CA2079223A1 - Anisotropic rare earth-fe-b system and rare earth-fe-co-b system magnet - Google Patents
Anisotropic rare earth-fe-b system and rare earth-fe-co-b system magnetInfo
- Publication number
- CA2079223A1 CA2079223A1 CA 2079223 CA2079223A CA2079223A1 CA 2079223 A1 CA2079223 A1 CA 2079223A1 CA 2079223 CA2079223 CA 2079223 CA 2079223 A CA2079223 A CA 2079223A CA 2079223 A1 CA2079223 A1 CA 2079223A1
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- Prior art keywords
- atomic
- molded body
- crystallized grains
- grain diameter
- crystallized
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0573—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes obtained by reduction or by hydrogen decrepitation or embrittlement
Abstract
ABSTRACT OF THE DISCLOSURE
A hot press molded body or an HIP molded body having one of a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, and a total amount of one or a plurality of Ga, Zr, and Hf: 0.001 - 5.5 atomic %, a remainder comprising Fe and unavoidable impurities;
or a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, and a total amount of one or a plurality of Ti, V, Nb, Ta, Al, and Si: 0.001 5.0 atomic %, a remainder comprising Fe and unavoidable impurities;
or a composition comprising Co: 0.1 50 atomic % added to one of the above compositions, having an aggregate structure of crystallized grains having as a main phase thereof a R2Fe14B type or R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains comprising more than 50 volume % of the total crystallized grains comprising the aggregate structure, have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
A hot press molded body or an HIP molded body having one of a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, and a total amount of one or a plurality of Ga, Zr, and Hf: 0.001 - 5.5 atomic %, a remainder comprising Fe and unavoidable impurities;
or a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, and a total amount of one or a plurality of Ti, V, Nb, Ta, Al, and Si: 0.001 5.0 atomic %, a remainder comprising Fe and unavoidable impurities;
or a composition comprising Co: 0.1 50 atomic % added to one of the above compositions, having an aggregate structure of crystallized grains having as a main phase thereof a R2Fe14B type or R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains comprising more than 50 volume % of the total crystallized grains comprising the aggregate structure, have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
Description
2~7~223 ~
SPECIFICATION
ANISOTROPIC RARE EART~-Fe-B SYSTEM AND R~RE EART~-Fe-Co-B
SYSTEM MAGNET
FIELD OF THE INVENTIQN
The pre~ent invention relates to a R twhere R
represents a~ lea~t one type of rare earth element including Y)-Fe-B ~ys~em and a R-Fe-Co-B system anisotropic magnet possessing Superior mag~etlc anisotropy and a small coerclve force temperature coefficient, ~nd relates more particularly ~o an anisGtropiC magnet comprislng a hot pre~s molded body or a hot isostatic press molded body.
PRIOR ART
In Japanese Patent Application, First Publicat~on, ~aid-Open no. Hei 1-132106, a R-Fe-B SyStem permanent magne~ic powder obtalned by means of the hydro~en treatment of a R-Fe-B ystem mother alloy, and a R-Fe-Co B syStem permanent magnetic powder obtained by the hydrogen treatment of a R-Fe-Co-B system mother alloy, are disclosed.
The above R-Fe-B ~ystem permanent magnetic powder ;~ :
utlllzes R-Fe-s system mother alloy as a raw material ~or ~ ::
the main ph~se of a R~Fel4B type intermetalllc com~ound phase (hereinbelow termed the "~2Fel4B type phase") wh~Gh is a ferromagnetic phase; after the heat treatment o thiæ
::
, 2 ~7~2~ ~
mother alloy raw material in a H~ atmosphere withln a speclfied temperature range and the foster:lng of a phase-changed sta~e in each vf the R~x, Fe2B, and the remaini~g Fe phases, the H2 is removed from the raw rnat~rial by means of an H~-desorption process, and the R2Fe14B type phase, whic~ is the ferromagnetic phase, is recreated; t~e R2Fel4B ~.
~ystem perm~nent magnetlc powder obtained as a result has an aggregate structure ~uch that the main phase thereof i~
an extremely fine R2Fel4B type phase having a recrystallized structure and an average gr~n diameter of 0.05 - 3 ~m- :
Furthermore, in the same manner, the above R-Fe-Co~B
system permanent magnetic powder uses R-Fe-Co-B sysk~em mother alloy having as a main phase thereof R2(Fe, C0)l4B
type intermetallic compound (hereinbelow termed R2(Fe, Co)l4B type phase)~ which ls a ferromagnetic phase, a~ a raw material thereof, and this is processed in a manner ldentical to the c3se of ~he above R-Fe-B system; this has an aggrega~e structure hav~g as a main phase thereof an extremely fine R2~Fe, C0)1413 type phase with a recrystallized structure and an average grain diameter of 0.05 - 3 ~m~
The above R-Fe-B system and R-Fe-Co-~ system permanent magnetic powders are una~le to achieve sufficient magnet~ c anisotropy simply as a result of being formed as hot press molded bodies, so that, as disclosed in ~apanese Patent Appllcation, First Publica~ion, Laid~Open No. Hei 2-39503, by carrying out a hot rolling process su~h as hot roll~g or the like on the above hot pre~s molded bodies and thus 2~7~2~3 ~:
creating a rolled structure, the C axes o~ the crystal grains of ~he ~2~el9s phase or the R2(Fe, Co)l4B type phase are oriented, and the magnetic anisotropy thereo i~
increased.
However, R-Fe-~ system and ~e-Co-B system rolled magnets ob~ained by the further hot rolling of a hot pre s molded body possess superlor magnetic anisotropy; but in comparison with magnets wh~ch are produced by the hot pressing of the above R-Fe-B system and R-Fe~Co-13 SyStem permanent magnetic powders obtained by means of hydrogen treatment, the ~emperature coefficient of the coerciv~
force increases ln an undesirable manner, and in the case ln which such a rolled magnet is incorporated in a motor or the llke, the performance of such a motor or the like varles based on tempera~ure, and there is a problem in that .he stabill~y thereof is lacklng.
Fur~hermore, in the above ~-Fe-B syst~m and R-Fe-Co-B
~ystem rolled magnets, position21 variation in the degree of worX~ng causes variations in magnetic anisotropy, 80 that in order to prevent this, it is impossible to avo~d an increase in the complexity of the hot plastlc working processes.
Believing that the above lncrease in the temperature coefficient of the coerci~e force was caused as a result of the hot rolling of a hot press molded body, and base~ on the conviction that if ~ magnet having superior magnetic anisotropy could be obtained without the use of hot ~
rolling, ~his lncrease in th~ tempera~ure coefficient o~ -the coercive force would not occur, the present lnventors .:
~ ~7 ~ ~J ~?, 3 have conduct~d r~search, and have obtained the R-Fe-B
system and R~Fe-Co-B system anisotroplc rnagnets o~ the present invention.
DETAILED DESCRIPTION OF THE INV;EN~ION
The first anisotropic magnet in accordance with the pr~sent inventlon is a R-Fe-B system anisotropic mag~et which is a hot press molded body or a ho~ lsostatl~ pre~s molded body (hereinafter termed an "HIP molded body") having a compo~ition compriSing 10 - 20 atomic ~ Of R, 3 -20 atomlc % of B, and 0.001 - 5.0 atomic ~ of one or the total amount of a plurality of Ga, Zr~ and ~i~ the remainder comprising Fe and unavoidable lmpuritie~; the above hot pres~ molded body or HIP molded body has an ~ggregate structure of crystal gralns hav~ng dlme~sio~
such that the average grain diameter is 0.05 - 20 ~m and having as a main phase thereof a R2Fel4B type intermetallic compound with a tetragonal structure; in addition~ ~0 volume % or more of the total individual crystal grains comprlsing the above aggregate structure have a value of less than ~ for ~/at a for the smallest grain d~ameter and b for the largest grain diameter.
This first anisotropic magnet has a small coerci~e force temperature coef~icient, does not exhi~ he localized va~iations in magnetic anisotropy when compared with convention~l molded magne~s, and also possesses superior corrosion resistance.
Furth~rmore, as this first R-Fe-B system anisotro~lc 2~9~,3 magne~ possesses a crystal grain a~gregate structur~, lt possesses superlor magnetic anisotropy and a high coerc1ve force ln the vicinity of a R2Fe19B type compound composikion, that is to ~ay, in the viclnity of a R11.aFebalBs.9 ~atornic %) composition.
It is acceptable to add, to ~he first R-Fe-~ syst~m anisotropio magnet composition, one or a plurality of a group comprising A1, V, and Si, in a tota1 amount of 0.01 -2.0 atomic %. In such a case, the maximum energy product is further ~ncreased, more striking magnetic anisotropy i~
displayed, and the coercive force temperature coefficient 1s also sma11.
Next, a manufacturing method for the above R-Fe-B
~ystem anisotropic magne~ will be explained. .First, a R-Fe-B qystem mo~her alloy having a fixed component composition contalnlng Ga, Zr, and ~f, or a R-Fe-B system mother alloy comprising a fixed component composition containing Al, V, and Si, in addition to this alloy, is manufactured.
