CN1038281C

CN1038281C - Iron-based rare-earth permanent magnet containing niobium and its producing method

Info

Publication number: CN1038281C
Application number: CN92105409A
Authority: CN
Inventors: 饶晓雷; 胡伯平; 许建民; 刘贵川; 王亦忠; 高景兰; 宋琪; 刘蕾; 金国顺; 吴宗林; 刘英烈; 张澄覆; 尹林; 李华
Original assignee: Sanhuan New Material High Tech
Current assignee: Beijing Zhong Ke San Huan High Tech Co Ltd
Priority date: 1992-07-10
Filing date: 1992-07-10
Publication date: 1998-05-06
Anticipated expiration: 2007-07-10
Also published as: CN1082758A

Abstract

The present invention provides a method for preparing an iron-base rare-earth permanent magnet containing niobium (Nb), which comprises the following steps that metal containing Nb, vanadium, molybdenum, etc. is introduced to iron-base alloy so as to obtain magnetic powder with high saturation magnetization and high coercivity under certain condition, and then, the magnetic powder is rapidly shaped so as to prepare the iron-base rare-earth permanent magnet containing Nb. A proper amount of Nb is added to alloy in the present invention, and proper heat treatment is adopted to regulate the metallographic structure of the alloy, so after the cementation of X, the alloy can have high coercivity under the condition of retaining high remanence without the accomplishment of secondary crushing or with the accomplishment of proper secondary crushing only, and a square degree is improved. Therefore, the magnet has higher magnetic energy product.

Description

A kind of ferrous rare earth permanent magnet and manufacture method thereof that contains niobium

The present invention relates to a kind of powdered metallurgical material and technology field thereof, particularly utilize the explosive sintering moulding to make a kind of the have method that contains the ferro-niobium based permanent magnetic material of high saturation and magnetic intensity and high energy product and the R that the method institute directly prepares _α(Fe _L-x-yNb _xM _y) _{100-alpha-beta-β}X _βThe technical field of permanent magnetic material.

Permanent magnetic material is a kind of epochmaking electronics, electrical material, is widely used in industry, and science and technology is among aerospace and the civilian installation.

Since generation between nineteen eighty-three NdFeB permanent magnet, people have produced great interest to studying and seeking iron-based rare-earth permanent magnetic material of new generation, and found that in succession some promise to be the compound of permanent magnetic material, but also be difficult to for various reasons these compounds are made practical magnet.

Nineteen ninety, the European has found with rare-earth Sm and Fe to be the Th that has of main component ₂Zn ₁₇The R of structure ₂M phase (a kind of rare earth one transition intermetallic compounds) can produce the R with good intrinsic magnetic characteristic by the low temperature nitriding ₂M ₁₇The Ny compound, this compound has possessed the basis that can be made into rare-earth permanent magnet fully.This finds to have caused very soon the attention of world technology circle and industrial quarters.The Chinese science man finds ThMn again subsequently ₁₂1: 12 phase NdFe of structure ₁₁The nitride of Ti also has similar feature, and since rare earth element based on Nd, the relative amount of Fe is higher, therefore, compares Th ₂Zn ₁₇The Sm of structure ₂Fe ₁₇N _yHave more attraction.In recent years, many researchers are making great efforts this compound of research, and wish and can make magnet to it, can make comparatively desirable magnet to this compound but up to the present also have no talent, and its main cause is as follows:

R ₂M ₁₇Ny phase or NdFe ₁₁TiN _yBe a kind of metastable structure, can not smelt directly acquisition by raw material, can only be at a certain temperature by solid-gas-phase reaction, to R ₂M ₁₇Or NdFe ₁₇Nitriding obtains in the Ti, and above-mentioned alloy need wear into very thin powder (400 μ m), so that nitrogen can diffuse in the alloy lattice equably, obtains having the uniform R of same structure ₂M ₁₇N _yOr NdFe ₁₁TiNy.Simultaneously also just because R ₂M ₁₇Ny or NdFe ₁₁The metastable characteristic of TiNy, they just almost completely resolve into α-Fe and rare earth nitride at 700 ℃, and no longer can revert to original nitride phase, and traditional powder metallurgy process prepare magnet generally all be by behind the powder pressing forming high temperature (＞1000 ℃) down sintering form, obviously can not be suitable at this.This is to make bulk high density R ₂M ₁₇Ny or NdFe ₁₇The major obstacle that the TiNy permanent magnet is run into.

