CN101546642B - Preparation method of nitrogen-containing rare-earth magnetic powder - Google Patents
Preparation method of nitrogen-containing rare-earth magnetic powder Download PDFInfo
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- CN101546642B CN101546642B CN2008101027326A CN200810102732A CN101546642B CN 101546642 B CN101546642 B CN 101546642B CN 2008101027326 A CN2008101027326 A CN 2008101027326A CN 200810102732 A CN200810102732 A CN 200810102732A CN 101546642 B CN101546642 B CN 101546642B
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Abstract
The invention discloses a nitrogen-containing rare-earth magnetic powder prepared by taking ferrocene, cyclopentadienyl lanthanide, metallic iron and rare earth as the main raw materials. The nitrogen-containing rare-earth magnetic powder comprises the following component of R2Fe17-xMxNy, wherein the R is one or more kinds of 17 kinds of rare earth elements including Sc and Y, the M includes transitional elements except for Fe and is one or more kinds of Al, Ga, In, Si, Ge, Sn, Pb, Mg and Ca, the x is equal to 0 to 5, and the y is equal to 1 to 6; and the preparation method comprises the following steps: working procedure of preparation of the R2Fe17-xMx compound powder; working procedure of nitridation; and working procedure of magnetic powder refining and nitriding.
Description
Technical field
The present invention relates to rare earth permanent-magnetic material and preparing technical field thereof, particularly providing a kind of is the nitrogenous rare-earth magnetic and preparation method thereof of primary raw material preparation with ferrocene, luxuriant rare earth, metallic iron and rare earth.
Background technology
In nineteen ninety, Coey and Sun Hong have reported and have utilized gas-solid phase reaction, the N atom has been incorporated into R
2Fe
17In the compound, successfully synthetic R
2Fe
17N
xThe interstitial atom intermetallic compound has caused the very big concern of magnetics circle, and has entered the research climax rapidly.R
2Fe
17Compound is inhaled after the nitrogen, and crystal structure is constant, and unit-cell volume expands, and Curie temperature significantly improves.Sm
2Fe
17N
xCurie temperature be about 740K, compare Nd
2Fe
14About the high 160K of Curie temperature Tc (580K) of B.Sm
2Fe
17N
xRoom temperature anisotropy field H
ABeing 15～16T, approximately is Nd
2Fe
142～3 times of B compound, its J
SValue and theoretical magnetic energy product (BH)
MaxBe respectively 1.54T and 472kJ/m
3, compare Nd
2Fe
14Lower slightly (the Js=1.61T of B; (BH)
Max=509kJ/m
3).
At R
2Fe
17N
xIn the compound, Sm
2Fe
17N
xCompound has superior combination property, with Nd
2Fe
14B compares, and it has higher Curie temperature (exceeding nearly 160 ℃); Extra high magnetocrystalline anisotropy, H
A=11.2MA/m (140kOe) is only second to SmCo
5, be Nd
2Fe
142 times of B; Theoretical magnetic energy product is 472kJ/m
3(59.2MGOe), with Nd
2Fe
14B (509kJ/m
3) about the same; Its non-oxidizability and corrosion resistance all are better than Nd simultaneously
2Fe
14B.
At present both at home and abroad about R
2Fe
17N
xThe patent of magnetic mainly contains the patent CN02159665.4 and the CN03150162.1 of University of Science ﹠ Technology, Beijing's application, wherein patent CN02159665.4 provides a kind of method that adopts reduction-diffusion process to make the Sm-Fe-N permanent magnetic alloy powder, technological process is: raw material are selected and the proportioning → reactant mixing → metallothermic reduction of preliminary treatment → reactant and dehydrating → powder nitriding processing → manufacturing anisotropic bond Sm-Fe-N magnet of diffusion-alloying → product Chemical Decomposition → metal dust, with the granularity of rare earth-iron-boron and selection control alloying element iron powder, reducing agent is metal Ca and CaH
2, in 760-860 ℃ of lower temperature range, carry out reduction diffusion reaction, generate Sm-Fe alloy and accessory substance, through Sm-Fe alloyed powder after the Chemical Decomposition directly in nitrogenous gas nitriding obtain the Sm-Fe-N magnetic alloy powder; Patent CN03150162.1 provides a kind of method with prepared by mechanical alloy SmFeN permanent magnetic material, and pure Sm powder, Fe powder are pressed Sm
2Fe
17Composition is also added 1～30% Sm powder proportioning; be that final mass percentage is 25～30%Sm, 70～75%Fe; after the preliminary mixing of material powder, ball milling is 1～20 hour in high energy ball mill, and ball-milling medium is that every ball milling was shut down 5～20 minutes in 5～30 minutes in the nitrogen substance ball milling.
