent magnet and motor and generator using the same |
| CN102543340A (en) * | 2011-12-30 | 2012-07-04 | 北矿磁材科技股份有限公司 | High-performance samarium-cobalt magnetic powder and preparation method thereof |
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| CN102420037A (en) * | 2010-09-24 | 2012-04-18 | 株式会社东芝 | Permanent magnet and motor and generator using the same |
| CN102071339A (en) * | 2011-01-24 | 2011-05-25 | 宁波科星材料科技有限公司 | Samarium-cobalt permanent magnet material and preparation method thereof |
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