In addition, for obtaining higher HCJ, the alloy powder after the nitrogenize must further be ground to 1-5 μ m under non-oxidizing atmosphere, and this process will obviously reduce its saturation magnetization 4 π Ms.More seriously the demagnetization characteristic of nitrogenize powder is very poor, its squareness (outfield H of 90% 4 π Mr correspondences ₁With HCJ iH _cRatio H _k/ iH _c) be less than 0.5, and the squareness of General N dFeB is greater than 0.9.These two factors have seriously reduced R ₂M ₁₇N _yAnd NdFe ₁₁TiN _yThe magnetic energy product that should have.

People pass through at Sm at present ₂Fe ₁₇N _yOr NdFe ₁₁TiN _yThe middle element that strong affinity is arranged with N that adds, as Ti, Cr, V, Al, MO etc. improve the structural stability of alloy.But in this alloy, people still are used in and add low-melting-point metal (as Sn, Zn etc.) in the alloy, with the low-melting-point metal that melts the nitrogen powder are glued and make magnet, perhaps mix organic bond in the nitrogenize powder, as epoxy resin, make bonded permanent magnet.But these methods can't produce high performance magnet, and reason is the branch that has added non magnetic component, have reduced effective filling rate (percent by volume of magnet material) of magnet, and magnetic reduces.For example: Japanese patent application document JP 4-177806A.

The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, thereby provide a kind of in ferrous alloy, the introduction to contain metals such as niobium, vanadium, molybdenum, obtain high full the close magnetization and high-coercive force magnetic under certain condition, contain the R α (Fe of this method of ferro-niobium base rear earth permanent magnet and the preparation of employing the method again through the rapid shaping preparation _1-x-yNb _xMy) _{The 100-alpha-beta}X _βPermanent magnet.

The object of the present invention is achieved like this:

First, in above-mentioned ferrous alloy, introduce such as niobium, vanadium, the such element of molybdenum, by to containing the rare earth of niobium, molybdenum, vanadium---ferrous alloy carries out suitable heat treatment, form the precipitation molecule of nanometer scale at its intragranular, form the intracrystalline pinning mechanism of neticdomain wall, can guarantee on the one hand in the powder of larger particles degree, to obtain considerable HCJ, to improve the saturation magnetization of final manufactured goods; Can significantly improve the squareness of this material on the other hand, and then improve its magnetic energy product.

Second, set up a kind of any bonding agent that do not add, finish the high pressure-temperature Fast Sintering of nitrogenize powder in the time of decomposing much shorter than above-mentioned alloy nitride, to make filling rate almost 100%, magnet density reaches the technology of the magnet of its solid density more than 95%; And because so intergranular magnetic interaction of magnet internal magnetization of preparation further improves its squareness.

The 3rd, replace most of Co in traditional Sm-Co magnet by using Fe, and even, reduce the raw-material cost of magnet widely with replacement Sm such as Nd, Pr.

The present invention takes following several respects measure to realize purpose of the present invention:

One is by the adjustment of component:

Magnetic material among the present invention is based on the transiting group metal elements of Fe and based on the rare earth element of Sm or Nd, mixes Nb and makes alloy, infiltrates the following compound of X composition general formula then in this alloy: R α (Fe _1-x-yNb _xMy) _{The 100-alpha-beta}X _β

Wherein: R is single S m or Nd, Sm or Nd and more than one following element: Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, Pa, U, Np, Pu, the mixture of Y;

M is one or more following element: Co, Al, and Cu, Zr, Si, Ca, Sn, Ni,

In, Bi, Zn, Ti, Mo, W, V, Ge, Re, Hf, S, etc.

X is Elements C or C and H;

Each component content of atomic ratio is as follows:

α＝6-25

β＝5-30

X is 0.001-0.20

Y is 0-0.4; Its surplus is a unavoidable impurities

It is two by adopting five measures to achieve the goal on the manufacturing process:

(1) melting:

Melting is exactly the foundry alloy that will obtain the uniform as far as possible above-mentioned composition of composition

Fe and at least a based on Sm or Nd rare-earth element R and Nb by required composition proportion weighing; be placed under the vacuum that is higher than 1Pa or under 0.5-2 atmospheric inert gas atmosphere (as: Ar) protection and pass through induction heating; (temperature is: 1500-2300 ℃; time is: 10-90 minute) or under 0.5-2 atmospheric inert atmosphere electric arc melting; (temperature is: 1500-2300 ℃; time is: 2-10 minute), make composition foundry alloy as far as possible uniformly.