Japan Daido Steel Co., Ltd is at Chinese patents CN01123172.6, disclose a kind of isotropism SmFeN powder magnet material of producing resin-bonded magnet at the patent US2004144450 of U. S. application with at patent JP2004063666, JP2003173907, the JP2002057017 of Japanese publication, composition is Sm
xFe
100-x-vN
v, Sm
xFe
100-x-y-vM
1 yN
v, Sm
xFe
100-x-z-vM
2 zN
vM wherein
1Be selected from least a among Hf and the Zr; M
2Be selected from least a among Si, Nb, Ti, Ga, Al, Ta and the C; 7≤x≤12,0.1≤y≤1.5,0.1≤z≤1.0,0.5≤v≤20; Crystal structure is TbCu
7Type, the thickness of thin slice are 10～40 μ m, by the melt spinning molten alloy and with the alloyed powder of such gained in nitrogenous gas directly nitriding prepare magnet powder.
More than be that primary raw material is prepared the R-Fe powder generally about the patent of R-Fe-N magnetic with R and Fe, again directly in nitrogenous gas nitriding form the R-Fe-N magnetic, but there is the uneven phenomenon of nitrogen content continuous distribution in the R-Fe alloyed powder when beginning nitriding, needs to prolong nitriding time and impels magnetic nitriding homogenizing.And long-time nitriding meeting causes that the R-Fe-N magnetic is decomposed into RN and α-Fe, thereby causes R-Fe-N magnetic magnetic property to reduce.
Therefore research and develop new preparation technology, prepare the R of high nitrogen content, compact tissue, good magnetic property
2Fe
17N
xMagnetic becomes the focus of research.
The present invention considers the problems referred to above exactly, its objective is provide a kind of nitrogen content high and evenly, the R of compact tissue, good magnetic property
2Fe
17N
xMagnetic and preparation technology thereof.
Summary of the invention
Advantage of the present invention is:
The invention provides a kind of is the preparation method of the nitrogenous rare-earth magnetic of primary raw material preparation with ferrocene, luxuriant rare earth, metallic iron and rare earth.Add the organic compound that contains ferrocene and luxuriant rare earth and prepare nitrogenous rare-earth magnetic, can effectively strengthen the decomposition of nitriding medium, improve nitrogen content, quickening nitrogen-atoms is absorbed by alloy powder, increase the nitrogen diffusion velocity, nitrogen forms around rare earth atom easily to be assembled, and accumulates under certain conditions that high nitrogen concentration around the rare earth is easier to spread to internal transitions, increase the diffusion velocity of nitrogen, increase infiltration rate.Experiment showed, that interpolation contains ferrocene and luxuriant rare earth organic compounds prepares nitrogenous rare-earth magnetic, the fast 15-25% than not adding has improved labor productivity.
Nitrogenous rare-earth magnetic provided by the invention, because nitriding time is short, nitriding temperature is low, is difficult for being decomposed into RN and α-Fe, tissue, stable performance.
Summary of the invention is as follows:
The invention provides a kind of nitrogenous rare-earth magnetic, is the primary raw material preparation with ferrocene, luxuriant rare earth, metallic iron and rare earth, and its composition is R
2Fe
17-xM
xN
y, wherein R representative comprises one or more in 16 kinds of rare earth elements of Sc, Y except that Pm, M is one or more in the transition element, Al, Ga, In, Si, Ge, Sn, Pb, Mg, Ca except that Fe, x=0～5, y=1～6.