Next, the above R-Fe-B system mother alloy is heated in an atmosphere of hydrogen gas, and is subjected to ~eat processing at a ~emperature of 500 - 1000C in an atmosphere of hydrogen gas or.a mixed atmosphere of hydrogen gas and an inert gas; next, hydrogen de~orped processing 1s conducted at a tempera~ure of 500 - 1000C ~o as to create a vacuum atmosphere in ~hich the hydrogen gas pressure 1s below a level of 1 ~orr or to create an inert gas atmosphere in which the hydrogen gas partial pres~ure is less than 1 Torr~ this is cool~d, a~d thereby a R-Fe-B
- ' . ,. ~ ~ .
2 2 ~
system perman~nt magnetic powder possessing ~uperlor magnetic anisotropy and resistance to corrosion is obtained.
By addlng a homogenizing processing procedure ln which the above R-Fe-B system mother alloy is homogenized at a temperature of 600-1200C prior to the conducting o~ the above heat treatment, and by adding a heat processing procedure in which heat processing is conducted at a ~emperature of 300 - 1000C, after the above hydrogen desorped processing, it is possible to manufacture a R-Fe-.B
system permanent magnetic powder having even more superior magnetic anisotropy and corrosion resistance. The s~ructure of the R-Fe-B system permanent magnetic powder ma~ufactured in the above manner comprises a recrystalll~ed ;~
aggregate qtructure in which recrysta~lized grai~s of a R2Fe1~B t~pe intermetallio compound phase which are free of impurities and st~ains within the grains or at graln boundaries, are aggregated. It is suffic~ent if the average crystalli~ed graln diameter of the recrystallized gr~ins comprising the recrystallized aggregate structure ls wlthin a range of 0.05 - 20 ~m; however, a range of 0.~5 -3 ~m, which is close to the dimensions of the simple m~gnetic domain grain diameter (approximately 0.3 ~m) i~
more preferable.
It ls preferable that the individual recrystalli~ed grains having the above dimensions have a value of le~
than 2 for the ratlo b/a, the ratio between ~he smallest grain diameter a and the largest grain diameter b; it i~
necessary that recrystallized grains havlng ~hi~ form be , .
7 2 ~ 2 ~ ~
present in an amount greater than 50 volume ~ of the total recrystalllzed grains comprising the powder. By means of using recrystallized grains having a shape such that the rat~o b/a of the smal~est grain diameter a and the large~t grain dlameter b ls less than 2, the coerc.ive force of the R-Ft~B system permanent magnet~c po~der is improved, and the temperature coefficient aiHc of the co~erclve force wlthin the temperature range of 25 - 100C becom~s ~maller than 0.5~/C.
Next, by pressing the above R-E~e-B sys~em permanent magnetic powder to a green compact in a magnetic ~eld and then subjecting this green compact ~o hot pressing or as~
HIP process at a temperature of 600C - 900¢, it is po~slble to produce a R-Fe-B system anisotropic magnet which preserves the ~uperlor charac~eristlcs o~ the abo~e R-Fe-B ~ystem permanent mag~etic powder. Furthermore, after conducting hot pressing or an HIP process, by conducting, where necessary, heat processing a~ a temperature of 300C - 1000C, it is possible to improve the coercive force.
When the above green compact is sintered by means of a n~rmal sintering method, a5 the s~ntering ~empera~ure i~
in general, hlgh, the super~ine recrystallized grains of the R-Fe~B sy~tem permanent magnetic powder grow to lar~e cry~talllzed grains, and as the ~agnetic characteristics/
and in par~icular the coercive force, worsen, such a method is no~ preferred. ~ccordingly, it is not preYerable to utilize a normal si~tering method as a method for the manufacture of the R-Fe-B system anisotropic magnets o~ the .
~' , .
2079t~i?~3 presen~ i~ventlon; lt i~ neeessary, ra~her, to util:Lze a hot press method or a HIP method which enables sintering at comparatively low temperatures, and thus to control t~e ~rowth of crystallized grains. Furthermorçr a~ the lmpar~lng of magnetic anisotropy is conducted in a mag~tic field, there ls no necessity to conduct a thermoplastic process after hot pressing or the HIP process.
The rea~ons for the llmitation of the component composition~ a~erage crystallized grain diameter, and cryqtallized grain form of the first R-Fe-B ~ystem anisotropic magnet are as follows.
(a3 R
R exhlbit~ one or a plurality of Nd, Pr, Tb, Dy~ La, Ce, Ho, Er, Eu, Sm, Gd, Tm, Yb, Lu, and Y; ln ~eneral~ Nd is used as a main element, and to this are added other rare eartb elements, and in particular, Tb, Dy, and ~r have the effect of increaslng the coercive force iHc. If the amount of R contained is less ~han 10 atomic ~, or if this amou~t ls greater than 20 atomic %, the coercive force of the anisotropic magnet is reduced, and superior magnetic characterl~tlcs cannot be obtaLned. Accordlngly, the amount of ~ contained is set at a level of 10 - 20 atomic "6 ' ~
(~) B
If the amoun~ of ~ contained is less than 3 atomic %, or ~f this amount is greater than 20 atomic ~, the coerclve force of the an~sotropic magnet is reduced, ~d 3uper~or ~ ~9~
rnagnetic cha~acteris~ics cannot be obtained, 50 that the amount of B contained is set at a level of 3 - 20 atomii c ~ .
It is possible to ~iuhstitute one or a plurallty of C, N, 0~
- P, and F for a port~on of B; th~s is also the cace with the qecond - fourth an~sotropic magnets described hereinafte~. :
!
~c) Ga, Zr, and H~
Ga, Zr, and Hf have ~che function of increasing the coercive force and also stably imparting superior magneltic anisotropy and resistance to corrosion; however, i~ one or a plurali ty of Ga, Zr, and ~f are contained in a ~otal amount of less than 0.001 atomic ~, the deslred efects cannot be ob~ained, while cn the other hand, when the total ~mount contained is greater than 5 . O atomic %, the magnetic characteristics worsen. ~ccordingly, the total amount contained of 1 or a plurallty of ~a, Zr, and Hf i~ ~et to a level of 0.001 - S.O atomic ~d) Al, V, and Si Where necessary, Al, V, and Si may be added a~
components of the R-Fe-B system anisotropic magnet. T~e~ie exhibit the effect of increasing the coercive force;
however, if one or a plurali~y of Al, V, and Si are containPd in a total amount of less than 0.01 atomic ~ th~
deslred ef~ects canno~ be obtained, while on the other hand, when this amount exceeds 2.0 atomic %, the magnetic characte~lstics woxsen. Accordingly, it is preferable that one or a plurality of Al, V, and Si be contained ln a to~al amoun~ of 0.01 ~ 2.0 atomic %.
, . . , :
, : .
`
lo ~ 2~
(e~ Average Cry~tallized Grain Diameter ancl Form Thereof If the average crystallized graln diameter of the crystallized grains comprising ~he struc~ure of the ani~otropic magnet is smaller ~han 0.05 ~m, magnetization ~eco~es a problem, so that this is not deslrable, while on the other hand, at a value of more than 20 ~m, the coexcive force and the angularity of the hysteresis loop is reducedr and furthermore, the temperature coefficient of the coercive force increases, so that this is also not desirable. Accordlngly~ the average crystall~zed grain diameter is set to a value of 0.05 - 2~ ~m. It is more preferable that the average crystalli~ed grain diamet~r be within the range of 0 05 - 3 ~m, which is close ~o the dimension~ of the Yimple magnetlc domain grain diameter ~0.3 ~m). It is preferable that the individual crystallized grain~ have a value of less than 2 for the ratio b/a, the ratio of the smallest grain diameter a a~d the largest grain diameter b; it is necessary that crys~allized gralns ha~ing such a form be present in an amount of greater than 50 volume % of the ~otal crystallized grains. By means of so setting the form of the cryst~llized grains so tha~ a value of less than 2 ~s obtained for the ra~io b/a between the smallest graln diameter a and ~he laxgest grain diameter b, the coercive force of the R-Fe-B system anisotropic magnet ls lmpro~ed~
the re~ist~nce to corrosion increases, and the ~empera~ur~
coefficient of the coerclve force is reduced. Accordingly, the value of b/a of the ~ndl~idual crystalli~ed gralns is set to less than 2.
The second anisotropic magnet in accordanc~ with the present inventlon ls a R-Fe-B system anisotropic ma~et wh~ch i~ a hot press molded body or a ~IP molded body having a composition comprising 10 - 20 atom~c % o~ R, 3 -20 atomtc % of B, and one or a plurality of Ti, V~ Nb~ Ta, Al, and Si in a.total amount of G.001 - 5.0 atomic ~, where~n the remainder comprlses Fe or unavoldable ~
impuritles; the hot press molded body or HIP molded body ;:
above has an aggregate structure of crystallized graln~
having as a rnain phase thereof an R2Fe14B type intermetallic compound with a tetragonal structure, the crystaliized gralns ha~ing an average grain diameter of 0.05 - ~0 ~m, and S0 volume % or more of the individual crystalllzed gralns forming the above aggregate structure have a ratio b/a of the smallest grain diameter a and the largest grain diameter b having a value o~ less than 2. In this second R-Fe-B system anisotropic magnet, as well, :~' superior effects which are identical to tho~e of the above first anisotropic magnet can be obtained.