Wherein R is the 6-25 atomic percent, and Fe is the 75-95 atomic percent, and Nb accounts for the 0.1-20 atomic percent of total iron-holder.

Co or at least a M can replace part Fe equally as required and join in the foundry alloy when melting, but the addition of Co and M is limited to respectively in the following atomic percent scope:

Co 0-50 Al 0-20 Si 0-10 Ca 0-15

Cu 0-15 Zr 0-10 Ni 0-10 S 0-5

Hf 0-10 Sb 0-7 Ge 0-5 W 0-7

Mo 0-7 Ti 0-10 V 0-10 Sn 0-10

In 0-5 Bi 0-5 Zn 0-10

The magnetic that exceeds these composition range magnets will descend.

General all in the foundry alloy that obtains after the melting may there be certain component segregation, such as α-Fe, SmFe ₃This component segregation can cause the final magnet performance decrease, therefore to seek out the magnet of even more ideal performance, can adopt alloy pig is carried out homogenizing heat treatment, heat treatment temperature can be chosen between 950-1400 ℃, and heat treatment time can be chosen between 2 hours to 60 days.

Foundry alloy can obtain by liquid phase quick cooling method (revolving the method for quenching as liquid phase) or mechanical alloying method equally.

(2) Low Temperature Heat Treatment of micro-structural adjustment:

Alloy the 500-700 ℃ of heat treatment of carrying out 0.5-2 hour, to form nano level precipitation micro-structural, is cooled fast to room temperature then in being better than the vacuum of 1Pa.This is one of committed step of the present invention.

(3) fragmentation:

Key component X among the present invention can't be obtained the structure of X calking by direct melting in the alloy, and must be solid by oozing X method warp---gas-phase reaction joins X in the alloy, in order to make the X can be fully and enter into foundry alloy equably, before oozing X, foundry alloy must be crushed to certain particle.

Fragmentation can be adopted any method; as comminution by gas stream; swing crushing, hydrogen embrittlement fragmentation etc., main purpose is to obtain the foundry alloy powder that particle mean size is the 0.5-200 micron; because the easy oxidation of alloy among the present invention; so in the alloy crushing process, especially when particle size is enough thin, should adopt certain anti-oxidation means; to prevent that alloy oxidation from causing the magnet performance that finally produces to reduce, as being better than under the vacuum condition of 1Pa or (as: N under the non-oxidizing gas protection ₂, Ar) operation, or broken under the little organic solvent of the solubility of oxygen and water (as: gasoline, acetone, benzinum etc.) protection.

(4) ooze X:

Oozing X also is one of committed step among the present invention, because foundry alloy itself has not had the Hard Magnetic characteristic, have only by X is penetrated in the lattice of foundry alloy, make 2: 17 phases in the foundry alloy or mutually become the alloy that contains the X interstitial atom at 1: 12 just to have had good Hard Magnetic characteristic.

Wherein X is Elements C or C and H;

Oozing X is broken good foundry alloy to be put in the atmosphere with certain X chemical potential carry out, and oozing X atmosphere can be single CH ₄, C ₂H ₂, C ₄H ₃CO also can be the mixture of two or more above-mentioned gas.

Because oxygen can reduce the magnetic of magnet, so in oozing X atmosphere, oxygen content should be lower than 5000ppm, therefore require in oozing the X process, foundry alloy to be put into the X gas that (is better than 3Pa) in the high as far as possible vacuum and then feeds purity＞99.9% earlier, the gas pressure that oozes X can be arbitrarily, can to cause oozing the speed of X slow excessively but cross low pressure, makes and ooze the X overlong time; And too high pressure can cause production equipment complicated, so the pressure that adopts can be within the 0.1-10 barometric pressure range.

Ooze the X temperature and can be chosen between 100-650 ℃, concrete temperature is selected can be according to oozing the X time and oozing X atmosphere and the pressure decision, and it is low more to ooze the X temperature, and it is low more to ooze X pressure, and it is long more then to ooze the X time.When temperature is lower than 100 ℃, the speed of oozing X will be too slow, and when temperature was higher than 650 ℃, the performance of magnet appearred reducing greatly in α in the alloy-Fe.

Oozing the X time can be chosen between 0.5-50 hour, and concrete selection of time is according to oozing the X temperature and oozing the decision of X atmosphere pressures.After oozing the end of X process, magnetic should be as cold as room temperature soon, to keep the precipitation structure in the step (2).