The invention provides a kind of nitrogenous rare-earth magnetic, is the primary raw material preparation with ferrocene, luxuriant Sm or luxuriant Nd, metallic iron, rare earth metal, and its composition is R
2Fe
17-xM
xN
yWherein R represents one or more in the mixture of mixture, Nd and other rare earths of Sm, Nd, Sm and other rare earths, M is among transition element except that Fe, Al, Ga, In, Si, Ge, Sn, Pb, Mg, the Ca one or more, x=0～5, y=1～6.
A kind of method for preparing nitrogenous rare-earth magnetic provided by the invention may further comprise the steps:
A) powder process operation
Adopt casting sheet method, quick quenching technique, ball-milling method, mechanical alloying method, hydrogenation discrimination method or reduction-diffusion process prepare RFeM principal component alloyed powder;
B) nitrogenize operation
Add the organic compound that contains ferrocene, luxuriant rare earth in above-mentioned RFeM principal component alloy powder, organic compound content is 1wt%-20wt%, and wherein the content of ferrocene and luxuriant rare earth is 2wt%-100wt% in the organic compound; And feeding N
2, NH
3, NH
3-H
2Mist, N
2-NH
3Mist, N
2-H
2At least a in the mist; The described organic compound of ferrocene, luxuriant rare earth that contains is except that ferrocene that contains 20wt%-90wt% and luxuriant rare earth, also contain urea and potassium ferrocyanide, perhaps except that ferrocene that contains 20wt%-80wt% and luxuriant rare earth, also contain alcohols, alcohols comprises and at least a in methyl alcohol, ethanol, butanols, the propyl alcohol perhaps except that ferrocene that contains 30wt%-70wt% and luxuriant rare earth, also contains the isobutyric acid ammonium, isomeric acid, in the naphthenic acid rare earth one or more;
C) refinement nitrogenize magnetic operation
Rare earth permanent magnet powder after the pulverizing nitrogenize, the particle medium particle diameter is 0.3-20 μ m.
Fig. 1 is Sm
2Fe
17X-ray diffractogram before and after the nitriding.
Description of drawings
With example nitrogenous rare-earth magnetic of the present invention and preparation method thereof is further described below, will helps to understand better the characteristics and the advantage of nitrogenous rare-earth magnetic of the present invention and preparation method thereof.Protection range of the present invention is not limited by the following examples, and protection scope of the present invention is determined by claims.
Embodiment
Embodiment 1
The Sm-FeCo alloy that melting is obtained melts under inert gas shielding, and the pore through container bottom is ejected on the water-cooled copper roller outer rim of high speed rotating under pressure, cools off fast and forms amorphous state or crystallite strip.Be broken into the powder that granularity is 20-40 μ m after the Sm-FeCo amorphous state that obtains or crystallite strip homogenizing handled.Add the organic compound of 20wt%, wherein organic compound ingredient be 20wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 49) and surplus be isobutanol, propyl alcohol and isopropyl alcohol (isobutanol: propyl alcohol: isopropyl alcohol=1: 1: 1), be evacuated to less than 3 * 10
-3Feed N behind the Pa
2To 1atm, be incubated 1 hour obtaining composition down at 450 ℃ is Sm
2Fe
15.2Co
1.8N
1.0Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 0.3-10 μ m to ball milling again.The magnetic property and the nitrogen content of magnetic are as shown in table 1.
Comparative example 1
But composition is compared with embodiment 1 identical performance and the embodiment 1 that does not add the nitrogenous rare-earth magnetic of the organic compound that contains ferrocene, luxuriant rare earth with preparation technology, and the result is as shown in table 1.
With raw material melting in crucible, then alloy liquid is cast on the water cooled rolls of rotation by the mode of casting groove with planar flows, form the alloy casting piece of Sm-FeAlCrGa.The Sm-FeAlCrGa alloy casting piece that obtains is broken into the powder that granularity is 30-40 μ m.Add the organic compound of 1wt%, wherein organic compound ingredient be 80wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 4) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Feed NH behind the Pa
3-H
2Mist is to 1atm, and be incubated 1 hour obtaining composition down at 450 ℃ is Sm
2Fe
16(Al
0.03Cr
0.03Ga
0.04) N
2.8Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again.The magnetic property and the nitrogen content of magnetic are as shown in table 1.