In manufacturing this second anisotropic magnet~
flrst, a R-Fe~B system mother alloy having a ~ixed component compo~iti~n containing one or a plurality of TiJ :
V, Nb, Ta, Al, and Si i~ sub~ec~ed to melt casting, and lt is ~hen acceptable, using thls as a raw material, to conduct processing in exactly the same manner as that o~
the first anisotropic magnet above.
With respect to Ti, V, Nb, Ta, Al, and Si, by me~n3 of addlng one or a plurality of the~e elements ~o the 12 ~7~2~
components of the ~-Fe B system anisotropic magnet~ the effects of an increase in the coercive force and the stable imparting of superlor magnetic anisotropy ,~nd reslstance to corrosion ca~ be obtalned; however, when t'he total amount of these elements which ~s contained is less t~han 0.001 atomic %~ ~he desired ePfects cannot be obtained, while on the other hand, when thi~ amount exceed~ 5.0 a~omic ~, t~e magnetic characteristics worsen. Accordingly, the tota:l amoun~ of one or a plurality of Ti, V, Nb, Ta, Al, and S1 which is contalned i5 set to a value in the range of 0.001 - 5.0 atomic ~.
Furthermore, in the case o~ this second anl~otropic magnet, even in the case in which at least one o~ Go, Ni, Cu, Zn, Ga, Ge, Zrr Mo, Hf r and W is contained ln an amou~t of 0.001 - 5.0 atomic % in addition to the above composit~on, superior magnetic aniso~ropy and re~i~tance to corrosion can be obtained.
The third anisotropic magnet in accordance with the present invention i9 a R-Fe-CQ-B system anisotroplc magnet comprising a hot press molded body or an HIP molded body having a composition comprising 10 - 20 ato~ic % o~ ~, 0.1 - 50 atomic % of Co, 3 - 20 a~o~ic % of B, and one or a pluro.lity o Gcl~ Pr~ ~nd llf in ~ tot~ mount of 0,001 -5.0 atomic %, whereln ~he remainder comprises Fe or unavoidable lmpurit1es: the hot press molded ~ody or HIP
molded body above has an aggregate s~ructure of crystallizcd grains having as a main phase th~r~of a R2~Fe~
CO)l~B type intermetallic compound having a tetragona:L
structure, the crystallized grains pos~essing an aver,age 13 2~7~23 grain diameter of 0 . 05 - 20 ~m, and ~ore th~n 50 volume ~
of the lndivldual crystallized grains comprisin~ the above a~gregate structure have a ra~io b/a of the smallest grain diameter a and the largest grain diameter b having a value le ~ than 2.
This third anisotropic magnet, as in the cases of the first and 4econd anisotropic magnets above~ also has a tempera~ure coe~fic~ent of the coercive force wh~ch ~s small, and in comparison with the conventivnal rolled magnets, has almost no localized variations in magnetic anisotropy and also possesses superior resistance to corrosion Furthermore, as the magnet has a crystalllzed grain aggregate structure, it has superlor magnetlc anisotropy and a high coercive force ln the vicinity of a R2~Fe, Co)14B type compound composition, that is ~o say, In the vcinity of a R11.g(Fe, Co)balB5.g (atomic %1 composition.
It is acceptable to add one or a plurality of ~1~ V~
and Si in a total amount of 0.01 - 2.0 atomic % ~o the composition of this third anisotropic magnet. In such a case, the maximum energy product will ~e further increa~ed.
In manufacturing this third R-Fe-Co-B system anisotropic magnet, ~irst, a R-Fe-Co-B system mo~he~ alloy havin~ a fixed componen~ composi~cion possessing Ga, Zr9 ancl Hf, or a R-Fe-Co-B syStem mother alloy having a flxed component compositlon In which Al~ V, and Si are added to the above alloy~ ~s manufactured.
Next, this R-Fe-Co-B system mother alloy is hea~ed in an atmosphere of hydroge~ gas, is subjected to heat 1.~ 2~9~
treatment a~ a temperature of 500 - 1000C in an atmosphere of hydrogen gas or a mixed atmosphere of hydrogen gas and an lnert gas, and then hydrogen removal processing ls carr 3 ed out at a temperature of 500 - 1000C so as to produce a vacuum atmosphere having a hydrogen gas pxessure of less than 1 Torr or an inert gas atmosphere ln which the partial pres3ure of hydro~en gas is less than 1 Toxr, and by cooling thls, a R-Fe-Co-B system permanent magnetic powder is obtained~ -By means of the addition of a procedure for homogenizing processing at a temperature of 600 - 1200~
prior to the conducting of the above heat trea~ment of the R-Fe-Co-B sy~tem mother alloy above, and by mean~ of t~e addition of a procedure for heat treatment at a temperature of 300 - 1000C after the hydrogen desorped proce~sl~g above, it is possible ~o create a R-Fe-Co-B system permanent magnetic powder having more superior magnetic anlsotropy and resistance to corrosion.
The struc~ure of the R-Fe-Co-B system permanent magnetic powder produced in the above manner compri~es a recrys~allized aggregate structure in which R2(Fe, Co~l~B
type lntermetallic compound phase recrystallized qr~lns, which are free of impuri~ies or strains wlthin the grains ox a~ the grain boundarles, are aggrega~ed. The average recrystalllzed grain ~lameter of the recrystall~zed grain~
comprlslng this recrystallized aggregate structure is sufflciently within a range of 0.05 - 20 ~m; howe~er, a range of 0.05 - 3 ~m, which is close to ~he dimensions of a single magnetic domain grain diameter (approximately 0.3 1S 2~ 7922~
~m), is more preferable.
It ls preferable that the lndividual recrystallized grains having the above dimensions have a ~oxm such that the value of the ratio b/a of the smallest grain dlameter a and the largest graln diame~er b be less than 2; it is necessary that recrystalli~ed grains having th~s form be pre~ent ln an amount of more than 50 volume % of the total recrystallized grains comprising the s*ructure of t~e individual powders, By means of setting the form of the recrystallized gralns so that the ratio b/~ of the ~mallest grain diameter a and the largest grain diameter b have a value of less than 2~ the coercive force of the R-Fe-Co-B
system permanent magnetic powder is improved, and th~
coercive force tempexature coefficient ~Hc in the temperature range o 25C - lOO~C becomes smaller than 0.6 Furthermore~ as the recrystallized structure o~ the R-Fe-Co-B System permanent magnetic powder produced in thls manner has a recrystallized aggregate structure compriSing materially only ~2(Fe, Co)14B type intermetallic compound pha~e in whlCh a grain boundary phase ls almost nonexistent, it is possible to raise the magnetization values of only the portion having no gra~n boundary phase~
corroslon proceeding along the grain boundary phase is halted, and fu~thermore, as stress de~or~ation resultlng from thermoplastic processes does not exists, the likelihood of stress corrosion is small, and the resistance tv corroslon thus increases.
Next, the R~Fe-Co-B system permanent magnetic powder ~92~
above is pres~ed to a green compact in a magnetlc ~ield, and ~y sub jecting t:his g~een compact ~o hot pressing or a HIP proce~s at a temperature of 600C - 900C, it 1~
possihle to produce a R-Fe-Co-B system anisotropic magnet whlch preserves the superior characteristics of the R-Fe~
Co-B system permanent magnetic powder above. Furthermore, by conducting heat processing at 300C - 1000C where necessary, it is posslble to increase the ,coercive ~orce.
When the green compact above is sintered by a conventional method, as the sintering tempera~ure is normally high, the fine recrystallized grains of the R-~e-Co-B system permanent magnetic powder grow into larye crysta.Llized grains, and as the ma~netic characteristlc~
and pa~ticularly the coercive force, worsen, this i~ not preferable. Furthermore, as the imparting of magnetic anisotropy is conducted in a magnetic field, it is not necessary to conduct a thermoplastic prQCeS5 after hot pressln~ or the HIP process. ~:~
Among the components comprisin~ this thiFd anisotropic magnet, the reason for the limltations of the conta~-ned amount of ~, B, and one or a plurality of Ca, Zr~ and ~, and the reasons for the limitation of the average crystallized grain diameter and crystallized grain ~oxm~
are the same as in the case of the f irst anisotropia magnet which was discussed previously.
With respect to the amount of Co contained, by ad~ing CG to the.composition of the anisotropic ma~net, the coercive force and magnetic temperature characteristics. :~
(for example, the Curie point) of the anisotropic magnet ~`~ 7 ~
are improvedr and moreover, the effec~ of an increase in the resistance to corrosion is obtained; however, when the amount contalned thereof is less than 0.1 ,atomic %, these effects cannot be obtained, while on the other hand, when the amount exceeds 50 atomic %, the magnetic characterist.lcs worsen, so that this i9 not preferable~
Accordingly, the amount of Co contained is set to a range of 0.1 - 50 atomlc ~. When the amount of Co contained i~
in a range o 0.1 - 20 a~omic %, ~he coercive foxce increases to the ~reatest extent, so that it is most preferable to set the amount of Co contained to 0.1 - 20 atomlc ~
Furthermore, the rea~ons for the limitation of the preferable range of amounts o Al, V, and Sl contai~ed are the same as ln the case of the first aniso~ropic magnet which was discussed prevlo~sly.
