CN105225781A - A kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet and preparation method thereof - Google Patents
A kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to rare-earth permanent-magnet material technical field, relate to a kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet and preparation method thereof.This permanent magnet adopts powder to inhale hydrogen control oxygen, the preparation of presintering dehydrogenating technology; In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and the chemical formula of this permanent magnet is expressed as by mass percentage: (Ce, Re)
afe
100-a-b-cb
btM
c, by having (Pr, the La that following granularity is different, magnetocrystalline anisotropy constant k is different, Ce, Nd)-Fe-B, (Nd, Pr)-Fe-B and (Dy, Ho, Gd, Er) the magnetic preparation of-Fe-B many Hard Magnetic principal phases: the chemical formula of each principal phase is respectively: (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1, (Nd
ypr
1-y)
a2fe
100-a2-b2-c2b
b2tM
c2, [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3-b3-c3b
b3tM
c3; Wherein, 0.25 & lt; X≤1.0,0≤y≤1.0,0 & lt; Z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2, a1 ~ a3, b1 ~ b3, the span of c1 ~ c3 is identical with a, b, c respectively, and Re is selected from rare earth element, and RL is containing light rare earth, and RH is containing heavy rare earth element, TM is one or more in Ga, Co, Cu, Nb, Al element.The present invention has high corrosion-resistant and little specific of weight-loss ratio, and its technology of preparing is suitable for through engineering approaches large-scale production.
Description
Technical field
The invention belongs to rare-earth permanent-magnet material technical field, particularly relate to a kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet and preparation method thereof.
Background technology
Up to now, neodymium iron boron is still the permanent magnetic material with peak performance, has irreplaceability.Nd
2fe
14b is synthesized by Russian scientists very early as a kind of intermetallic compound, and the patent of invention relating to NdFeB is a lot of, and composition patent mainly contains US Naval Research Laboratory (DLN.Koon), and it only covers the U.S..Hitachi Metals company (inherits in SUMITOMO CHEMICAL particulate metal company, SSMC) and the composition patent of Magnequench company (inheriting in General Motors Overseas Corporation, GM) (Dr.J.Croat etc.) then cover Japan, the U.S., Europe.But from 2002, these patents expired successively, to the end of the year 2014, comprise the original patent of Hitachi, Ltd and all will expire.Based on the consideration of interests, on August 17th, 2012, FDAC metal Co., Ltd. (HitachiMetals, and affiliated company's Hitachi Metals North Carolina company (HitachiMetalsNorthCarolina Ltd.), Ltd.), before Patent expiry, take the measure of some necessity in advance, according to " Tariff Act of 1930 " Section 337 regulation, propose to American I TC, 29 enterprises such as China, the U.S. are to u.s. export, invaded its patent at U.S. Register at imported from America or at the sintering rare-earth magnet of U.S.'s sale.Force 8 companies of China and HIT to sign patent selling license contract, the patent life-span extending Japan reaches 5-10, limits the development of Chinese most of Rare Earth Enterprises overseas market.
In the research with Ce, La Some substitute Nd, General Research Inst. of Iron and Steel, Ministry of Metallurgical Industry and Magnequench (Tianjin) Co., Ltd. propose Chinese patent application CN1035737A and CN101694797 respectively, but the method proposed according to above-mentioned patent/patent application all needs the alloy of melting Multiple components when preparing different trade mark magnet, improve production cost; On the other hand, although also with the addition of Re (Re is La, Ce, Pr, Dy, Tb, Ho etc.) rare earth element in above-mentioned magnet, but directly Re is fused in alloy, can Re be made, the Nd that what especially La, Ce were too much instead of in principal phase and the performance of severe exacerbation magnet.In view of, Re
2fe
14anisotropy field HA and the magnetic moment Js of B are different, Iron and Steel Research Geueral Inst proposes Chinese patent application CN102436892A, CN102800454A and CN103714939A respectively, be characterized in the magnet constituting two (Hard Magnetic) principal phase structure, reduce sintering temperature, and give full play of the Re with different anisotropy constant k (correspond to different anisotropy field HA)
2fe
14physics, chemical property that B crystal grain (or particle) is unique, make full use of between these particles, and the magnetic interaction between granular boundary, and compare with single alloy magnet of generic ingredients, coercive force significantly improves.In addition, it is maximum that the common feature of patent application CN1035737A, CN102436892A and CN101694797 is that Nd accounts for the weight of magnet middle rare earth total amount, still belong to the category of Nd-Fe-B magnet, and patent application CN103714939A and CN102800454A is La, Ce respectively, and to account for the weight of magnet middle rare earth total amount maximum, do not belong to the category of Nd-Fe-B magnet, but above-mentioned patent application belongs to two (Hard Magnetic) principal phase magnet, and La, Ce, the corrosion resistance of magnet has much room for improvement.
Summary of the invention
An object of the present invention, is to provide a kind of high corrosion-resistant, (Pr, La, Ce)-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Ho, Gd, Er)-Fe-B/ ... many Hard Magnetics principal phase Ce permanent magnet.
Another object of the present invention, is to provide the preparation method of above-mentioned high corrosion-resistant, many Hard Magnetics principal phase Ce permanent magnet.
To achieve these goals, the invention provides following technical scheme:
The invention provides a kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet, this permanent magnet adopts powder to inhale hydrogen control oxygen, presintering Oxidative Dehydrogenation is standby;
In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and final magnet is made up of multiple Hard Magnetic principal phases that magnetocrystalline anisotropy constant k is different, and these Hard Magnetic principal phases all have 2:14:1 type structure, is combined by following three class principal phases:
I) light rare earth phase: based on Ce, La abundant rare earth element (Pr, La, Ce, Nd)-Fe-B phase, can contain a small amount of Pr, Nd, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower;
II) Nd-Fe-B phase: based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher;
III) heavy rare earth phase: be that belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, but not containing Ce, La and Tb;
The chemical formula of described three class principal phases and final permanent magnet can be expressed as by mass percentage: (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1, (Nd
ypr
1-y)
a2fe
100-a2-b2-c2b
b2tM
c2, [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3-b3-c3b
b3tM
c3(Ce, Re)
afe
100-a-b-cb
btM
c; Wherein, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2, a1 ~ a3, b1 ~ b3, the span of c1 ~ c3 is identical with a, b, c respectively, Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, and TM is Ga, Co, one or more in Cu, Nb, Al element.