If the foundry alloy powder is too tiny when oozing X, such as less than 1 micron, before oozing X and ooze in the X process, the easy oxidation of alloyed powder, thus cause the performance of magnetic to reduce, for anti-oxidation, in above-mentioned technology, must strictly observe salvo.

(5) alloyed powder moulding in magnetic field:

Particle mean size is less than 5 microns alloyed powder, ooze X after, directly compression moulding under magnetic field of alloyed powder,

After 5-100 micron alloyed powder oozes X, is further to improve coercive force as particle mean size, alloyed powder can be through second-time breakage, and the particle mean size that makes alloyed powder is less than 5 microns, then reshaping in magnetic field.

Briquetting pressure is 0.5-6 ton/square centimeter, and adding magnetic field intensity in the forming process is 10-20KOe.

(6) final molding:

In order to make magnet density reach about 95% of solid density value, need to pass through final rapid shaping again by the pressed compact after step (4) moulding.

The pressed compact of compression moulding is put into-the metal jacket seals, this metal jacket material therefor can be to have the metal material of certain toughness arbitrarily (as metallic aluminium, copper, carbon steel, steel alloy etc.), final molding realizes by apply a high-speed molding pressure field on the metal jacket, promptly in the extremely short time, set up a high-voltage field, be added on the metal jacket, the effect that the interior metal powder of jacket is subjected to high-voltage field runs foul of each other and rubs, and produces certain temperature rise, under high pressure makes pressed compact sinter molding in the jacket.The pressure field of using among the present invention is 10 ³～10 ⁸MPa, the time of setting up this pressure field is the 0.01-100 microsecond.

(7) annealing:

Just obtained the actual magnet of density through step (6) greater than solid density 90%, but magnet to some composition, suitable annealing in process can further be improved the performance of magnet, annealing temperature is chosen between 150 ℃-650 ℃ among the present invention, and annealing time is between 0.2-20 hour, but annealing temperature is when being lower than 150 ℃, the DeGrain of annealing, when annealing temperature is higher than 650 ℃, the principal phase of magnet inside will be decomposed, and magnet performance is sharply descended.Annealing back magnet must be as cold as room temperature soon.

The permanent magnet technological process has following four kinds of modes:

Its manufacturing process 1:

Batching-melting-(homogenizing heat treatment)-broken 5-100 micron-ooze X-[second-time breakage (0.5-5 micron)]-pressing under magnetic field-final molding

Technology 2:

Batching-melting-(homogenizing heat treatment)-carrying out precipitation treatment---broken (5-100 micron)-[second-time breakage (0.5-5 micron)] oozes X-pressing under magnetic field-final molding. Technology 3:

Batching-mechanical alloying-(heat treatment)-ooze X-pressing under magnetic field-final molding. Technology 4:

Batching-melting-liquid phase chilling powder process-fragmentation-(heat treatment)-ooze X-(second-time breakage)-pressing under magnetic field-final molding.

Wherein the technology of () is represented that this technical process can adopt and also can.

The ferrous rare earth permanent magnet and the manufacture method thereof of the present invention's preparation are provided by following embodiment and accompanying drawing:

Accompanying drawing 1:Sm ₂Fe ₁₇And Sm ₂Fe ₁₇N ₃The x-ray diffractogram of powder of compound

Accompanying drawing 2:Sm ₂Fe ₁₇The demagnetization curve of Ny permanent magnet

Accompanying drawing 3:Sm ₂(Fe _0.95Nb _0.05) ₁₇And the x-ray diffractogram of powder of nitride

Accompanying drawing 4:Sm ₂(Fe _0.95Nb _0.05) ₁₇The magnet HCJ and the squareness of Ny alloy different heat treatment temperature correspondence.

Accompanying drawing 5:Sm ₂(Fe _1-xNb _x) ₁₇N ₃The demagnetization curve of magnet before and after grinding

Accompanying drawing 6:Sm ₂(Fe _1-xNb _x) ₁₇N ₃The magnetic property of magnet is with the variation of X,

Table 1:Sm ₂(Fe _1-xNb _x) ₁₇N _yMagnetic property

Table 2: difference is oozed Sm under the X condition ₂(Fe _0.95Nb _0.05) ₁₇N _yMagnetic property

Table 3: the part rare earth replaces the magnetic property of Sm

Table 4: part metals replaces the magnetic property of Fe

Describe in detail according to the concrete material composition of the present invention's proposition and preparation method's process detail below in conjunction with embodiment and accompanying drawing.