The fourth anisotropic magnet in accordance wl~h ~he pre~ent inYention is a R-~e-~o-B system anisotropic mag~et which is a hot press molded body or a HIP molded body having a composition containing 10 - 20 atom~c ~ of R~ 0.1 - 50 atomic % of Co, 3 - 20 atomic % of B, 1 or a plurality of Ti, ~, Nb, Ta, Al, and Si in a total amount of 0.001 -5.0 atomic %, where~n the remainder comprise~ Fe and unavoidable impurities; the hot press molded body or HIP
molded body above has an aggregate structure of crystallized grains having as a ~ain phase thereof R2~Fes Co) 14B type intermetallic compound having a tetragonal structure, the crystallized grains having an average grain diameter of 0.05 ~ 20 ~m, ~nd more than 50 volume % of ~he lb 2~ 7~7J3 to~al crystallized grains comprising the above aggregate structure have a ratio b/a of the smallest grai~ diametex a and the largest grain diameter b which has a value o~ less t~an 2.
As in the ca~e o~ the first through third anisotropic magnets a~ove, this ~ourth anisotropic magnet has a small coercive force temperature coefficient, has almost no localized variatlons in magnetic anisotropy in co~parison with conventional rolled magnetst has superior corroSion re~istance, and as this magnet possesses a crystallized ~`
grain a~gregate structure/ lt has superior magnetic anisotropy ~nd a high coercive force even in the vlcin~ty of a R2(Fe, Co)1gB type compound composition, that 1~ to say, in the vicinity of a R11,8 ~Fe, Co)balBs.3 (atomic %) composition.
In ~rder to produce this fourth anisotropic magnet, flr~t, a R-Fe-Co-B system mother alloy having a fixe~
componen~ composition containing one or a plurality of Ti, v, ~b, Ta, P.l, and Si is subjected to melt casting, and using this as a raw matçrial, it is acceptable to conduct proCeSSing whiCh is identical to that in the case of the third anisotropic magnet above.
The xeasons for the limitation of R, B~ Co~ the average crystallized grain diameter, and the crystallized grain form in the component composition of ~he anisotropic magnet of the present invention as given above are the same as in the case of t~e thir~ anisotropic magnet wh~ch was previously discussed. FurthermQre, the reason ~or thr limitation of the numerical value of the total contained - , 19 ~ ~ L~
amount o~ Ti, V, Nb, Ta, Al, and Si is the same as in the c,ase of the second anisotropic ma~net previously discussed.
Even if this fourth anisotropic magnet contai~s at least one of Ni, Cu, Zn, Ga, Ge, Zr, Mo, Hf, and W in an amount of 0.001 - 5.0 atomic %, it possesses superior magnetlc anisotropy and resistance to eorroslon.
EXAMPLES
Next, the f1rst throuqh fourth anisotropic magn~t~ ln accordance with the presen~ invention were pr~duced in the ~ollowlng manner, and the characteristics thereof were determined.
(Examples of the E'irst Anlsotropic Magnet) Ingots of varlous alloys contaning one or a plural~ty of Ga, Zr, and Hf obtained by plasma mel~ing and casting, and ingots of alloys which contained no Ga, Zr, or Hf w~re sub~ected to homogenizing processin~ in an atmosphexe o~
argon gas at a temperature of 1130C for a period of 20 hours, and after this~ these homogenized processed ingots were crushed to a fineness o~ approximately 20 mm to create a raw material alloy.
The raw material alloy was ~aken from room temperature to a temperature of 830C in an atmosphere of hydro~en gas at 1 atmosphere, heat ~reatment was conducted in a hy~rogen atmosphere at a temperature of 830C for a peFiod of 4 hours, and next, hydrogen was desorped so as to obt~ln a vacuum degree of less than l X 1o-l Torr at a temperature of 830C, and lmmediat~ly thereafter, argon gas wa~
, ' :~ ', ~ :' ' 2 o 2 ~ 7 ~ ~ ~
introd~lced an~ rapid cooling conducted. After thiq, hydrogen treatment had been co~pleted, heat processing wa3 conducted in argon gas at a temperature of 650C. The raw material alloy which was obtained was crushed sll~htly in a mo~tar, and a R-Fe-B ~ystem permanent magnetic powder having a mean partlcle size of 50 ~m was 0]3tained.
A green compact was formed by press formlng these R-Fe-B permanent magnetlc powders in a ~S KOe magnetic field, and hot presslng these green compacts at a temperature o 720C and at a pressure of l.S Ton/cm2. By furthar heat processing these molded bodies in a vacuum at a temp~rature of 620C for a period of 2 hours, the R~Fe-B 8y9tem anlsotroplc magnets l - 26 of the presen~ invention and the ~-Fe-B system an~sotropic magnets 1 - 12 of the comparatlve R-Fe-B were obtained. The green compacts whlch wexe ~ormed in a magnetic field were arranged and subiected to hot pressi~g ln such a manner that the orienta~ion direct~on was identical to the dlrection of pressing at tne tlme o~
hot presslng.
On the other hand, the R-~e-B permanent magnetio powder which was produced from alloy ingots containing no Ga, Zr, or Hf was placed in a copper can in a.vacuum, thl~
was heated to a temperature of 720C, and rolling was conducted a number of times so that the rolling ratio re~ched a value of 80%~ and the convent~onal R-Fe B system anlsotrop~c magnet 1 was o~tained.
The component elements of the R-Fe-B system anisotropic magnets 1 - 26 of the present invention, the comparative R-Fe-B system anisotropic magnets 1 - 12, and ~' ' ' ' , ' 2~ ~ 3 ~ ~
the conventional R-Fe-B system anisotropic magnet 1 wh$ch were obtained in the above manner are shown ln Tables 1 -3.
Furthermore~ with respect to the R-Fe-B sy tem ani~otropic magnets 1 - 26, comparative R Fe-B ~y~t~m anisotropic magnets l -- 12 and the conventional ~Fe-B
system anlsotropic magnet 1 ha~ing the compo~ent element3 shown $n Tables 1 - 3, the a~erage crystallized grain dlametex, khe amount (volume %) of crystallized grain . :
present having a form such that the value of the largest grain diameter/smallest grain dlameter is less than 2, the coercive force temperature coefficient aiHc, and the magnetic characterl~tics were determined. These value~ are s~own $n Table~ 4 - 6.
The coerclve force ~c25 at ~5C and the coercive force iHCloo at 100C were measured, and ~he ~bo~e c~erc~ve for~e temperature coefficient aiHc has a value determined by the ~lYision of ~he proportional dlfference o the above coercive forces ~iHCloo - iHc2s~ / iHc2s divided by the temperature difference of 75C.
It was determined from the results of Tahles l - 6 that the R-~e-B system an~ sotropic magnets which were produced by the hot pressing of a green compact obtained by the press formation in a vacuum of R-Fe-B system permanent magnetic po~ders containing one or a plural I ty o~ Ga, Zr, and Hf, in accordance with the present inventlon, had superior magnetic characteristics, and in particular~ had superior maximum energy product ~8~)maX and residual magnetlc flux density Br, and had superior magnetic :~ ' ' ~' '' : ' 7 ~
anisotropy.
However, the comparative an~sotroplc magnets containing no Ga, ær, or Hf, and those comparati~e anisotropic magllets which did not fulflll the condlkion~ of the present invention, had poor magne~ic characterist~cs and magnetic anisotropy. Furthermore, in compari~on with the conventional anisotroplc magnet which was obtained by means of rolllng, the anisotropic magnets of the pxesent invent~on had magnetic characteristics which were essentially fdentical; however, the coerclve force temperature coefficient aiHc was clearly ~maller at a valu0 of approximately -0.5%/C.
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Nex~, vari.ous alloy in~ots having component compositlons containin~ one or a plurality of Al, V, and S1 in additlon to a R-Fe-~ syste~ alloy containing one or a plural~ty of Ga, Zr, and Hf, whlch were obta~ned by means of hlgh frequency lnduction melting and casting, were produced, these ~ngots were subjected to homogenizlng processing in an argon gas atmosphere under conditions such that the temperature was 1130C, and the time of processing was 30 hours, and then these h~mogeni7ing processed in~ot~
~re~e crushed to a fineness of approximately 20 mm to create a r~w material alloy.
The temperature of this raw material all~y was ralsed from room tcmperature to 850~C in an atmosphere of hydrogen gas at a pres~ure of 1 atmosphere, heat treatment was conducted in this hydrogen atmosphere at a temperat~re of 850C fo~ 30 minutes, hydrogen was desorped at a temperature of 850C so as to create a vacuum degree of less than 1 X 10 1 Torr, and immediately thereafter, Ar gas was introduced and rapid cooling was conducted. After this hydrogen treatment, the alloy was lightly crushed in a mortar and R-Fe-B sy~tem permanent magnetic powders havlng a mean partlcle s~ ze of ~0 ~m were obtaine~.