Described permanent magnet is prepared by following methods:
1) many major phase raw materials prepares: will not be prepared into containing the principal phase of Dy, Ho, Gd, Er heavy rare earth element and the principal phase containing Dy, Ho, Gd, Er heavy rare earth element rapid-hardening flake that average thickness is 0.1 ~ 0.5mm respectively and average thickness is the rapid tempering belt of 0.03 ~ 0.40mm,, dehydrogenation broken through hydrogen, obtain varigrained magnetic, carry out airflow milling or mechanical ball milling again, for subsequent use;
2) magnet blank is prepared: according to the equivalent component of final magnet, take prepared varigrained magnetic respectively in proportion and fully mix, regulate and control the hydrogen content of now magnetic at 200 ~ 2000ppm, magnetic oriented moulding in magnetic field of mixing, makes blank;
3) sinter: through 400 ~ 850 DEG C of scope classifications insulation, dehydrogenation, degassed, often improve 150 DEG C of insulations 30 minutes, totally 2 ~ 6 hours; Temperature 850 ~ 1050 DEG C of classification heat preservation sinterings 1 ~ 4 hour; Then the temper of 1 ~ 4 hour is carried out respectively 650 ~ 900 DEG C and 350 ~ 500 DEG C.
Described permanent magnet, by dehydrogenation, sintering and tempering process, makes the ceria of minute quantity in magnet transform into stable micro-cerium sesquioxide, suppresses the oxygen content in final magnet, improves the corrosion resistance of magnet.
The granularity of different principal phase magnetic is different, is respectively: the thick magnetic of the thin magnetic of particle diameter 0.1-2 μm, particle diameter 2-5 μm and nanocrystalline magnetic; In final magnet, the volume fraction shared by Hard Magnetic principal phase of different anisotropy constant k is not identical with granular size, has high corrosion-resistant and the little feature of weight-loss ratio.
Multiple Hard Magnetic principal phases of this permanent magnet comprise and are not limited to following combination:
1) be made up of mutually a Nd-Fe-B principal phase, light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B;
2) be made up of mutually different light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase of two components and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B;
3) be made up of mutually heavy rare earth (Dy, Ho, Gd, the Er)-Fe-B that light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase is different with two components;
4) be made up of light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase that a Nd-Fe-B principal phase is different from two components; Or
5) heavy rare earth (Dy, Ho, Gd, the Er)-Fe-B that Nd-Fe-B principal phase is different from two components is formed mutually.
Described permanent magnet has the 4th principal phase magnet, the 5th principal phase magnet or more principal phase magnet further.
Described permanent magnet has following many Hard Magnetics principal phase structure:
1) the four Hard Magnetic principal phase structures be made up of Ce-Fe-B and Nd-Fe-B, Pr-Fe-B, Dy-Fe-B; Or
2) the four Hard Magnetic principal phase structures be made up of (Pr, Ce)-Fe-B and Nd-Fe-B, (Pr, Gd)-Fe-B, (Ho, Gd)-Fe-B; Or
3) the five stiffness magnetic principal phase structure be made up of (Pr, Ce)-Fe-B and Nd-Fe-B, (Pr, Dy)-Fe-B, (Ho, Gd)-Fe-B, (Nd, Gd, Er)-Fe-B.
The invention provides a kind of preparation method of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet, according to the performance requirement of many Hard Magnetics principal phase Ce-Fe-B permanent-magnet alloy, design the main-phase alloy of different magnetocrystalline anisotropy constant k value, determine the phase structure composition of multiple difference many Hard Magnetics principal phase Ce-Fe-B permanent magnet; In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and all the other rare earths are the one or two or more mishmetal be selected from La, Nd, Pr, Dy, Ho, Gd, Er, and the method comprises following processing step:
(1) prepare multiple different Hard Magnetic main-phase alloy raw material respectively, these Hard Magnetic principal phases all have 2:14:1 type structure, are combined by following three class principal phases:
I) light rare earth phase: based on the abundant rare earth element of Ce, La (Pr, La, Ce)-Fe-B phase, a small amount of Pr, Nd can be contained, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower; Composition is (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1(wt.%);
II) Nd-Fe-B phase: based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher; Its composition is (Nd
ypr
1- y)
a2fe
100-a2-b2-c2b
b2tM
c2(wt.%);
III) heavy rare earth phase: be that belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, but not containing Ce, La and Tb; Its composition is [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3- b3-c3b
b3tM
c3(wt.%);
Wherein, the span of a1 ~ a3, b1 ~ b3, c1 ~ c3 respectively with final magnet (Ce, Re)
afe
100-a-b-cb
btM
c(wt.%) a in, b, c span is identical, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2; Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, and RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, TM is Ga, Co, Cu, one or more in Nb, Al element;
(2) distinguish the raw material that melting step (1) prepares, be poured on water-cooled copper alloy roller by the molten steel not containing Dy, Ho, Gd, Er heavy rare earth element, obtained average thickness is the rapid-hardening flake of 0.1 ~ 0.5mm;
Molten steel containing Dy, Ho, Gd, Er heavy rare earth element is obtained the rapid tempering belt of thickness at 0.03 ~ 0.40mm;
(3) rapid-hardening flake step (2) obtained respectively and rapid tempering belt carry out hydrogen fragmentation, and then, dehydrogenation, respectively through fragmentation, airflow milling or mechanical ball milling, obtains thick magnetic, thin magnetic and nanocrystalline magnetic;
(4) according to the equivalent component (Ce, Re) of final magnet
afe
100-a-b-cb
btM
c(wt.%), determine the content of each main-phase alloy of many principal phases magnet, take the different magnetic of granularity prepared by step (3) by a certain percentage respectively, additional lubricant, mix in batch mixer, and the hydrogen content regulating and controlling now magnetic is at 200 ~ 2000ppm; Under inert gas shielding atmosphere, magnetic oriented moulding in magnetic field will be mixed, make blank;
(5) then put into sintering furnace to be incubated 400 ~ 850 DEG C of scope classifications, dehydrogenation, degassed, often improve 150 DEG C of insulations 30 minutes, totally 2 ~ 6 hours, temperature 850 ~ 1050 DEG C of classification heat preservation sinterings 1 ~ 4 hour; Then the temper of 1 ~ 4 hour is carried out respectively 650 ~ 900 DEG C and 350 ~ 500 DEG C.
In step (2), molten steel not containing Dy, Ho, Gd, Er heavy rare earth element is poured on the water-cooled copper alloy roller that linear velocity is 1 ~ 4m/s, the molten steel containing Dy, Ho, Gd, Er heavy rare earth element is poured into the water-cooled molybdenum alloy roller that linear velocity is 15 ~ 40m/s.
In step (3), different principal phase magnetic is prepared into the different magnetic of granularity, is respectively: the thick magnetic of the thin magnetic of particle diameter 0.1-2 μm, particle diameter 2-5 μm and nanocrystalline magnetic.