Embodiment 1:

Use commercially available high-purity Sm; Fe (purity＞99%); press composition 10.5at%Sm; 89.5at%Fe (being Sm2Fe17) prepares the raw material that gross weight is 30 grams; wherein Sm is 7.2 grams; Fe is 22.8 grams; consider Sm highly volatile at high temperature; add Sm on the basis of the above again into 2 grams; still remain on about 10.5at% with Sm content in the alloy pig after the assurance melting; under the protection of an atmospheric Ar inert gas, be smelted into master alloy ingot with arc furnace, even for guaranteeing the master alloy ingot composition, congruent melting refining three times; at every turn 1700 ℃ of meltings 2 minutes; foundry alloy was handled six hours in 1000 ℃ of vacuum, and vacuum degree is better than 5Pa, then master alloy ingot was shaken in organic solvent (gasoline) that to be crushed to particle mean size be about 30 microns; alloyed powder is put into vacuum degree to be higher than in the vacuum tube furnace of 5Pa; feed atmospheric high-purity (＞a 99.9%) nitrogen again,, obtain Sm 520 ℃ of nitridings 2 hours ₂Fe ₁₇N _yAlloyed powder, Fig. 1 is the powder x-ray diffraction result after the nitriding.

Having oozed alloyed powder behind the nitrogen, to carry out the second time by ball milling broken, and ball milling carries out in gasoline, and ratio of grinding media to material is 20: 1, and the ball milling time is 8 hours, and the alloyed powder particle mean size is about 2 microns behind the ball milling.

Powder behind the ball milling is in moulding in 17KOe magnetic field under the 1.5 tons/cm2 pressure.Briquetting after the moulding with the sealing of Fe jacket, is adopted blast compression moulding, obtain final rapid shaping magnet.

Density measure shows that magnet density is 99% of solid density after the moulding, reaches 7.4 gram/cubic centimetres, and Fig. 2 is the demagnetization curve of magnet after powder, the powder after the second-time breakage and the moulding of just having oozed nitrogen.

Embodiment 2:

Be similar to embodiment 1, press composition 10.5at%Sm, 4.5at%Nb and 85.0at%Fe[promptly press Sm ₂(Fe _0.05Nb _0.05) ₁₇] the prescription weighing.

Alloy after the homogenizing processing finishes before fragmentation, respectively at 500 ℃, 600 ℃ and 700 ℃ of vacuum heat of carrying out 1 hour, vacuum degree is better than 5Pa, is as cold as room temperature soon after the heat treatment end.

The nitridation process condition is with embodiment 1.Powder X-ray-ray shoots figure such as Fig. 3 before and after the nitriding

The nitrogenize powder is pressed the process conditions rapid shaping of embodiment 1 without second-time breakage, and the HCJ of magnet and squareness are seen Fig. 4 after the moulding.

Embodiment 3:

Press the component prescription of table 1, other process conditions are with embodiment 2, but select the foundry alloy heat treatment temperature at 600 ℃, and other condition is constant.

The demagnetization curve of magnet is seen Fig. 5 a, and corresponding permanent magnetism performance sees Table 1 and Fig. 6 a, 6b, 6c, 6d.

Embodiment 4:

Process conditions such as embodiment 3 when nitriding finishes, the nitriding powder carries out the fragmentation second time by ball milling, ball milling carries out in gasoline, ratio of grinding media to material 20: 1, and the ball milling time is that the average particle size of alloyed powder is about 2 μ m (No.1's is smaller) behind 3 hours (but No.1 is 8 hours) ball millings

Moulding process such as embodiment 3.

The demagnetization curve of magnet is seen 5b, and corresponding permanent magnetism performance sees Table 1 and Fig. 6 a, 6b, 6c, 6d.