These R-Fe-B ~y~tem permanent magnetic powder~ were : r formed in a magnetic field so as to produce green compacts, these green compacts were vacuum filled and sealed in stainless steel vessels, an ~IP process was conducted under cond~tlon~ such that the temperature was 700C and the pressure was 1.8 Tonfcm2, and thereby, the R-Fe-B sys~em anisotropic magnets 27 - 36 of the present invention and the comparatlve R-Fe-B system anisotropic magnets 13 - 15 w~re pro~uced.
The component elements o~ the R-Fe-B system anl~otropic magnets 27 - 36 oE the present invention and the comparati~e R-Fe-B system anisotropic magnet 13 - 15 are shown ln Table 7. Furthermore, the average crystalltzed grain diametex, the amount (volume ~) of ~rystallized grains present for which the value of the ra~io of the largest grain diameter / smallest grain diameter was less than 2, the coercive force temperature coefflcient aiHc determined by the above method, and the magnetic characteri~tics of these anisotropic magnets were determined, and the results thereof are shown in Tablè 8.
As ls clear from the results of Tables 7 and 8, wi~h respect to anisotropic magnets in which one or a plural~ty of Ga, Zr, and Hf were added in a total amount of 0.001 -S.0 atomic % and one or a plurality of Al, V, and Si were adde~ in a total amount of 0.1 - 2.0 atomic %, the maxlmum energy product was further increased, and mor~ striking magnetlc anisotropy wa~ obtained, while the coercive force temperature coefficient aiHc was also reduced to a value of approximately ~0.5%/C.
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2 ~ . 2 3 ~xamples of the Second Anisotroplc Magnet) Next, a second anisotropic magnet ln accordance with the present invention was produced in the mann~r descri.bed hereinbelow, and the characteristic~ thereof wer2 determined.
I~gots of varlous alloys contai~iny on~e or a plurallty of Ti, V, Nb, Ta, Al, and Si, and ingots of alloys contalning none of Ti, V, Nb, Ta, Al, or Si, which were :
obtalned by means of plasma melting and casting, were sub~ected to homogenizing processing in an atmosphere of Ar gas under oonditions such tha~ the temperature thereof was 1140C, and the processing time was 20 hours, and these homogeniæing processed ingots were then crushed to a 1nenes~ o approxlmately 20 mm to produce raw material alloys.
These raw material alloys were rais~d in temperature from roo~ temperature to 840~C in an atmosphere of hydrogen gas at a pres~ure of 1 atmosphere, heat treatment was conducted in th15 hydrogen atmosphere at a temperature of 840C for a period of 1 hour, and then, hydrogen was desorped at a temperature of 830C so as to produce a ~acuum degree of 1 X lo-l Torr, and direetly thereafter, argon gas was introduced, and rapid cooling was conducted.
~fter the concluaion of this hydrogen treatment, heat processing was conducted in a vacuum at a temperature of 620C Xor a period of 2 hours. The raw material alloys ob~ained were then slightly crushed in a mortar, and magnetic powders h~v~ng a mean particle size of gO ~m were obtained.
2a~9~2~
The magnetic powders thus obtained were press formed in a magnetic f~eld of 25 KOe to produce green compacts, ar~d the~e green compacts were subjected to hot pressing at a temperatux~ of 730C and pressure of 1O5 To~/cm2, vr were sub~ected to a HIP process at a temperature of 700C and a pres~ure of 1.6 Ton/cm2, and furthermore, heat processing was conducted in a vacuum at a temperatu~e of 630C for a perlod of 2 hours. The g~een compacts ~hich were formed in a magnetic field were arranged and hot pressed in such a manner that the orientation direction was in agreement with the pressed dixection at the time of hot pressing.
Among the anisotropic magnets 37 - 78 of the present invent~on and comparative anisotropic magnets 16 - 2~ which were produced ln thls manner, the anisotropic magnets 37 -60 accordlng to the pres~nt lnvention and the comparatlve anl~otroplc magnets 16 - 22 were produced by means of the above hot pres~ing, while the anisot~opic magnet~ 61 - 78 of the presen~ invention and the comparative anisotropic magnets 23 - 29 were produced by means of a HIP prooess.
The densities thereof were all sui~ably accurate, being in a range of 7.5 - 7.6 g/cm3.
Furthermore~ for the purposes of comparison, a R Fe-B
system permanent maqnet1c powder produced from an ingot o~
an alloy containing no Ti, V, Nb, Ta, Al, or S1 ~as placed in a copper can in a ~acuum, this was heated to a temperature of 700QC, rolling was conducted a number of t~mss so that the rolling ratio thereof was 80%, and a conventional a~isotropic magnet 2 was thereby obtained.
The component compositions of the anisotropic ~agnets :
2 ~
37 - 78 of th~ present invention, the comparative anisotroplc magnets 16 - 29 and the conventional an~sotropic ma~net 2 are shown in Tables 9 - 1~.
Fuxthermore, the average crystallized grain diameter, the amount ~volume %) of crystallized grains present having a form in whlch the value of the ra~io of the largest grain dlameter / smallest grain diameter was less than 2, the magnetic characteristics and the coercive force temperature coefficient ~iHc of the various anisotropic magnets was measured, and these values are shown in Tables 15 - 19.
The calculation method o the coercive force temperature coeff~cient ~lHc was identical to that given above.
From the results of Table 15 - 19, it is clear that the anisotropic magnets 37 - 78 of the present invention, whlch were produced by conductlng hot pressing or a ~IP
process on green compacts which were press formed in a magnetic field and con~ained one or a plurality of Ti~ V, Nb, Ta, A1, and S~ had superior magne~ic character~ic~, and in particular, had superior maximum energy product (~H)maX and residual magnetic flux density Br, and with respect to magnet~c anisotropy, had characteristics whlch were equiYalent or superior to those of the conventional anisotropic magnet 2 obtained by means of rolling, and furthermore, with respect to the coercive force temperature coef~lcient aiHc~ the value thereof was clearly smaller than in the case of the conventional anisotropic maqnet 2.
However~ as can be ~een from comparative anlsotropic magn~ts 16 ~ 29, if the contained amounts of one or a plurality of Ti, V, Nb, Ta, Al, and Si diverged from ~he ran~es of the present invention, magnetic anisotrop~
worse~edr so that this was not preferable.
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SPECIFICATION
ANISOTROPIC RARE EART~-Fe-B SYSTEM AND R~RE EART~-Fe-Co-B
SYSTEM MAGNET
FIELD OF THE INVENTIQN
The pre~ent invention relates to a R twhere R
represents a~ lea~t one type of rare earth element including Y)-Fe-B ~ys~em and a R-Fe-Co-B system anisotropic magnet possessing Superior mag~etlc anisotropy and a small coerclve force temperature coefficient, ~nd relates more particularly ~o an anisGtropiC magnet comprislng a hot pre~s molded body or a hot isostatic press molded body.
PRIOR ART
In Japanese Patent Application, First Publicat~on, ~aid-Open no. Hei 1-132106, a R-Fe-B SyStem permanent magne~ic powder obtalned by means of the hydro~en treatment of a R-Fe-B ystem mother alloy, and a R-Fe-Co B syStem permanent magnetic powder obtained by the hydrogen treatment of a R-Fe-Co-B system mother alloy, are disclosed.
The above R-Fe-B ~ystem permanent magnetic powder ;~ :
utlllzes R-Fe-s system mother alloy as a raw material ~or ~ ::
the main ph~se of a R~Fel4B type intermetalllc com~ound phase (hereinbelow termed the "~2Fel4B type phase") wh~Gh is a ferromagnetic phase; after the heat treatment o thiæ
::
, 2 ~7~2~ ~
mother alloy raw material in a H~ atmosphere withln a speclfied temperature range and the foster:lng of a phase-changed sta~e in each vf the R~x, Fe2B, and the remaini~g Fe phases, the H2 is removed from the raw rnat~rial by means of an H~-desorption process, and the R2Fe14B type phase, whic~ is the ferromagnetic phase, is recreated; t~e R2Fel4B ~.
~ystem perm~nent magnetlc powder obtained as a result has an aggregate structure ~uch that the main phase thereof i~
an extremely fine R2Fel4B type phase having a recrystallized structure and an average gr~n diameter of 0.05 - 3 ~m- :
Furthermore, in the same manner, the above R-Fe-Co~B
system permanent magnetic powder uses R-Fe-Co-B sysk~em mother alloy having as a main phase thereof R2(Fe, C0)l4B
type intermetallic compound (hereinbelow termed R2(Fe, Co)l4B type phase)~ which ls a ferromagnetic phase, a~ a raw material thereof, and this is processed in a manner ldentical to the c3se of ~he above R-Fe-B system; this has an aggrega~e structure hav~g as a main phase thereof an extremely fine R2~Fe, C0)1413 type phase with a recrystallized structure and an average grain diameter of 0.05 - 3 ~m~
The above R-Fe-B system and R-Fe-Co-~ system permanent magnetic powders are una~le to achieve sufficient magnet~ c anisotropy simply as a result of being formed as hot press molded bodies, so that, as disclosed in ~apanese Patent Appllcation, First Publica~ion, Laid~Open No. Hei 2-39503, by carrying out a hot rolling process su~h as hot roll~g or the like on the above hot pre~s molded bodies and thus 2~7~2~3 ~:
creating a rolled structure, the C axes o~ the crystal grains of ~he ~2~el9s phase or the R2(Fe, Co)l4B type phase are oriented, and the magnetic anisotropy thereo i~
increased.