Compared with prior art, beneficial effect of the present invention is:
First be the structure regulating technology of the many principal phases being similar to " plain concrete construction ", the magnetic of different principal phase is prepared into thin magnetic, thick magnetic, nanocrystalline magnetic etc., through overmulling powder, after orientation die mould and liquid-phase sintering, cause the defect in final magnet and hole to reduce, improve intergranular phase corrosion resistance;
Next adopts powder to inhale hydrogen control oxygen, and presintering De-hydrogen Technology, suppresses the oxygen content in final magnet, reduces the current potential of intergranular phase and principal phase, thus reduces intercrystalline corrosion.This does not have in other prior art;
Again, the use of mishmetal, the waste that the further separation avoiding rare earth brings.
The present invention only needs several composition quick setting belt of melting, just can make the magnet of the serial trade mark, has the adjustable degree of freedom of higher composition.In order to avoid different principal phase, intergranular unit have diffusion, present invention employs low temperature sintering technology, than the neodymium iron boron magnetic body of routine and single alloy Ce magnet sintering temperature low 20 ~ 50 DEG C, sintering time shortens 30 ~ 60 minutes.Although the present invention prepares the magnetic energy product of magnet at (BH)
max=25 ~ 45MGOe, in genus, low range, select and the comparable Ce magnet of conventional magnet, the weight-loss ratio of magnet under wet heat condition (130 DEG C, 100%RH) Ce content being accounted for total amount of rare earth 20% is less than 3mg/m
2, the 6mg/m of Ce neodymium iron boron magnetic body is contained far below single alloy of routine
2; The electrochemical current Icorr of magnet in 3.5%NaOH solution Ce content being accounted for total amount of rare earth 30% is less than 8 × 10
-6(Acm
2); In (35 DEG C, 5%NaCl) salt fog, corrode the weight-loss ratio after 168 hours and be less than 2%.Its technology of preparing is suitable for through engineering approaches large-scale production (see Fig. 1 and 2, table 1 and 2).
The corrosion current of Ce magnet, conventional N33 and N45 neodymium iron boron magnetic body and current potential in table 1 running water
The corrosion current of table 2 Ce magnet, conventional N33 and N45 magnet in 3.5%NaOH solution and current potential
Accompanying drawing explanation
Fig. 1 is that Ce magnet of the present invention compares with the electrochemical corrosion behavior (polarization curve) of conventional N33, N45 neodymium iron boron magnetic body in running water;
Fig. 2 is that Ce magnet of the present invention compares with the electrochemical corrosion behavior (polarization curve) of conventional N33, N45 neodymium iron boron magnetic body in 3.5%NaOH solution;
Fig. 3 be the embodiment of the present invention 1 magnet organize schematic diagram;
Fig. 4 be the embodiment of the present invention 4 magnet organize schematic diagram.
Reference numeral is wherein:
1. be Nd-Fe-B main phase grain
2. be Ce-Fe-B main phase grain
3. be Dy-Fe-B main phase grain
4. be Pr-Fe-B main phase grain
5. be Gd-Fe-B main phase grain
Embodiment
Below in conjunction with embodiment, the present invention is further described.
The present invention does not require that many principal phases magnet must be have (Nd, Pr)-Fe-B principal phase, light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B to form mutually; Also can be made up of mutually different light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase of two components and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B; Also can be made up of mutually heavy rare earth (Dy, Ho, Gd, the Er)-Fe-B that light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase is different with two components; Can also be made up of light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase that (Nd, Pr)-Fe-B principal phase is different from two components; Or (Nd, Pr)-Fe-B principal phase heavy rare earth (Dy, Ho, Gd, Er)-Fe-B different from two components is formed mutually; Etc. multiple combination.
Here key is that the saturated pole intensity Js between the different principal phase of adjustment has obvious gap with anisotropy field HA phase, and the granular size of different principal phase, and then make the structure of magnet tightr, and by inhaling hydrogen control oxygen, presintering dehydrogenation, reduce the oxygen content in magnet and impurity, improve the purity of magnet, improve corrosion resistance simultaneously.
The invention provides a kind of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet, in final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and form the different (Pr of magnetocrystalline anisotropy constant k, La, Ce)-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Ho, Gd, Er)-Fe-B/ ... many principal phases (being greater than two) grain structure.
This permanent magnet adopts powder to inhale hydrogen control oxygen, presintering dehydrogenation, and sintering, tempering process process cerium oxide the attribute that appraises at the current rate realize hypoxemia preparation.
In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, final magnet is made up of multiple Hard Magnetic principal phases that magnetocrystalline anisotropy constant k is different, these Hard Magnetic principal phases have identical 2:14:1 type structure, but component is different, its component belongs to two classes in following three class principal phase types or three classes:
One class is based on the abundant rare earth element of Ce, La (Pr, La, Ce)-Fe-B phase, a small amount of Pr, Nd can be contained, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower;
One class is based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, and not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher;
One class is containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, and belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd, but not containing Ce, La and Tb;
The chemical formula of described three class principal phases and final permanent magnet can be expressed as by mass percentage: (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1, (Nd
ypr
1-y)
a2fe
100-a2-b2-c2b
b2tM
c2, [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3-b3-c3b
b3tM
c3(Ce, Re)
afe
100-a-b-cb
btM
c; Wherein, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2, a1 ~ a3, b1 ~ b3, the span of c1 ~ c3 is identical with a, b, c respectively, Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, and TM is Ga, Co, one or more in Cu, Nb, Al element.
Also four principal phase magnets, five principal phase magnets can be designed as required, etc.
Magnet is by many principal phases (being greater than two) (La, Ce)-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Ho, Gd, Er)-Fe-B/ ... grain structure forms, and the volume fraction shared by Hard Magnetic principal phase of different anisotropy constant k and granular size are different.Why require that different Hard Magnetic phase granular size is different, it is the control technique being similar to " plain concrete construction " owing to present invention employs, the magnetic of different principal phase is prepared into thin magnetic, thick magnetic, nanocrystalline magnetic etc., cause final magnet density to improve, the defect in magnet and space are reduced.We know, cerium is very easily oxidized, and form the ceria of anoxic, CeO
2what have uniqueness stores oxygen performance, has unique function in water-gas shift, reforming reaction.Meanwhile, CeO
2also there is the fluorite structure of open to the outside world, solid solution can be formed with many transition metal oxides.The present invention is directed to the attribute that appraises at the current rate of cerium oxide, by the setting of dehydrogenation and sintering, tempering process, make the ceria (CeO of minute quantity in magnet
2) transform into stable micro-cerium sesquioxide (Ce
2o
3), suppress the oxygen content in final magnet, cause the corrosion proof raising of magnet, this is technology never in Ce permanent magnet.The mishmetal that the present invention also can directly use composition to determine.