Table 1.Sm ₂(Fe _1-xNb _x) ₁₇N _yThe magnetic property sample number 123456 remarks X 0 0.005 0.01 0.05 0.1 0.2l (8/cm of rapid shaping magnet ³) 7.4 7.4 7.4 7.4 7.4 7.4 Br 4.9 8.0 10.5 11.2 9.3 6.1 * (kGs) 9.0 9.4 9.6 10.5 8.0 4.1 ** iHc 0.8 3.1 4.2 6.3 4.5 1.0 * (kOe) 0.2 8.0 8.1 8.0 6.9 1.6 **Hk/iHc 0.3 20.2 35.0 43.6 30.2 10.0 * (％) 20.1 34.8 35.2 44.5 20.2 10.1 ** (BH)max 1.5 7.0 13.8 18.0 11.1 2.0 * (MGOe) 13.5 17.0 17.3 20.1 10.2 1.8 **

* be before the regrind, see embodiment 3

* is the process regrind, corresponding embodiment 4

Example 5:

Among the embodiment 2 after 600 ℃ of one hour vacuum heat broken particle mean size be foundry alloy powder about 30 microns, under the high pure nitrogen atmosphere under 0.5 atmospheric pressure, 540 ℃ of nitridings 3 hours, to utilize then with example 4 ball millings and condition of molding, other process conditions are equally manufactured with embodiment 2.

What obtain the results are shown in Table 2.

Example 6:

Nitriding pressure in the example 5 is changed into 3 atmospheric pressure, and nitriding temperature is 430 ℃, and nitriding time changes 2 hours into, and other process conditions are with example 5.

What obtain the results are shown in Table 2.

Example 7:

Nitriding condition in the example 5 is changed into the mist of an atmospheric 50%NH3 of containing and 50%H2, oozed 2 hours, obtain Sm (Fe at 420 ℃ _0.95NbNB _0.05) ₁₇(N ₉₆H ₄) the y alloyed powder, other process conditions are with example 2,

What obtain the results are shown in Table 2.

Example 8:

Nitriding in the example 5 is changed into carburizing, is the particle mean size that is same as example 5 that foundry alloy powder about 30 microns is put into an atmospheric high-purity C ₂H ₂In, 500 ℃ of following carburizings 2 hours, other process conditions were with example 2.

What obtain the results are shown in Table 2.

Example 9:

Master alloy ingot is prepared with example 2, is the alloy pig swing crushing about 30 microns to particle mean size, ball milling nitriding after 6 hours then, and the nitriding condition is under an atmospheric high pure nitrogen atmosphere, 420 ℃ of nitridings 1 hour.

Powder straight forming after the nitriding, moulding process is with example 2.

What obtain the results are shown in Table 2

Table 2. embodiment Br (kGs) iHc (kOe) H _k/ iHc (%) is max (MGOe) (BH)

5 10.2 7.8 42 19.5

6 10.6 8.2 45 20.2

7 10.5 8.5 44 20.0

8 9.8 7.9 40 18.0

9 9.5 8.3 41 17.0

Example 10-14

Virgin alloy composition in the example 2 is changed into following composition (being atomic percent): Sm10Er0.5Fe85.0Nb4.5; Actual batching Sm:7.1+2.1g Er:0.3g

Fe:20.6g Nb2.0g Sm10Gd0.5Fe85.0Nb4.5; Actual batching Sm:7.1+2.1g Gd:0.34g

Fe:20.56g Nb2.0gSm10Dy0.5Fe85.0 Nb4.5; Actual batching Sm:7.1+2.1g Dy:0.36g

Fe:20.54g Nb2.0gSm9.5Pr1Fe85.0 Nb4.5; Actual batching Sm:6.5+1.9g Pr:0.64g

Fe:20.86g Nb2.0gSm9.5Nd1Fe85.0 Nb4.5; Actual batching Sm:6.5+1.9g Nd:0.65gFe:20.85g Nb2.0g

Other process conditions are with example 4.

Gained the results are shown in Table 3.

Table 3:

	Br iHc (BH) max Tc density (kGs) (kOe) (MGOe) (℃) (g/cm ³)
	Br iHc (BH) max Tc density (kGs) (kOe) (MGOe) (℃) (g/cm ³)	Sm10Er0.5Fe85.0 Nb4.5 Sm10Gd0.5Fe85.0 Nb4.5 Sm10Dy0.5Fe85.0 Nb4.5 Sm9.5Pr1Fe85.0 Nb4.5 Sm9.5Nd1Fe85.0 Nb4.5	9.7 8.5 16.8 467 7.3 8.8 8.4 13.9 471 7.3 9.0 8.3 15.4 468 7.3 10.7 7.8 15.0 468 7.4 10.8 7.9 17.2 468 7.4

Example 15-19: transiting group metal elements adds

Virgin alloy composition in the example 2 is changed into following composition: (atomic percent) Sm10.5Fe63.0Co22Nb4.5; Actual batching Sm:7.1+2.1g Fe:15g Co:5.8g