However, R-Fe-~ system and ~e-Co-B system rolled magnets ob~ained by the further hot rolling of a hot pre s molded body possess superlor magnetic anisotropy; but in comparison with magnets wh~ch are produced by the hot pressing of the above R-Fe-B system and R-Fe~Co-13 SyStem permanent magnetic powders obtained by means of hydrogen treatment, the ~emperature coefficient of the coerciv~
force increases ln an undesirable manner, and in the case ln which such a rolled magnet is incorporated in a motor or the llke, the performance of such a motor or the like varles based on tempera~ure, and there is a problem in that .he stabill~y thereof is lacklng.
Fur~hermore, in the above ~-Fe-B syst~m and R-Fe-Co-B
~ystem rolled magnets, position21 variation in the degree of worX~ng causes variations in magnetic anisotropy, 80 that in order to prevent this, it is impossible to avo~d an increase in the complexity of the hot plastlc working processes.
Believing that the above lncrease in the temperature coefficient of the coerci~e force was caused as a result of the hot rolling of a hot press molded body, and base~ on the conviction that if ~ magnet having superior magnetic anisotropy could be obtained without the use of hot ~
rolling, ~his lncrease in th~ tempera~ure coefficient o~ -the coercive force would not occur, the present lnventors .:
~ ~7 ~ ~J ~?, 3 have conduct~d r~search, and have obtained the R-Fe-B
system and R~Fe-Co-B system anisotroplc rnagnets o~ the present invention.
DETAILED DESCRIPTION OF THE INV;EN~ION
The first anisotropic magnet in accordance with the pr~sent inventlon is a R-Fe-B system anisotropic mag~et which is a hot press molded body or a ho~ lsostatl~ pre~s molded body (hereinafter termed an "HIP molded body") having a compo~ition compriSing 10 - 20 atomic ~ Of R, 3 -20 atomlc % of B, and 0.001 - 5.0 atomic ~ of one or the total amount of a plurality of Ga, Zr~ and ~i~ the remainder comprising Fe and unavoidable lmpuritie~; the above hot pres~ molded body or HIP molded body has an ~ggregate structure of crystal gralns hav~ng dlme~sio~
such that the average grain diameter is 0.05 - 20 ~m and having as a main phase thereof a R2Fel4B type intermetallic compound with a tetragonal structure; in addition~ ~0 volume % or more of the total individual crystal grains comprlsing the above aggregate structure have a value of less than ~ for ~/at a for the smallest grain d~ameter and b for the largest grain diameter.
This first anisotropic magnet has a small coerci~e force temperature coef~icient, does not exhi~ he localized va~iations in magnetic anisotropy when compared with convention~l molded magne~s, and also possesses superior corrosion resistance.
Furth~rmore, as this first R-Fe-B system anisotro~lc 2~9~,3 magne~ possesses a crystal grain a~gregate structur~, lt possesses superlor magnetic anisotropy and a high coerc1ve force ln the vicinity of a R2Fe19B type compound composikion, that is to ~ay, in the viclnity of a R11.aFebalBs.9 ~atornic %) composition.
It is acceptable to add, to ~he first R-Fe-~ syst~m anisotropio magnet composition, one or a plurality of a group comprising A1, V, and Si, in a tota1 amount of 0.01 -2.0 atomic %. In such a case, the maximum energy product is further ~ncreased, more striking magnetic anisotropy i~
displayed, and the coercive force temperature coefficient 1s also sma11.
Next, a manufacturing method for the above R-Fe-B
~ystem anisotropic magne~ will be explained. .First, a R-Fe-B qystem mo~her alloy having a fixed component composition contalnlng Ga, Zr, and ~f, or a R-Fe-B system mother alloy comprising a fixed component composition containing Al, V, and Si, in addition to this alloy, is manufactured.
Next, the above R-Fe-B system mother alloy is heated in an atmosphere of hydrogen gas, and is subjected to ~eat processing at a ~emperature of 500 - 1000C in an atmosphere of hydrogen gas or.a mixed atmosphere of hydrogen gas and an inert gas; next, hydrogen de~orped processing 1s conducted at a tempera~ure of 500 - 1000C ~o as to create a vacuum atmosphere in ~hich the hydrogen gas pressure 1s below a level of 1 ~orr or to create an inert gas atmosphere in which the hydrogen gas partial pres~ure is less than 1 Torr~ this is cool~d, a~d thereby a R-Fe-B
- ' . ,. ~ ~ .
2 2 ~
system perman~nt magnetic powder possessing ~uperlor magnetic anisotropy and resistance to corrosion is obtained.
By addlng a homogenizing processing procedure ln which the above R-Fe-B system mother alloy is homogenized at a temperature of 600-1200C prior to the conducting o~ the above heat treatment, and by adding a heat processing procedure in which heat processing is conducted at a ~emperature of 300 - 1000C, after the above hydrogen desorped processing, it is possible to manufacture a R-Fe-.B
system permanent magnetic powder having even more superior magnetic anisotropy and corrosion resistance. The s~ructure of the R-Fe-B system permanent magnetic powder ma~ufactured in the above manner comprises a recrystalll~ed ;~
aggregate qtructure in which recrysta~lized grai~s of a R2Fe1~B t~pe intermetallio compound phase which are free of impurities and st~ains within the grains or at graln boundaries, are aggregated. It is suffic~ent if the average crystalli~ed graln diameter of the recrystallized gr~ins comprising the recrystallized aggregate structure ls wlthin a range of 0.05 - 20 ~m; however, a range of 0.~5 -3 ~m, which is close to the dimensions of the simple m~gnetic domain grain diameter (approximately 0.3 ~m) i~
more preferable.
It ls preferable that the individual recrystalli~ed grains having the above dimensions have a value of le~
than 2 for the ratlo b/a, the ratio between ~he smallest grain diameter a and the largest grain diameter b; it i~
necessary that recrystallized grains havlng ~hi~ form be , .
7 2 ~ 2 ~ ~
present in an amount greater than 50 volume ~ of the total recrystalllzed grains comprising the powder. By means of using recrystallized grains having a shape such that the rat~o b/a of the smal~est grain diameter a and the large~t grain dlameter b ls less than 2, the coerc.ive force of the R-Ft~B system permanent magnet~c po~der is improved, and the temperature coefficient aiHc of the co~erclve force wlthin the temperature range of 25 - 100C becom~s ~maller than 0.5~/C.
Next, by pressing the above R-E~e-B sys~em permanent magnetic powder to a green compact in a magnetic ~eld and then subjecting this green compact ~o hot pressing or as~
HIP process at a temperature of 600C - 900¢, it is po~slble to produce a R-Fe-B system anisotropic magnet which preserves the ~uperlor charac~eristlcs o~ the abo~e R-Fe-B ~ystem permanent mag~etic powder. Furthermore, after conducting hot pressing or an HIP process, by conducting, where necessary, heat processing a~ a temperature of 300C - 1000C, it is possible to improve the coercive force.
When the above green compact is sintered by means of a n~rmal sintering method, a5 the s~ntering ~empera~ure i~
in general, hlgh, the super~ine recrystallized grains of the R-Fe~B sy~tem permanent magnetic powder grow to lar~e cry~talllzed grains, and as the ~agnetic characteristics/
and in par~icular the coercive force, worsen, such a method is no~ preferred. ~ccordingly, it is not preYerable to utilize a normal si~tering method as a method for the manufacture of the R-Fe-B system anisotropic magnets o~ the .
~' , .
2079t~i?~3 presen~ i~ventlon; lt i~ neeessary, ra~her, to util:Lze a hot press method or a HIP method which enables sintering at comparatively low temperatures, and thus to control t~e ~rowth of crystallized grains. Furthermorçr a~ the lmpar~lng of magnetic anisotropy is conducted in a mag~tic field, there ls no necessity to conduct a thermoplastic process after hot pressing or the HIP process.
The rea~ons for the llmitation of the component composition~ a~erage crystallized grain diameter, and cryqtallized grain form of the first R-Fe-B ~ystem anisotropic magnet are as follows.
(a3 R
R exhlbit~ one or a plurality of Nd, Pr, Tb, Dy~ La, Ce, Ho, Er, Eu, Sm, Gd, Tm, Yb, Lu, and Y; ln ~eneral~ Nd is used as a main element, and to this are added other rare eartb elements, and in particular, Tb, Dy, and ~r have the effect of increaslng the coercive force iHc. If the amount of R contained is less ~han 10 atomic ~, or if this amou~t ls greater than 20 atomic %, the coercive force of the anisotropic magnet is reduced, and superior magnetic characterl~tlcs cannot be obtaLned. Accordlngly, the amount of ~ contained is set at a level of 10 - 20 atomic "6 ' ~
(~) B
If the amoun~ of ~ contained is less than 3 atomic %, or ~f this amount is greater than 20 atomic ~, the coerclve force of the an~sotropic magnet is reduced, ~d 3uper~or ~ ~9~
rnagnetic cha~acteris~ics cannot be obtained, 50 that the amount of B contained is set at a level of 3 - 20 atomii c ~ .