The invention provides a kind of high corrosion-resistant, many principal phases Ce permanent magnet preparation method, according to the performance requirement of many Hard Magnetics principal phase Ce-Fe-B permanent-magnet alloy, the main-phase alloy of design different value of K (anisotropy constant), thus determine the phase structure composition of different many Hard Magnetics principal phase Ce-Fe-B permanent magnet, as the many Hard Magnetics principal phase structure be made up of Ce-Fe-B and Nd-Fe-B, Pr-Fe-B, Dy-Fe-B, or by (Pr, Ce)-Fe-B and Nd-Fe-B, (Pr, Dy) many Hard Magnetics principal phase structure of-Fe-B, (Ho, Gd)-Fe-B formation; In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, separately has account for rare earth total content 0% ~ 75% to be substituted by the one or two or more mishmetal in La, Nd, Pr, Dy, Ho, Gd, Er.The method comprises following processing step:
(1) prepare multiple different Hard Magnetic main-phase alloy raw material respectively, these Hard Magnetic principal phases have identical 2:14:1 type structure, but component is different, and its component belongs to two classes in following three class principal phase types or three classes:
One class is based on the abundant rare earth element of Ce, La (Pr, La, Ce)-Fe-B phase, a small amount of Pr, Nd can be contained, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower; Composition is (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1(wt.%);
One class is based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, and not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher; Its composition is (Nd
ypr
1-y)
a2fe
100-a2-b2- c2b
b2tM
c2(wt.%);
One class is containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, and belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd, but not containing Ce, La and Tb; Its composition is [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3-b3-c3b
b3tM
c3(wt.%);
Wherein, the span of a1 ~ a3, b1 ~ b3, c1 ~ c3 respectively with final magnet (Ce, Re)
afe
100-a-b-cb
btM
c(wt.%) a in, b, c span is identical, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2; Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, and RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, TM is Ga, Co, Cu, one or more in Nb, Al element;
Also can need to add the 4th principal phase, the 5th principal phase with micrometer structure or nanocrystalline structure, the 6th principal phase according to design, etc.
(2) distinguish the raw material that melting step (1) prepares, be poured on the water-cooled copper alloy roller that linear velocity is 1 ~ 4m/s by the molten steel not containing Dy, Ho, Gd, Er heavy rare earth element, obtained average thickness is the rapid-hardening flake of 0.1 ~ 0.5mm;
Molten steel containing Dy, Ho, Gd, Er heavy rare earth element is poured on water-cooled molybdenum alloy roller that linear velocity is 15 ~ 40m/s, obtains the rapid tempering belt of thickness at 0.03 ~ 0.40mm.
(3) rapid-hardening flake step (2) obtained respectively and rapid tempering belt carry out hydrogen fragmentation, and then, dehydrogenation, obtains coarse crushing magnetic, then carries out airflow milling or mechanical ball milling.
(4) according to the equivalent component (Ce, Re) of final magnet
afe
100-a-b-cb
btM
c(wt.%) many principal phases magnet (Pr, La, is determined, Ce, Nd)-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Ho, Gd, Er)-Fe-B/ ... in the content of each main-phase alloy, take the different magnetic of granularity prepared by step (3) by a certain percentage respectively, additional lubricant, mix in batch mixer, and the hydrogen content regulating and controlling now magnetic is at 200 ~ 2000ppm; Under inert gas shielding atmosphere, magnetic oriented moulding in magnetic field will be mixed, make blank.
(5) then put into sintering furnace to be incubated 400 ~ 850 DEG C of scope classifications, dehydrogenation, degassed, often improve 150 DEG C of insulations 30 minutes, totally 2 ~ 6 hours, temperature 850 ~ 1050 DEG C of classification heat preservation sinterings 1 ~ 4 hour; Then the temper of 1 ~ 4 hour is carried out respectively 650 ~ 900 DEG C and 350 ~ 500 DEG C.At high temperature cerium is very easily oxidized, and forms the ceria of anoxic, there is considerable oxide thing phase between ceria with cerium sesquioxide, all unstable.Hydrogen reduction ceria CeO in the process
2transform into stable cerium sesquioxide (Ce
2o
3), cerium becomes 3 valencys by 4 valencys and appraises at the current rate, and decreases the oxygen content in magnet.
In step (2), molten steel not containing Dy, Ho, Gd, Er heavy rare earth element is poured on the water-cooled copper alloy roller that linear velocity is 1 ~ 4m/s, the molten steel containing Dy, Ho, Gd, Er heavy rare earth element is poured into the water-cooled molybdenum alloy roller that linear velocity is 15 ~ 40m/s.
In step (3), different principal phase magnetic is prepared into the different magnetic of granularity, is respectively: the thick magnetic of the thin magnetic of particle diameter 0.1-2 μm, particle diameter 2-5 μm and nanocrystalline magnetic.
Elaborate to the embodiment under premised on technical solution of the present invention below, the present invention may be better understood.But it should be noted that following examples only for the purpose of illustration, protection scope of the present invention is not limited to following embodiment.
Embodiment 1-is Ce-Fe-B/Nd-Fe-B/Dy-Fe-B tri-Hard Magnetic principal phase structure
Design mix (Ce
0.5nd
0.45pr
0.05)
29fe
68.1b
0.9tM
2(TM=Ga, Co, Cu, Nb).
(1) according to alloy mass percent composition Ce
29fe
68.15b
0.85tM
2, Nd
28.5fe
68.6b
0.9tM
2and Dy
29.1fe
68.9b
1tM
2preparation raw material respectively.
(2) the raw material melting respectively will prepared.First raw material are put into medium frequency induction melting furnace rapid hardening crucible, reach 10 in vacuum degree
-2power transmission preheating during more than Pa, treats that vacuum degree reaches 10 again
-2stop after more than Pa vacuumizing and being filled with high-purity Ar, make Ar air pressure in stove reach 0.08MPa and carry out melting.After raw material all melt, impose electromagnetic agitation refining, be cast to by molten steel subsequently on water-cooled copper roller that linear velocity is 4m/s, obtained average thickness is the rapid-hardening flake of 0.3mm.
(3) after three kinds of rapid-hardening flake obtained by are respectively charged into and carry out hydrogen fragmentation in hydrogenation furnace, take out dehydrogenation, under protective atmosphere, broken to oxidation lubricant and hydrogen magnetic is mixed according to the ratio of 3 ~ 7ml/kg.Carry out airflow milling respectively more subsequently, Ce
29fe
68.15b
0.85tM
2and Nd
28.5fe
68.6b
0.9tM
2when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 3000r/min, and obtained granularity of magnet powder is about 3 μm; Dy
29.1fe
68.9b
1tM
2when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 5000r/min, and obtained granularity of magnet powder is about 2 μm.