Comparative example 2
But composition is compared with embodiment 2 identical performance and the embodiment 2 that do not add the nitrogenous rare-earth magnetic of the organic compound that contains ferrocene, luxuriant rare earth with preparation technology, and the result is as shown in table 1.
Embodiment 3
With industrial simple metal Sm, Fe, Zr, Nb makes raw material, smelts under argon shield and is cast into the Sm-FeZrNb alloy cast ingot, coarse crushing to 30 μ m behind the Sm-FeZrNb alloy cast ingot homogenizing annealing with vaccum sensitive stove.Add the organic compound of 5wt%, wherein organic compound ingredient be 70wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 9) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 1.5atm, and be incubated 1 hour obtaining composition down at 450 ℃ is Sm
2Fe
15.5(Zr
1.0Nb
0.5) N
2.9Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 4
Coarse crushing behind the Sm-FeVSiMn alloy homogenizing annealing that melting is obtained is carried out HDDR again and is handled in the HDDR Hydrotreat Stove, to become granularity be the powder of 20-35 μ m to ball milling again.Add the organic compound of 10wt%, wherein organic compound ingredient be 58wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 10) and surplus be methyl alcohol and ethanol (methyl alcohol: ethanol=1: 1), be evacuated to less than 3 * 10
-3Fill N behind the Pa
2To 8atm, be incubated 2 hours obtaining composition down at 450 ℃ is Sm
2Fe
15.8(V
0.04Si
0.04Mn
0.04) N
2.1Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 5
With Fe powder, Sm
2O
3Powder, Ca grain and anhydrous CaCl
2Prepare by reduction diffusion reaction after mixing briquetting, carry out the water mill cleaning again and separate the also dry Sm-Fe powder that granularity is 30-40 μ m that obtains.Add the organic compound of 15wt%, wherein organic compound ingredient be 30wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 15) and surplus be methyl alcohol and butanols (methyl alcohol: butanols=5: 1), be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3To 5atm, be incubated 3 hours obtaining composition down at 450 ℃ is Sm
2Fe
17N
3.5Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 6
With industrial simple metal Sm, Fe, Cu, Ni, Zn makes raw material, smelts under argon shield and is cast into the Sm-FeCuNiZn alloy cast ingot, coarse crushing to 30 μ m behind the Sm-FeCuNiZn alloy cast ingot homogenizing annealing with vaccum sensitive stove.Add the organic compound of 18wt%, wherein organic compound ingredient be 20wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 18) and surplus be urea and potassium ferrocyanide (urea: potassium ferrocyanide=5: 1), be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 10atm, and be incubated 5 hours obtaining composition down at 450 ℃ is Sm
2Fe
16.1(Cu
0.03Ni
0.03Zn
0.03) N
5.6Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 7
With industrial simple metal Sm, Pr, Fe, Cu, Ni, Zn makes raw material, smelts under argon shield and is cast into the SmPr-FeCuNiZn alloy cast ingot, coarse crushing to 30 μ m behind the SmPr-FeCuNiZn alloy cast ingot homogenizing annealing with vaccum sensitive stove.Add the organic compound of 3wt%, wherein organic compound ingredient be 90wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 25) and surplus be urea and potassium ferrocyanide (urea: potassium ferrocyanide=5: 1), be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 2atm, and be incubated 2 hours obtaining composition down at 450 ℃ is Sm
1.4Pr
0.6Fe
16.1(Cu
0.03Ni
0.03Zn
0.03) N
3.0Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-16 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 8
With granularity is 50-70 μ m; purity is that 99.9% Fe powder and purity are 99.9%; granularity is that the Sm powder of 1-3 μ m mixes; pack in the planetary type ball-milling; under argon shield more than the diffusion annealing 40h; obtain amorphous Sm-Fe stratiform hybrid particles, diffusion annealing under 700 ℃ of argon shields then, forming granularity is the nanocrystalline Sm-Fe powder of 40 μ m.Add the organic compound of 6wt%, wherein the organic compound adding ingredient be 70wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 33) and surplus be urea and potassium ferrocyanide (urea: potassium ferrocyanide=5: 1), be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 10atm, and be incubated 5 hours obtaining composition down at 450 ℃ is Sm
2Fe
17N
6.0Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 9
The Sm that melting is obtained
2Fe
16.3(V
0.04Mg
0.01Mo
0.01Cd
0.01) coarse crushing behind the alloy homogenizing annealing, in the HDDR Hydrotreat Stove, carry out HDDR again and handle, to become granularity be the powder of 35-40 μ m to ball milling again.Add the organic compound of 16wt%, wherein organic compound ingredient be 50wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 16) and surplus be urea and potassium ferrocyanide (urea: potassium ferrocyanide=5: 1), be evacuated to less than 3 * 10
-3Fill N behind the Pa
2To 1atm, be incubated 2 hours obtaining composition down at 450 ℃ is Sm