It is possible to ~iuhstitute one or a plurallty of C, N, 0~
- P, and F for a port~on of B; th~s is also the cace with the qecond - fourth an~sotropic magnets described hereinafte~. :
!
~c) Ga, Zr, and H~
Ga, Zr, and Hf have ~che function of increasing the coercive force and also stably imparting superior magneltic anisotropy and resistance to corrosion; however, i~ one or a plurali ty of Ga, Zr, and ~f are contained in a ~otal amount of less than 0.001 atomic ~, the deslred efects cannot be ob~ained, while cn the other hand, when the total ~mount contained is greater than 5 . O atomic %, the magnetic characteristics worsen. ~ccordingly, the total amount contained of 1 or a plurallty of ~a, Zr, and Hf i~ ~et to a level of 0.001 - S.O atomic ~d) Al, V, and Si Where necessary, Al, V, and Si may be added a~
components of the R-Fe-B system anisotropic magnet. T~e~ie exhibit the effect of increasing the coercive force;
however, if one or a plurali~y of Al, V, and Si are containPd in a total amount of less than 0.01 atomic ~ th~
deslred ef~ects canno~ be obtained, while on the other hand, when this amount exceeds 2.0 atomic %, the magnetic characte~lstics woxsen. Accordingly, it is preferable that one or a plurality of Al, V, and Si be contained ln a to~al amoun~ of 0.01 ~ 2.0 atomic %.
, . . , :
, : .
`
lo ~ 2~
(e~ Average Cry~tallized Grain Diameter ancl Form Thereof If the average crystallized graln diameter of the crystallized grains comprising ~he struc~ure of the ani~otropic magnet is smaller ~han 0.05 ~m, magnetization ~eco~es a problem, so that this is not deslrable, while on the other hand, at a value of more than 20 ~m, the coexcive force and the angularity of the hysteresis loop is reducedr and furthermore, the temperature coefficient of the coercive force increases, so that this is also not desirable. Accordlngly~ the average crystall~zed grain diameter is set to a value of 0.05 - 2~ ~m. It is more preferable that the average crystalli~ed grain diamet~r be within the range of 0 05 - 3 ~m, which is close ~o the dimension~ of the Yimple magnetlc domain grain diameter ~0.3 ~m). It is preferable that the individual crystallized grain~ have a value of less than 2 for the ratio b/a, the ratio of the smallest grain diameter a a~d the largest grain diameter b; it is necessary that crys~allized gralns ha~ing such a form be present in an amount of greater than 50 volume % of the ~otal crystallized grains. By means of so setting the form of the cryst~llized grains so tha~ a value of less than 2 ~s obtained for the ra~io b/a between the smallest graln diameter a and ~he laxgest grain diameter b, the coercive force of the R-Fe-B system anisotropic magnet ls lmpro~ed~
the re~ist~nce to corrosion increases, and the ~empera~ur~
coefficient of the coerclve force is reduced. Accordingly, the value of b/a of the ~ndl~idual crystalli~ed gralns is set to less than 2.
The second anisotropic magnet in accordanc~ with the present inventlon ls a R-Fe-B system anisotropic ma~et wh~ch i~ a hot press molded body or a ~IP molded body having a composition comprising 10 - 20 atom~c % o~ R, 3 -20 atomtc % of B, and one or a plurality of Ti, V~ Nb~ Ta, Al, and Si in a.total amount of G.001 - 5.0 atomic ~, where~n the remainder comprlses Fe or unavoldable ~
impuritles; the hot press molded body or HIP molded body ;:
above has an aggregate structure of crystallized graln~
having as a rnain phase thereof an R2Fe14B type intermetallic compound with a tetragonal structure, the crystaliized gralns ha~ing an average grain diameter of 0.05 - ~0 ~m, and S0 volume % or more of the individual crystalllzed gralns forming the above aggregate structure have a ratio b/a of the smallest grain diameter a and the largest grain diameter b having a value o~ less than 2. In this second R-Fe-B system anisotropic magnet, as well, :~' superior effects which are identical to tho~e of the above first anisotropic magnet can be obtained.
In manufacturing this second anisotropic magnet~
flrst, a R-Fe~B system mother alloy having a ~ixed component compo~iti~n containing one or a plurality of TiJ :
V, Nb, Ta, Al, and Si i~ sub~ec~ed to melt casting, and lt is ~hen acceptable, using thls as a raw material, to conduct processing in exactly the same manner as that o~
the first anisotropic magnet above.
With respect to Ti, V, Nb, Ta, Al, and Si, by me~n3 of addlng one or a plurality of the~e elements ~o the 12 ~7~2~
components of the ~-Fe B system anisotropic magnet~ the effects of an increase in the coercive force and the stable imparting of superlor magnetic anisotropy ,~nd reslstance to corrosion ca~ be obtalned; however, when t'he total amount of these elements which ~s contained is less t~han 0.001 atomic %~ ~he desired ePfects cannot be obtained, while on the other hand, when thi~ amount exceed~ 5.0 a~omic ~, t~e magnetic characteristics worsen. Accordingly, the tota:l amoun~ of one or a plurality of Ti, V, Nb, Ta, Al, and S1 which is contalned i5 set to a value in the range of 0.001 - 5.0 atomic ~.
Furthermore, in the case o~ this second anl~otropic magnet, even in the case in which at least one o~ Go, Ni, Cu, Zn, Ga, Ge, Zrr Mo, Hf r and W is contained ln an amou~t of 0.001 - 5.0 atomic % in addition to the above composit~on, superior magnetic aniso~ropy and re~i~tance to corrosion can be obtained.
The third anisotropic magnet in accordance with the present invention i9 a R-Fe-CQ-B system anisotroplc magnet comprising a hot press molded body or an HIP molded body having a composition comprising 10 - 20 ato~ic % o~ ~, 0.1 - 50 atomic % of Co, 3 - 20 a~o~ic % of B, and one or a pluro.lity o Gcl~ Pr~ ~nd llf in ~ tot~ mount of 0,001 -5.0 atomic %, whereln ~he remainder comprises Fe or unavoidable lmpurit1es: the hot press molded ~ody or HIP
molded body above has an aggregate s~ructure of crystallizcd grains having as a main phase th~r~of a R2~Fe~
CO)l~B type intermetallic compound having a tetragona:L
structure, the crystallized grains pos~essing an aver,age 13 2~7~23 grain diameter of 0 . 05 - 20 ~m, and ~ore th~n 50 volume ~
of the lndivldual crystallized grains comprisin~ the above a~gregate structure have a ra~io b/a of the smallest grain diameter a and the largest grain diameter b having a value le ~ than 2.
This third anisotropic magnet, as in the cases of the first and 4econd anisotropic magnets above~ also has a tempera~ure coe~fic~ent of the coercive force wh~ch ~s small, and in comparison with the conventivnal rolled magnets, has almost no localized variations in magnetic anisotropy and also possesses superior resistance to corrosion Furthermore, as the magnet has a crystalllzed grain aggregate structure, it has superlor magnetlc anisotropy and a high coercive force ln the vicinity of a R2~Fe, Co)14B type compound composition, that is ~o say, In the vcinity of a R11.g(Fe, Co)balB5.g (atomic %1 composition.
It is acceptable to add one or a plurality of ~1~ V~
and Si in a total amount of 0.01 - 2.0 atomic % ~o the composition of this third anisotropic magnet. In such a case, the maximum energy product will ~e further increa~ed.
In manufacturing this third R-Fe-Co-B system anisotropic magnet, ~irst, a R-Fe-Co-B system mo~he~ alloy havin~ a fixed componen~ composi~cion possessing Ga, Zr9 ancl Hf, or a R-Fe-Co-B syStem mother alloy having a flxed component compositlon In which Al~ V, and Si are added to the above alloy~ ~s manufactured.
Next, this R-Fe-Co-B system mother alloy is hea~ed in an atmosphere of hydroge~ gas, is subjected to heat 1.~ 2~9~
treatment a~ a temperature of 500 - 1000C in an atmosphere of hydrogen gas or a mixed atmosphere of hydrogen gas and an lnert gas, and then hydrogen removal processing ls carr 3 ed out at a temperature of 500 - 1000C so as to produce a vacuum atmosphere having a hydrogen gas pxessure of less than 1 Torr or an inert gas atmosphere ln which the partial pres3ure of hydro~en gas is less than 1 Toxr, and by cooling thls, a R-Fe-Co-B system permanent magnetic powder is obtained~ -By means of the addition of a procedure for homogenizing processing at a temperature of 600 - 1200~
prior to the conducting of the above heat trea~ment of the R-Fe-Co-B sy~tem mother alloy above, and by mean~ of t~e addition of a procedure for heat treatment at a temperature of 300 - 1000C after the hydrogen desorped proce~sl~g above, it is possible ~o create a R-Fe-Co-B system permanent magnetic powder having more superior magnetic anlsotropy and resistance to corrosion.