(4) three kinds of magnetics step (3) prepared according to design mix fully mix in proportion, and the equivalent component of mixing magnetic is (Ce
0.5nd
0.45pr
0.05)
29fe
68.1b
0.9tM
2(TM=Ga, Co, Cu, Nb).Regulate and control the hydrogen content of now magnetic at 1000ppm; Under inert gas shielding atmosphere, be oriented moulding in the magnetic field of 2.3T in magnetic field intensity by mixing magnetic, then carry out isostatic cool pressing, make blank.
(5) then put into sintering furnace and be warmed up to 400 DEG C of beginnings, be incubated 30 minutes, then often improve 150 DEG C insulation 30 minutes, dehydrogenation, degassed complete after, temperature is risen to 1010 DEG C sintering 4 hours.Then the temper of 4 hours is carried out respectively 800 DEG C and 450 DEG C.
Final acquisition many principal phases Ce-Fe-B/Nd-Fe-B/Dy-Fe-B structure magnet, adopts NIM-2000HF permanent magnetic material standard measuring equipment to survey the magnetic property of magnet, and weight-loss ratio under wet heat condition (130 DEG C, 100%RH) is as shown in table 3.
The magnetic property of table 3 embodiment 1 magnet and weight-loss ratio
Embodiment 2-is (La, Ce, Nd)-Fe-B/Nd-Fe-B/ (Ho, Dy, Pr, Nd)-Fe-B three principal phase structure
Equivalent component (Ce
0.45la
0.05nd
0.3pr
0.15ho
0.02dy
0.03)
30fe
68.39b
0.94tM
0.67(TM=Ga, Co, Cu, Nb).
(1) according to mass percent (La
0.08ce
0.75nd
0.05pr
0.12)
30fe
68.4b
0.9tM
0.7, Nd
30fe
68.3b
1.1tM
0.6(Ho
0.15dy
0.25nd
0.4pr
0.2)
30fe
68.4b
1tM
0.6preparation raw material respectively.
(2) the raw material melting respectively will prepared.First raw material are put into medium frequency induction melting furnace rapid hardening crucible, reach 10 in vacuum degree
-2power transmission preheating during more than Pa, treats that vacuum degree reaches 10 again
-2stop after more than Pa vacuumizing and being filled with high-purity Ar, make Ar air pressure in stove reach 0.08Mpa and carry out melting, after raw material all melt, impose electromagnetic agitation refining, subsequently by (La
0.08ce
0.75nd
0.05pr
0.12)
30fe
68.4b
0.9tM
0.7and Nd
30fe
68.3b
1.1tM
0.6molten steel is cast on the water-cooled copper roller that linear velocity is 4m/s, and obtained average thickness is the rapid-hardening flake of 0.3mm.By (Ho
0.15dy
0.25nd
0.4pr
0.2)
30fe
68.4b
1tM
0.6molten steel is poured on the water-cooled molybdenum alloy roller that linear velocity is 23m/s, obtains the rapid tempering belt of thickness at about 0.1mm.
(3) after the rapid-hardening flake obtained by and rapid tempering belt are respectively charged into and carry out hydrogen fragmentation in hydrogenation furnace, take out dehydrogenation, under protective atmosphere, broken to oxidation lubricant and hydrogen magnetic is mixed according to the ratio of 3 ~ 7ml/kg.Carry out airflow milling respectively more subsequently, Nd
30fe
68.3b
1.1tM
0.6(La
0.08ce
0.75nd
0.05pr
0.12)
30fe
68.4b
0.9tM
0.7when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 3000r/min, and obtained granularity of magnet powder is about 3 μm; (Ho
0.15dy
0.25nd
0.4pr
0.2)
30fe
68.4b
1tM
0.6when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 5000r/min, and obtained granularity of magnet powder is about 2 μm, then by high-energy ball milling, the granularity of magnetic to be further reduced to be about 0.10 μm.
(4) three kinds of magnetics step 3 prepared according to design mix fully mix in the ratio of 11:8:1, and the equivalent component of mixing magnetic is (Ce
0.45la
0.05nd
0.3pr
0.15ho
0.02dy
0.03)
30fe
68.39b
0.94tM
0.67(TM=Ga, Co, Cu, Nb).Regulate and control the hydrogen content of now magnetic at 200ppm; Be oriented moulding in the magnetic field of 2.3T in magnetic field intensity by mixing magnetic, make blank.
(5) then put into sintering furnace and be warmed up to 450 DEG C of beginnings, be incubated 30 minutes, then often improve 125 DEG C insulation 30 minutes, dehydrogenation, degassed complete after, temperature is risen to 1020 DEG C sintering 4 hours.Then the temper of 4 hours is carried out respectively 870 DEG C and 460 DEG C.
Many principal phase (the La of final acquisition, Ce, Nd)-Fe-B/Nd-Fe-B/ (Ho, Dy, Pr, Nd)-Fe-B structure magnet, adopt NIM-2000HF permanent magnetic material standard measuring equipment to survey the magnetic property of magnet, and weight-loss ratio under wet heat condition (130 DEG C, 100%RH) is as shown in table 4.
The magnetic property of table 4 embodiment 2 magnet and weight-loss ratio
Embodiment 3-is (Ce, Nd)-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Nd)-Fe-B three Hard Magnetic principal phase structure
Design mix (Nd
0.34ce
0.35dy
0.08pr
0.23)
31fe
67b
1.5tM
0.5(TM=Ga, Cu, Al).
(1) according to alloy mass percent composition (Ce
0.6nd
0.4)
31fe
67b
1.5tM
0.5, (Nd
0.9pr
0. 1)
31fe
67b
1.5tM
0.5(Dy
0.7nd
0.3)
31fe
67b
1.5tM
0.5preparation raw material respectively, wherein, the mishmetal that Ce, La, Nd, Pr adoption rate is determined.
(2) the raw material melting respectively will prepared.First raw material are put into medium frequency induction melting furnace rapid hardening crucible, reach 10 in vacuum degree
-2power transmission preheating during more than Pa, treats that vacuum degree reaches 10 again
-2stop after more than Pa vacuumizing and being filled with high-purity Ar, make Ar air pressure in stove reach 0.08Mpa and carry out melting.Electromagnetic agitation refining is imposed, subsequently by (Ce after raw material all melt
0.6nd
0.4)
31fe
67b
1.5tM
0.5(Nd
0.9pr
0.1)
31fe
67b
1.5tM
0.5molten steel is cast on the water-cooled copper roller that linear velocity is 4m/s, and obtained average thickness is the rapid-hardening flake of 0.3mm.By (Dy
0.7nd
0. 3)
31fe
67b
1.5tM
0.5molten steel is poured on the water-cooled molybdenum alloy roller that linear velocity is 26m/s, obtains the rapid tempering belt of thickness at about 0.09mm.