2Fe
16.3(V
0.04Mg
0.01Mo
0.01Cd
0.01) N
1.5Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 15-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 10
With confected materials melting in crucible, then alloy liquid is cast on the water cooled rolls of rotation by the mode of casting groove with planar flows, form the alloy casting piece of Sm-FeAlInGeSn.The Sm-FeAlInGeSn alloy casting piece that obtains is broken into the powder that granularity is 30-38 μ m.Add the organic compound of 2wt%, wherein organic compound ingredient is the cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 4), be evacuated to less than 3 * 10 of 100wt%
-3Fill NH behind the Pa
3-H
2Mist is to 1atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Sm
2Fe
16.6(Al
0.01In
0.01Ge
0.01Sn
0.01) N
4.4Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-15 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 11
The Sm-FeCoPbCa alloy that melting is obtained melts under inert gas shielding, and the pore through container bottom is ejected on the water-cooled copper roller outer rim of high speed rotating under pressure, cools off fast and forms amorphous state or crystallite strip.To be broken into the powder that granularity is 22-30 μ m after the Sm-FeCoPbCa homogenizing processing that obtain.Add the organic compound of 2wt%, wherein organic compound ingredient be 70wt% cyclopentadinyl compound (ferrocene: luxuriant Sm=1: 45) and surplus be isobutyric acid ammonium and isomeric acid (isobutyric acid ammonium: isomeric acid=5: 1), be evacuated to less than 3 * 10
-3Fill N behind the Pa
2-H
2Mist is to 1atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Sm
2Fe
16.7Co
0.1Pb
0.005Ca
0.005N
2.5Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 5-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 12
With confected materials melting in crucible, then alloy liquid is cast on the water cooled rolls of rotation by the mode of casting groove with planar flows, form the alloy casting piece of SmTbDy-Fe.The SmTbDy-Fe alloy casting piece that obtains is broken into the powder that granularity is 30-40 μ m.Add the organic compound of 12wt%, wherein organic compound ingredient be 35wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 48) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 1atm, and be incubated 1 hour obtaining composition down at 450 ℃ is Sm
19.8Tb
0.01Dy
0.01Fe
17N
2.8Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-20 μ m to ball milling again.The magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 13
The SmGdLaCe-FeCo alloy that melting is obtained melts under inert gas shielding, and the pore through container bottom is ejected on the water-cooled copper roller outer rim of high speed rotating under pressure, cools off fast and forms amorphous state or crystallite strip.To be broken into the powder that granularity is 22-30 μ m after the SmGdLaCe-FeCo homogenizing processing that obtain.Add the organic compound of 19wt%, wherein organic compound ingredient be 30wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 29) and surplus be carboxylic acid rare earth and naphthenic acid rare earth (carboxylic acid rare earth: naphthenic acid rare earth=5: 1), be evacuated to less than 3 * 10
-3Fill N behind the Pa
2-H
2Mist is to 1atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Sm
1.9Gd
0.05La
0.025Ce
0.025Fe
16.7Co
0.3N
2.6Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 5-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 14
With confected materials melting in crucible, then alloy liquid is cast on the water cooled rolls of rotation by the mode of casting groove with planar flows, form the alloy casting piece of Nd-Fe.The Nd-Fe alloy casting piece that obtains is broken into the powder that granularity is 30-38 μ m.Add the organic compound of 14wt%, wherein the organic compound adding ingredient be 42wt% cyclopentadinyl compound (ferrocene: luxuriant Nd=1: 19) and surplus be carboxylic acid rare earth and naphthenic acid rare earth (carboxylic acid rare earth: naphthenic acid rare earth=5: 1), be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 2atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Nd
2Fe
17N
4.0Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-15 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 15
With confected materials melting in crucible, then alloy liquid is cast on the water cooled rolls of rotation by the mode of casting groove with planar flows, form the alloy casting piece of SmErTmYbLuScY-Fe.The SmErTmYbLuScY-Fe alloy casting piece that obtains is broken into the powder that granularity is 30-38 μ m.Add the organic compound of 20wt%, wherein organic compound ingredient be 2wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 41) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 1atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Sm
1.8Er
0.05Tm
0.05Yb
0.03Lu
0.03Sc
0.02Y
0.02Fe
17N
3.8Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-15 μ m to ball milling again, goes up the magnetic property of test magnetic at VSM (vibrating specimen magnetometer), the result is as shown in table 1.