Nb2.0gSm10.5Fe74.5Al10.5Nb4.5; Actual batching Sm:7.5+2.23g Fe:19.2g

Al:1.3g Nb2.0gSm10.5Fe76.5Ni85.0Nb4.5; Actual batching Sm:7.2+2.2g Fe:18.6g

Ni:2.2g Nb2.0gSm10.5Fe82.5Ti2.5Nb4.5; Actual batching Sm:7.2+2.2g Fe:20.2g

Ti:0.6g Nb2.0gSm10.5Fe62.5Co18A14.5 Nb4.5; Actual batching Sm:7.3+2.2g Fe:15.3g

Co：4.9g

Al：0.5 Nb：2.0g

Other process conditions are with example 4.

Gained the results are shown in Table 4.

Table 4:

	Br iHc (BH) max Tc density (kGs) (kOe) (MGOe) (℃) (g/cm ³)
	Br iHc (BH) max Tc density (kGs) (kOe) (MGOe) (℃) (g/cm ³)	Sm10.5Fe63.0Co22Nb4.5 Sm10.5Fe74.5Al10.5Nb4.5 Sm10.5Fe76.5Ni8.5Nb4.5 Sm10.5Fe82.5Ti2.5Nb4.5 Sm10.5Fe62.5Co18A14.5 Nb4.5	11.0 7.8 22.1 311 7.4 8.8 8.2 15.4 373 7.4 8.9 8.2 14.6 445 7.4 8.5 9.7 13.9 482 7.4 8.2 9.8 14.1 381 7.4

Embodiment 20,

Press NdFe _10.5Nb _0.5Mo ₂The atomic ratio prescription is considered the volatilization of Nd, and Nd adds 5wt% during batching.The purity of Nd and Mo is better than 99%, and the purity of Fe is with embodiment 1.

Other technical processs are with embodiment 2, and thus obtained permanent magnet magnetic performance is:

Density p=7.8 (g/cm ³)

Remanent magnetism Br=8kGs

HCJ iHc=7kOe

Magnetic energy product (BH) _Max=14MGOe

Embodiment 21:

Press NdFe _10.5Nb _0.5Ti atomic ratio prescription, other process conditions and embodiment 19 are same, and permanent magnet performance is as follows:

ρ＝7.8(g/cm ³)

Br＝7.5kGs

iHc＝6kOe

(BH) _max＝12MGOe

6, effect:

Because the present invention adds an amount of Nb in alloy, and the structure of alloy is adjusted in the appropriate heat treatment of process, thereby alloy can be without second-time breakage after oozing X, or only carry out suitable second-time breakage, namely can under the prerequisite that keeps higher remanent magnetism, obtain considerable coercivity, and squareness improves, so magnetic has the possibility that obtains than the high energy product magnet.

Because the alloy among the present invention is at high temperature unstable, make actual magnet so can not use traditional powder sintering method, as adopt and add the low-melting-point metal low-temperature sintering method, the organic binder bond method, because non-magnetic phase adds the remanent magnetism that has reduced magnet, so can not obtain high remanent magnetism magnet by the method, the present invention has adopted rapid shaping technique, above-mentioned two kinds of obstacles have been overcome simultaneously, neither use the high temperature sintering method, do not add nonmagnetic substance yet, but obtained density greater than 95% the high-performance magnet that almost contains hundred-percent Magnetic Phase of the solid density of above-mentioned 2: 17 or 1: 12 phase.

The present invention is by new forming technique, do not adopt traditional sintering method, but obtained the permanent magnet the same with sintering method, on this basis, we can adopt with sintering method in like the follow-up heat treatment phase process change the permanent magnet internal organizational structure and improve the magnet magnetic property.

The present invention uses Fe to replace most of Co in traditional Sm-Co magnet, so even be starkly lower than traditional Sm-Co magnet with replacement Sm magnet costs such as Nd, Pr.

The present invention is being better than the NdFeB magnet aspect the Curie temperature Tc of magnet and the anisotropy field Ha, so heat endurance is better than the NdFeB magnet.

Primary product of the present invention is the X compound that contains the rare earth-iron base alloy of Nb, so its anticorrosion properties, also is better than the NdFeB magnet, and is especially all the more so when X is N.