(3) after three kinds of rapid-hardening flake obtained by are respectively charged into and carry out hydrogen fragmentation in hydrogenation furnace, take out dehydrogenation, under protective atmosphere, broken to oxidation lubricant and hydrogen magnetic is mixed according to the ratio of 3 ~ 7ml/kg.Carry out airflow milling respectively more subsequently, (Nd
0.9pr
0.1)
31fe
67b
1.5tM
0.5(Ce
0.6nd
0. 4)
31fe
67b
1.5tM
0.5when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 3000r/min, and obtained granularity of magnet powder is about 3 μm; (Dy
0.7nd
0.3)
31fe
67b
1.5tM
0.5when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 5000r/min, and obtained granularity of magnet powder is about 2 μm.
(4) three kinds of magnetics step 3 prepared according to design mix fully mix in proportion, and the equivalent component of mixing magnetic is (Nd
0.34ce
0.35dy
0.08pr
0.23)
31fe
67b
1.5tM
0.5(TM=Ga, Co, Cu, Nb), regulates and controls the hydrogen content of now magnetic at 1000ppm; Under inert gas shielding atmosphere, be oriented moulding in the magnetic field of 2.3T in magnetic field intensity by mixing magnetic, then carry out isostatic cool pressing, make blank.
(5) then put into sintering furnace and be warmed up to 400 DEG C of beginnings, be incubated 30 minutes, then often improve 150 DEG C insulation 30 minutes, dehydrogenation, degassed complete after, temperature is risen to 1050 DEG C sintering 4 hours.Then the temper of 4 hours is carried out respectively 800 DEG C and 450 DEG C.
The many principal phases (Ce, Nd) of final acquisition-Fe-B/ (Nd, Pr)-Fe-B/ (Dy, Nd)-Fe-B magnet.Adopt NIM-2000HF permanent magnetic material standard measuring equipment to survey the magnetic property of magnet, and weight-loss ratio under wet heat condition (130 DEG C, 100%RH) is as shown in table 5.
The magnetic property of table 5 embodiment 3 magnet and weight-loss ratio
Embodiment 4--is Ce-Fe-B/Nd-Fe-B/Pr-Fe-B/Gd-Fe-B tetra-Hard Magnetic principal phase structure
Design mix (Ce
0.6pr
0.1nd
0.25gd
0.05)
31fe
67.39b
0.94tM
0.67(TM=Ga, Cu, Al).
(1) according to alloy mass percent composition Ce
31fe
67.39b
0.94tM
0.67, Nd
31fe
67.39b
0.94tM
0.67, Pr
31fe
67.39b
0.94tM
0.67(Gd
0.65nd
0.35)
31fe
67.39b
0.94tM
0.67preparation raw material respectively.
(2) the raw material melting respectively will prepared.First raw material are put into medium frequency induction melting furnace rapid hardening crucible, reach 10 in vacuum degree
-2power transmission preheating during more than Pa, treats that vacuum degree reaches 10 again
-2stop after more than Pa vacuumizing and being filled with high-purity Ar, make Ar air pressure in stove reach 0.08Mpa and carry out melting.Electromagnetic agitation refining is imposed, subsequently by Ce after raw material all melt
31fe
67.39b
0.94tM
0.67, Nd
31fe
67.39b
0.94tM
0.67and Pr
31fe
67.39b
0.94tM
0.67molten steel is cast on the water-cooled copper roller that linear velocity is 4m/s, and obtained average thickness is the rapid-hardening flake of 0.3mm.By (Gd
0.65nd
0.35)
31fe
67.39b
0.94tM
0.67molten steel is poured on the water-cooled molybdenum alloy roller that linear velocity is 22m/s, obtains the rapid tempering belt of thickness at about 0.12mm.
(3) after four kinds of rapid-hardening flake obtained by are respectively charged into and carry out hydrogen fragmentation in hydrogenation furnace, take out dehydrogenation, under protective atmosphere, broken to oxidation lubricant and hydrogen magnetic is mixed according to the ratio of 3 ~ 7ml/kg.Carry out airflow milling respectively more subsequently, Ce
31fe
67.39b
0.94tM
0.67and Nd
31fe
67.39b
0.94tM
0.67when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 3000r/min, and obtained granularity of magnet powder is about 3 μm; Pr
31fe
67.39b
0.94tM
0.67(Gd
0.65nd
0.35)
31fe
67.39b
0.94tM
0.67when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 5000r/min, and obtained granularity of magnet powder is about 2 μm.
(4) three kinds of magnetics step 3 prepared according to design mix fully mix in proportion, and the equivalent component of mixing magnetic is (Ce
0.6pr
0.1nd
0.25gd
0.05)
31fe
67.39b
0.94tM
0.67(TM=Ga, Cu, Al).Regulate and control the hydrogen content of now magnetic at about 1500ppm; Under inert gas shielding atmosphere, be oriented moulding in the magnetic field of 2.3T in magnetic field intensity by mixing magnetic, then carry out isostatic cool pressing, make blank.
(5) then put into sintering furnace and be warmed up to 350 DEG C of beginnings, be incubated 30 minutes, then often improve 150 DEG C insulation 30 minutes, dehydrogenation, degassed complete after, temperature is risen to 1030 DEG C sintering 4 hours.Then the temper of 4 hours is carried out respectively 830 DEG C and 450 DEG C.
Many (permanent magnetism) principal phase Ce-Fe-B/Nd-Fe-B/Pr-Fe-B/Gd-Fe-B magnet of a kind of trade mark of final acquisition, NIM-2000HF permanent magnetic material standard measuring equipment is adopted to survey the magnetic property of magnet, and weight-loss ratio under wet heat condition (130 DEG C, 100%RH) is as shown in table 6.
The magnetic property of table 6 embodiment 4 magnet and weight-loss ratio
Embodiment 5-be (Ce, Nd)-Fe-B/Nd-Fe-B/ (Gd, Ho, Er)-Fe-B three Hard Magnetic principal phase
Design mix (Ce
0.7nd
0.24gd
0.03ho
0.02er
0.01)
31fe
67.39b
0.94tM
0.67(TM=Ga, Cu, Al).