Embodiment 16
With industrial simple metal Sm, Ho, Fe, Zn makes raw material, smelts under argon shield and is cast into the SmHo-FeZn alloy cast ingot, coarse crushing to 30 μ m behind the SmHo-FeZn alloy cast ingot homogenizing annealing with vaccum sensitive stove.Add the organic compound of 10wt%, wherein the organic compound adding ingredient be 46wt% cyclopentadinyl compound (ferrocene: luxuriant rare earth=1: 40) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Fill NH behind the Pa
3-H
2Mist is to 1atm, and be incubated 2 hours obtaining composition down at 450 ℃ is Sm
1.4Ho
0.6Fe
16.7Zn
0.03N
2.9Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 10-16 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
Embodiment 17
The Nd-FeCo alloy that melting is obtained melts under inert gas shielding, and the pore through container bottom is ejected on the water-cooled copper roller outer rim of high speed rotating under pressure, cools off fast and forms amorphous state or crystallite strip.To be broken into the powder that granularity is 22-30 μ m after the Nd-FeCo homogenizing processing that obtain.Add the organic compound of 11wt%, wherein the organic compound adding ingredient be 44wt% cyclopentadinyl compound (ferrocene: luxuriant Nd=1: 4) and surplus be methyl alcohol, be evacuated to less than 3 * 10
-3Fill N behind the Pa
2-H
2Mist is to 2atm, and be incubated 3 hours obtaining composition down at 450 ℃ is Nd
2Fe
16.7Co
0.3N
2.9Nitrogenous rare-earth magnetic, to become granularity be the magnetic of 5-20 μ m to ball milling again, the magnetic property and the nitrogen content of magnetic are as shown in table 1.
The nitrogen content of the nitrogenous rare-earth magnetic of table 1 and magnetic property
| Embodiment 7 | 1.4 | 520 | 292 | 3.0 |
| Embodiment 8 | 0.78 | 480 | 90 | 6.0 |
| Embodiment 9 | 1.1 | 391.2 | 220 | 1.5 |
| Embodiment 10 | 0.9 | 382.4 | 229 | 4.4 |
| Embodiment 11 | 1.0 | 336 | 231 | 2.5 |
| Embodiment 12 | 1.1 | 532 | 244 | 2.8 |
| Embodiment 13 | 1.0 | 333 | 235 | 2.6 |
| Embodiment 14 | 0.8 | 350 | 220 | 4.0 |
| Embodiment 15 | 0.9 | 366 | 220 | 3.8 |
| Embodiment 16 | 1.4 | 530 | 280 | 2.9 |
| Embodiment 17 | 1.0 | 320 | 248 | 2.9 |
Claims (7)
1. one kind is R with ferrocene, luxuriant rare earth, metallic iron and rare earth for the primary raw material prepared composition
2Fe
17-xM
xN
yThe method of nitrogenous rare earth permanent magnet powder, wherein R represents one or more in 16 kinds of rare earth elements that comprise Sc, Y except that Pm, M is among transition element except that Fe, Al, Ga, In, Si, Ge, Sn, Pb, Mg, the Ca one or more, x=0～5, y=1～6, it is characterized in that, may further comprise the steps:
A) powder process operation
Adopt casting sheet method, quick quenching technique, ball-milling method, mechanical alloying method, hydrogenation discrimination method or reduction-diffusion process prepare RFeM principal component alloyed powder;
B) nitrogenize operation
Add the organic compound that contains ferrocene, luxuriant rare earth in above-mentioned RFeM principal component alloy powder, organic compound content is 1wt%-20wt%, and wherein the content of ferrocene and luxuriant rare earth is 2wt%-100wt% in the organic compound; And feeding N
2, NH
3, NH
3-H
2Mist, N
2-NH
3Mist, N
2-H
2At least a in the mist;
C) refinement nitrogenize magnetic operation
Rare earth permanent magnet powder after the pulverizing nitrogenize, the particle medium particle diameter is 0.3-20 μ m.