Claims

1, a kind of ferrous rare earth permanent magnet that contains niobium, its general formula is:

Rα(Fe _1-x-yNb _xM _y) _100-α-βX _β

Wherein: R is single S m or Nd, Sm or Nd and more than one following Elements C e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, Pa, U, Np, Pu, the mixture of Y;

M is one or more following element: Co, Al, Cu, Zr, Si, Ca, Sn, Ni, In, Bi, Zn, Ti, Mo, W, V, Ge, Re, Hf, S;

X is Elements C or C and H;

Press the atomic percent component:

α is 6-25

β is 5-30

X is 0.001-0.20

Y is 0-0.4

The addition of M is limited to respectively in the following atomic percent scope: Co 0-50 Al 0-20 Si 0-10 Ca 0-15 Cu 0-15 Zr 0-10 Ni 0-10 S 0-5 Hf 0-10 Sb 0-7 Ge 0-5 W 0-7 Mo 0-7 Ti 0-10 V 0-10 Sn 0-10 In 0-5 Bi 0-5 Zn 0-10

2, a kind of direct described method that contains the ferro-niobium base rear earth permanent magnet of claim 1 for preparing, after forming weighing, through anti-oxidation heating smelting temperature is under 1500-2300 ℃, melting 2-90 minute, the gained foundry alloy is again after homogenizing is handled (also can not handling), carry out the Low Temperature Heat Treatment that micro-structural is adjusted, under anti-oxidation condition, pulverize foundry alloy then and obtain the alloyed powder that particle mean size is about 0.5-200 μ m; Then ooze X, earlier alloyed powder is put into vacuum degree and is better than in the 3Pa vacuum chamber, feed the high-purity X of containing atmosphere again, oxygen content must be lower than 5000ppm in this atmosphere, oozing the X atmosphere pressures is the 0.1-10 atmospheric pressure, and temperature is at 100-700 ℃, and oozing the X time is 0.5-50 hour; The alloyed powder that oozes behind the X is placed in the magnetic field of 10-20 kilo-oersted, and briquetting pressure is under 0.5-6 ton/square centimeter, is pressed into base, and the preparation of final molding contains ferro-niobium base rare earth R α (Fe then _1-x-yNb _xM _y) _{The 100-alpha-beta}X _βThe method of permanent magnet is characterized in that: again the pressed compact of moulding is put into the metal jacket and seals, the sealing jacket put into one the 0.01-100 microsecond set up rapidly 10 ³-10 ⁸Final rapid shaping in the high pressure field of force of MPa, permanent magnet also can be taked annealing in process after the moulding.

3, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: said anti-oxidation heating melting is that induction heating temperature is 1500-2300 ℃ under the vacuum of 1-5Pa, and the time is 10-90 minute;

4, by the described method for preparing ferrous rare earth permanent magnet of claim 2, it is characterized in that: said anti-oxidation heating melting is arc heating under the atmospheric inert atmosphere protection of 0.5-2 under the 1500-2300 ℃ of temperature 2-10 minute.

5, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: it is under 900-1300 ℃ of temperature that said foundry alloy homogenizing is handled, in a vacuum or heated under inert gas shielding 2 hours to 60 days again.

6, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: the Low Temperature Heat Treatment of described micro-structural adjustment is in being better than the vacuum of 5Pa, and insulation is 0.5-3 hour under the 500-700 ℃ of temperature, and is as cold as room temperature soon.

7, the method that contains the ferro-niobium base rear earth permanent magnet by the described preparation of claim 2; it is characterized in that: said take under certain anti-oxidation condition foundry alloy is crushed to particle mean size for 0.5-200 μ be better than operation under the 10Pa in vacuum degree, in operation under the inert gas shielding, at organic solvent: operate in gasoline, acetone, the benzinum, crumbling method is comminution by gas stream, Mechanical Crushing, hydrogen embrittlement fragmentation.

8, contain the method for ferro-niobium base rear earth permanent magnet by any one described preparation in the claim 2,4,5,7, it is characterized in that: described inert gas is that the purity of Ar, He, its inert gas of Ne is at 99.5%-99.99%.

9, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: said X is Elements C or C and H; The atmosphere of oozing X can be single CH ₄, C ₂H ₄, C ₄H ₈, CO, also can be the mixture of two or more above-mentioned gas.

10, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: said metal jacket is that metal materials such as aluminium that certain toughness is arranged, copper, carbon steel, steel alloy are made.

11, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: said final rapid shaping is the explosive sintering technology.

12, contain the method for ferro-niobium base rear earth permanent magnet by the described preparation of claim 2, it is characterized in that: said annealing in process is to anneal 0.2-20 hour down at temperature 150-650 ℃.