(1) according to alloy mass percent composition (Ce
0.9nd
0.1)
31fe
67.39b
0.94tM
0.67, Nd
31fe
67.39b
0.94tM
0.67, [(Gd, Ho, Er)
0.7nd
0.3]
31fe
67.39b
0.94tM
0.67preparation raw material respectively.
(2) the raw material melting respectively will prepared.First raw material are put into medium frequency induction melting furnace rapid hardening crucible, reach 10 in vacuum degree
-2power transmission preheating during more than Pa, treats that vacuum degree reaches 10 again
-2stop after more than Pa vacuumizing and being filled with high-purity Ar, make Ar air pressure in stove reach 0.08Mpa and carry out melting.Electromagnetic agitation refining is imposed, subsequently by (Ce after raw material all melt
0.9nd
0.1)
31fe
67.39b
0.94tM
0.67and Nd
31fe
67.39b
0.94tM
0.67molten steel is cast on the water-cooled copper roller that linear velocity is 4m/s, and obtained average thickness is the rapid-hardening flake of 0.3mm.By [(Gd, Ho, Er)
0.6nd
0.4]
31fe
67.39b
0.94tM
0.67molten steel is poured on the water-cooled molybdenum alloy roller that linear velocity is 26m/s, obtains the rapid tempering belt of thickness at about 0.1mm.
(3) after three kinds of rapid-hardening flake obtained by are respectively charged into and carry out hydrogen fragmentation in hydrogenation furnace, take out dehydrogenation, under protective atmosphere, broken to oxidation lubricant and hydrogen magnetic is mixed according to the ratio of 2 ~ 6ml/kg.Carry out airflow milling respectively more subsequently, (Ce
0.9nd
0.1)
31fe
67.39b
0.94tM
0.67and Nd
31fe
67.39b
0.94tM
0.67when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 2500r/min, and obtained granularity of magnet powder is about 3 μm; [(Gd, Ho, Er)
0.6nd
0.4]
31fe
67.39b
0.94tM
0.67when hydrogen breaks powder airflow milling, the rotary speed of separation wheel controls at 5200r/min, and obtained granularity of magnet powder is about 2 μm, then.By high-energy ball milling, the granularity of magnetic being further reduced to is about 0.15 μm.
(4) three kinds of magnetics step 3 prepared according to design mix fully mix in proportion, and the equivalent component of mixing magnetic is (Ce
0.7nd
0.24gd
0.03ho
0.02er
0.01)
31fe
67.39b
0.94tM
0.67.Regulate and control the hydrogen content of now magnetic at about 900ppm; Under inert gas shielding atmosphere, be oriented moulding in the magnetic field of 2.3T in magnetic field intensity by mixing magnetic, then carry out isostatic cool pressing, make blank.
(5) then put into sintering furnace and be warmed up to 350 DEG C of beginnings, be incubated 30 minutes, then often improve 150 DEG C insulation 30 minutes, dehydrogenation, degassed complete after, temperature is risen to 1010 DEG C sintering 4 hours.Then the temper of 4 hours is carried out respectively 830 DEG C and 450 DEG C.
Many Hard Magnetics principal phase (Ce, Nd)-Fe-B/Nd-Fe-B/ (Gd, Ho, the Er)-Fe-B magnet of a kind of trade mark of final acquisition.Adopt NIM-2000HF permanent magnetic material standard measuring equipment to survey the magnetic property of magnet, and the weight-loss ratio under wet heat condition (130 DEG C, 100%RH) is as table 7.
The magnetic property of table 7 embodiment 4 magnet and weight-loss ratio
Claims (10)
1. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet, is characterized in that: this permanent magnet adopts powder to inhale hydrogen control oxygen, presintering Oxidative Dehydrogenation is standby;
In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and final magnet is made up of multiple Hard Magnetic principal phases that magnetocrystalline anisotropy constant k is different, and these Hard Magnetic principal phases all have 2:14:1 type structure, is combined by following three class principal phases:
I) light rare earth phase: based on Ce, La abundant rare earth element (Pr, La, Ce, Nd)-Fe-B phase, can contain a small amount of Pr, Nd, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower;
II) Nd-Fe-B phase: based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher;
III) heavy rare earth phase: be that belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, but not containing Ce, La and Tb;
The chemical formula of described three class principal phases and final permanent magnet can be expressed as by mass percentage: (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1, (Nd
ypr
1-y)
a2fe
100-a2-b2-c2b
b2tM
c2, [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3-b3-c3b
b3tM
c3(Ce, Re)
afe
100-a-b-cb
btM
c; Wherein, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2, a1 ~ a3, b1 ~ b3, the span of c1 ~ c3 is identical with a, b, c respectively, Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, and TM is Ga, Co, one or more in Cu, Nb, Al element.
2. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, is characterized in that: described permanent magnet is prepared by following methods:
1) many major phase raw materials prepares: will not be prepared into containing the principal phase of Dy, Ho, Gd, Er heavy rare earth element and the principal phase containing Dy, Ho, Gd, Er heavy rare earth element rapid-hardening flake that average thickness is 0.1 ~ 0.5mm respectively and average thickness is the rapid tempering belt of 0.03 ~ 0.40mm,, dehydrogenation broken through hydrogen, obtain varigrained magnetic, carry out airflow milling or mechanical ball milling again, for subsequent use;
2) magnet blank is prepared: according to the equivalent component of final magnet, take prepared varigrained magnetic respectively in proportion and fully mix, regulate and control the hydrogen content of now magnetic at 200 ~ 2000ppm, magnetic oriented moulding in magnetic field of mixing, makes blank;
3) sinter: through 400 ~ 850 DEG C of scope classifications insulation, dehydrogenation, degassed, often improve 150 DEG C of insulations 30 minutes, totally 2 ~ 6 hours; Temperature 850 ~ 1050 DEG C of classification heat preservation sinterings 1 ~ 4 hour; Then the temper of 1 ~ 4 hour is carried out respectively 650 ~ 900 DEG C and 350 ~ 500 DEG C.
3. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, it is characterized in that: described permanent magnet is by dehydrogenation, sintering and tempering process, the ceria of minute quantity in magnet is made to transform into stable micro-cerium sesquioxide, suppress the oxygen content in final magnet, improve the corrosion resistance of magnet.
4. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, is characterized in that: the granularity of different principal phase magnetic is different, is respectively: the thick magnetic of the thin magnetic of particle diameter 0.1-2 μm, particle diameter 2-5 μm and nanocrystalline magnetic; In final magnet, the volume fraction shared by Hard Magnetic principal phase of different anisotropy constant k is not identical with granular size, has high corrosion-resistant and the little feature of weight-loss ratio.
5. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, is characterized in that:
Multiple Hard Magnetic principal phases of this permanent magnet comprise and are not limited to following combination:
1) be made up of mutually a Nd-Fe-B principal phase, light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B;
2) be made up of mutually different light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase of two components and heavy rare earth (Dy, Ho, Gd, Er)-Fe-B;
3) be made up of mutually heavy rare earth (Dy, Ho, Gd, the Er)-Fe-B that light rare earth (Ce, La, Nd, Pr)-Fe-B principal phase is different with two components;
4) be made up of light rare earth (Ce, La, Nd, the Pr)-Fe-B principal phase that a Nd-Fe-B principal phase is different from two components; Or
5) heavy rare earth (Dy, Ho, Gd, the Er)-Fe-B that Nd-Fe-B principal phase is different from two components is formed mutually.
6. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, is characterized in that: described permanent magnet has the 4th principal phase magnet, the 5th principal phase magnet or more principal phase magnet further.
7. high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 5, is characterized in that: described permanent magnet has following many Hard Magnetics principal phase structure:
1) the four Hard Magnetic principal phase structures be made up of Ce-Fe-B and Nd-Fe-B, Pr-Fe-B, Dy-Fe-B; Or
2) the four Hard Magnetic principal phase structures be made up of (Pr, Ce)-Fe-B and Nd-Fe-B, (Pr, Gd)-Fe-B, (Ho, Gd)-Fe-B; Or
3) the five stiffness magnetic principal phase structure be made up of (Pr, Ce)-Fe-B and Nd-Fe-B, (Pr, Dy)-Fe-B, (Ho, Gd)-Fe-B, (Nd, Gd, Er)-Fe-B.
8. the preparation method of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 1, it is characterized in that: according to the performance requirement of many Hard Magnetics principal phase Ce-Fe-B permanent-magnet alloy, design the main-phase alloy of different magnetocrystalline anisotropy constant k value, determine the phase structure composition of multiple difference many Hard Magnetics principal phase Ce-Fe-B permanent magnet; In final magnet, Ce is the rare earth element dividing content maximum by mass percentage, and all the other rare earths are the one or two or more mishmetal be selected from La, Nd, Pr, Dy, Ho, Gd, Er, and the method comprises following processing step:
(1) prepare multiple different Hard Magnetic main-phase alloy raw material respectively, these Hard Magnetic principal phases all have 2:14:1 type structure, are combined by following three class principal phases:
I) light rare earth phase: based on the abundant rare earth element of Ce, La (Pr, La, Ce)-Fe-B phase, a small amount of Pr, Nd can be contained, but not containing Dy, Ho, Gd, Er heavy rare earth element, belong to low saturated pole intensity Js and less anisotropy field HA phase, magnetic reversal ability is lower; Composition is (RL
1-x, Ce
x)
a1fe
100-a1-b1-c1b
b1tM
c1(wt.%);
II) Nd-Fe-B phase: based on rare earth element nd, Pr (Nd, Pr)-Fe-B phase, not containing Ce, La, also not containing Dy, Ho, Gd, Er heavy rare earth element, belong to just saturated pole intensity Js and comparatively high anisotropy field HA phase, magnetic reversal ability is higher; Its composition is (Nd
ypr
1- y)
a2fe
100-a2-b2-c2b
b2tM
c2(wt.%);
III) heavy rare earth phase: be that belong to low saturated pole intensity Js and high HA phase, magnetic reversal ability is very high, can contain Pr, Nd containing Dy, Ho, Gd, Er heavy rare earth element (Dy, Ho, Gd, Er)-Fe-B phase, but not containing Ce, La and Tb; Its composition is [RH
z, (Nd, Pr)
1-z]
a3fe
100-a3- b3-c3b
b3tM
c3(wt.%);
Wherein, the span of a1 ~ a3, b1 ~ b3, c1 ~ c3 respectively with final magnet (Ce, Re)
afe
100-a-b-cb
btM
c(wt.%) a in, b, c span is identical, 0.25<x≤1.0,0≤y≤1.0,0<z≤1.0,27≤a≤31,0.8≤b≤1.5,0.5≤c≤2; Re is several in La, Nd, Pr, Dy, Ho, Gd, Er rare earth element, and RL is one or more in La, Pr, Nd rare earth element, and RH is one or more in Dy, Ho, Gd, Er rare earth element, TM is Ga, Co, Cu, one or more in Nb, Al element;
(2) distinguish the raw material that melting step (1) prepares, be poured on water-cooled copper alloy roller by the molten steel not containing Dy, Ho, Gd, Er heavy rare earth element, obtained average thickness is the rapid-hardening flake of 0.1 ~ 0.5mm;
Molten steel containing Dy, Ho, Gd, Er heavy rare earth element is obtained the rapid tempering belt of thickness at 0.03 ~ 0.40mm;
(3) rapid-hardening flake step (2) obtained respectively and rapid tempering belt carry out hydrogen fragmentation, and then, dehydrogenation, respectively through fragmentation, airflow milling or mechanical ball milling, obtains thick magnetic, thin magnetic and nanocrystalline magnetic;
(4) according to the equivalent component (Ce, Re) of final magnet
afe
100-a-b-cb
btM
c(wt.%), determine the content of each main-phase alloy of many principal phases magnet, take the different magnetic of granularity prepared by step (3) by a certain percentage respectively, additional lubricant, mix in batch mixer, and the hydrogen content regulating and controlling now magnetic is at 200 ~ 2000ppm; Under inert gas shielding atmosphere, magnetic oriented moulding in magnetic field will be mixed, make blank;
(5) then put into sintering furnace to be incubated 400 ~ 850 DEG C of scope classifications, dehydrogenation, degassed, often improve 150 DEG C of insulations 30 minutes, totally 2 ~ 6 hours, temperature 850 ~ 1050 DEG C of classification heat preservation sinterings 1 ~ 4 hour; Then the temper of 1 ~ 4 hour is carried out respectively 650 ~ 900 DEG C and 350 ~ 500 DEG C.
9. the preparation method of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 7, it is characterized in that: in step (2), molten steel not containing Dy, Ho, Gd, Er heavy rare earth element is poured on the water-cooled copper alloy roller that linear velocity is 1 ~ 4m/s, the molten steel containing Dy, Ho, Gd, Er heavy rare earth element is poured into the water-cooled molybdenum alloy roller that linear velocity is 15 ~ 40m/s.
10. the preparation method of high corrosion-resistant many Hard Magnetics principal phase Ce permanent magnet according to claim 7, it is characterized in that: in step (3), different principal phase magnetic is prepared into the different magnetic of granularity, is respectively: the thick magnetic of the thin magnetic of particle diameter 0.1-2 μm, particle diameter 2-5 μm and nanocrystalline magnetic.
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