2. the preparation method of nitrogenous rare earth permanent magnet powder according to claim 1 is characterized in that, the organic compound described in the step b also contains urea and potassium ferrocyanide except that containing ferrocene, luxuriant rare earth.
3. according to the preparation method of the nitrogenous rare earth permanent magnet powder described in the claim 2, it is characterized in that the content of ferrocene and luxuriant rare earth is 20wt%-90wt% in the described organic compound.
4. the preparation method of nitrogenous rare earth permanent magnet powder according to claim 1 is characterized in that, the organic compound described in the step b also contains alcohols except that containing ferrocene, luxuriant rare earth, and alcohols comprises at least a in methyl alcohol, ethanol, butanols and the propyl alcohol.
5. according to the preparation method of the nitrogenous rare earth permanent magnet powder described in the claim 4, it is characterized in that the content of ferrocene and luxuriant rare earth is 20wt%-80wt% in the described organic compound.
6. the preparation method of nitrogenous rare earth permanent magnet powder according to claim 1 is characterized in that, the organic compound described in the step b also contains the isobutyric acid ammonium except that containing ferrocene, luxuriant rare earth, isomeric acid, in the naphthenic acid rare earth one or more.
7. according to the preparation method of the nitrogenous rare earth permanent magnet powder described in the claim 6, it is characterized in that the content of ferrocene and luxuriant rare earth is 30wt%-70wt% in the described organic compound.
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| CN102768891B (en) * | 2011-05-06 | 2015-11-04 | 有研稀土新材料股份有限公司 | The product of the nitrogenous magnetic preparation technology of rare earth and equipment and preparation |
| CN102938283A (en) * | 2012-11-14 | 2013-02-20 | 天津邦特磁性材料有限公司 | High-magnetism high-mechanical-strength bonded neodymium iron boron (NdFeB) permanent magnet and preparation method thereof |
| CN103785847A (en) * | 2014-02-26 | 2014-05-14 | 江门市新会区宇宏科技有限责任公司 | Method for preparing 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through reduction diffusion method |
| CN109982791B (en) * | 2016-11-28 | 2022-02-22 | 国立大学法人东北大学 | Rare earth iron-nitrogen-based magnetic powder and method for producing same |
| JP7095310B2 (en) * | 2018-02-28 | 2022-07-05 | 大同特殊鋼株式会社 | Sm-Fe-N magnet material and Sm-Fe-N bond magnet |
| CN108777204B (en) * | 2018-05-08 | 2020-05-22 | 华南理工大学 | Preparation method of samarium-iron-nitrogen permanent magnet powder |
| KR102357085B1 (en) * | 2018-08-10 | 2022-01-28 | 주식회사 엘지화학 | Magnetic powder and manufacturing method of magnetic powder |
| CN109273182B (en) * | 2018-10-19 | 2020-06-16 | 广东省稀有金属研究所 | Single crystal magnetic powder and preparation method and application thereof |
| CN109273183B (en) * | 2018-10-19 | 2020-06-16 | 广东省稀有金属研究所 | Corrosion-resistant monocrystalline magnetic powder and preparation method and application thereof |
| CN111014714B (en) * | 2019-12-31 | 2022-10-04 | 浙江工业大学 | Preparation method of samarium-iron alloy powder integrating spray pyrolysis and iron oxide reduction in one step |
| CN111180160A (en) * | 2020-01-17 | 2020-05-19 | 杭州史宾纳科技有限公司 | Process for reducing and diffusing isotropic samarium-iron-nitrogen powder and magnet |
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