The struc~ure of the R-Fe-Co-B system permanent magnetic powder produced in the above manner compri~es a recrys~allized aggregate structure in which R2(Fe, Co~l~B
type lntermetallic compound phase recrystallized qr~lns, which are free of impuri~ies or strains wlthin the grains ox a~ the grain boundarles, are aggrega~ed. The average recrystalllzed grain ~lameter of the recrystall~zed grain~
comprlslng this recrystallized aggregate structure is sufflciently within a range of 0.05 - 20 ~m; howe~er, a range of 0.05 - 3 ~m, which is close to ~he dimensions of a single magnetic domain grain diameter (approximately 0.3 1S 2~ 7922~
~m), is more preferable.
It ls preferable that the lndividual recrystallized grains having the above dimensions have a ~oxm such that the value of the ratio b/a of the smallest grain dlameter a and the largest graln diame~er b be less than 2; it is necessary that recrystalli~ed grains having th~s form be pre~ent ln an amount of more than 50 volume % of the total recrystallized grains comprising the s*ructure of t~e individual powders, By means of setting the form of the recrystallized gralns so that the ratio b/~ of the ~mallest grain diameter a and the largest grain diameter b have a value of less than 2~ the coercive force of the R-Fe-Co-B
system permanent magnetic powder is improved, and th~
coercive force tempexature coefficient ~Hc in the temperature range o 25C - lOO~C becomes smaller than 0.6 Furthermore~ as the recrystallized structure o~ the R-Fe-Co-B System permanent magnetic powder produced in thls manner has a recrystallized aggregate structure compriSing materially only ~2(Fe, Co)14B type intermetallic compound pha~e in whlCh a grain boundary phase ls almost nonexistent, it is possible to raise the magnetization values of only the portion having no gra~n boundary phase~
corroslon proceeding along the grain boundary phase is halted, and fu~thermore, as stress de~or~ation resultlng from thermoplastic processes does not exists, the likelihood of stress corrosion is small, and the resistance tv corroslon thus increases.
Next, the R~Fe-Co-B system permanent magnetic powder ~92~
above is pres~ed to a green compact in a magnetlc ~ield, and ~y sub jecting t:his g~een compact ~o hot pressing or a HIP proce~s at a temperature of 600C - 900C, it 1~
possihle to produce a R-Fe-Co-B system anisotropic magnet whlch preserves the superior characteristics of the R-Fe~
Co-B system permanent magnetic powder above. Furthermore, by conducting heat processing at 300C - 1000C where necessary, it is posslble to increase the ,coercive ~orce.
When the green compact above is sintered by a conventional method, as the sintering tempera~ure is normally high, the fine recrystallized grains of the R-~e-Co-B system permanent magnetic powder grow into larye crysta.Llized grains, and as the ma~netic characteristlc~
and pa~ticularly the coercive force, worsen, this i~ not preferable. Furthermore, as the imparting of magnetic anisotropy is conducted in a magnetic field, it is not necessary to conduct a thermoplastic prQCeS5 after hot pressln~ or the HIP process. ~:~
Among the components comprisin~ this thiFd anisotropic magnet, the reason for the limltations of the conta~-ned amount of ~, B, and one or a plurality of Ca, Zr~ and ~, and the reasons for the limitation of the average crystallized grain diameter and crystallized grain ~oxm~
are the same as in the case of the f irst anisotropia magnet which was discussed previously.
With respect to the amount of Co contained, by ad~ing CG to the.composition of the anisotropic ma~net, the coercive force and magnetic temperature characteristics. :~
(for example, the Curie point) of the anisotropic magnet ~`~ 7 ~
are improvedr and moreover, the effec~ of an increase in the resistance to corrosion is obtained; however, when the amount contalned thereof is less than 0.1 ,atomic %, these effects cannot be obtained, while on the other hand, when the amount exceeds 50 atomic %, the magnetic characterist.lcs worsen, so that this i9 not preferable~
Accordingly, the amount of Co contained is set to a range of 0.1 - 50 atomlc ~. When the amount of Co contained i~
in a range o 0.1 - 20 a~omic %, ~he coercive foxce increases to the ~reatest extent, so that it is most preferable to set the amount of Co contained to 0.1 - 20 atomlc ~
Furthermore, the rea~ons for the limitation of the preferable range of amounts o Al, V, and Sl contai~ed are the same as ln the case of the first aniso~ropic magnet which was discussed prevlo~sly.
The fourth anisotropic magnet in accordance wl~h ~he pre~ent inYention is a R-~e-~o-B system anisotropic mag~et which is a hot press molded body or a HIP molded body having a composition containing 10 - 20 atom~c ~ of R~ 0.1 - 50 atomic % of Co, 3 - 20 atomic % of B, 1 or a plurality of Ti, ~, Nb, Ta, Al, and Si in a total amount of 0.001 -5.0 atomic %, where~n the remainder comprise~ Fe and unavoidable impurities; the hot press molded body or HIP
molded body above has an aggregate structure of crystallized grains having as a ~ain phase thereof R2~Fes Co) 14B type intermetallic compound having a tetragonal structure, the crystallized grains having an average grain diameter of 0.05 ~ 20 ~m, ~nd more than 50 volume % of ~he lb 2~ 7~7J3 to~al crystallized grains comprising the above aggregate structure have a ratio b/a of the smallest grai~ diametex a and the largest grain diameter b which has a value o~ less t~an 2.
As in the ca~e o~ the first through third anisotropic magnets a~ove, this ~ourth anisotropic magnet has a small coercive force temperature coefficient, has almost no localized variatlons in magnetic anisotropy in co~parison with conventional rolled magnetst has superior corroSion re~istance, and as this magnet possesses a crystallized ~`
grain a~gregate structure/ lt has superior magnetic anisotropy ~nd a high coercive force even in the vlcin~ty of a R2(Fe, Co)1gB type compound composition, that 1~ to say, in the vicinity of a R11,8 ~Fe, Co)balBs.3 (atomic %) composition.
In ~rder to produce this fourth anisotropic magnet, flr~t, a R-Fe-Co-B system mother alloy having a fixe~
componen~ composition containing one or a plurality of Ti, v, ~b, Ta, P.l, and Si is subjected to melt casting, and using this as a raw matçrial, it is acceptable to conduct proCeSSing whiCh is identical to that in the case of the third anisotropic magnet above.
The xeasons for the limitation of R, B~ Co~ the average crystallized grain diameter, and the crystallized grain form in the component composition of ~he anisotropic magnet of the present invention as given above are the same as in the case of t~e thir~ anisotropic magnet wh~ch was previously discussed. FurthermQre, the reason ~or thr limitation of the numerical value of the total contained - , 19 ~ ~ L~
amount o~ Ti, V, Nb, Ta, Al, and Si is the same as in the c,ase of the second anisotropic ma~net previously discussed.
Even if this fourth anisotropic magnet contai~s at least one of Ni, Cu, Zn, Ga, Ge, Zr, Mo, Hf, and W in an amount of 0.001 - 5.0 atomic %, it possesses superior magnetlc anisotropy and resistance to eorroslon.
EXAMPLES
Next, the f1rst throuqh fourth anisotropic magn~t~ ln accordance with the presen~ invention were pr~duced in the ~ollowlng manner, and the characteristics thereof were determined.
(Examples of the E'irst Anlsotropic Magnet) Ingots of varlous alloys contaning one or a plural~ty of Ga, Zr, and Hf obtained by plasma mel~ing and casting, and ingots of alloys which contained no Ga, Zr, or Hf w~re sub~ected to homogenizing processin~ in an atmosphexe o~
argon gas at a temperature of 1130C for a period of 20 hours, and after this~ these homogenized processed ingots were crushed to a fineness o~ approximately 20 mm to create a raw material alloy.
The raw material alloy was ~aken from room temperature to a temperature of 830C in an atmosphere of hydro~en gas at 1 atmosphere, heat ~reatment was conducted in a hy~rogen atmosphere at a temperature of 830C for a peFiod of 4 hours, and next, hydrogen was desorped so as to obt~ln a vacuum degree of less than l X 1o-l Torr at a temperature of 830C, and lmmediat~ly thereafter, argon gas wa~
, ' :~ ', ~ :' ' 2 o 2 ~ 7 ~ ~ ~
introd~lced an~ rapid cooling conducted. After thiq, hydrogen treatment had been co~pleted, heat processing wa3 conducted in argon gas at a temperature of 650C. The raw material alloy which was obtained was crushed sll~htly in a mo~tar, and a R-Fe-B ~ystem permanent magnetic powder having a mean partlcle size of 50 ~m was 0]3tained.
A green compact was formed by press formlng these R-Fe-B permanent magnetlc powders in a ~S KOe magnetic field, and hot presslng these green compacts at a temperature o 720C and at a pressure of l.S Ton/cm2. By furthar heat processing these molded bodies in a vacuum at a temp~rature of 620C for a period of 2 hours, the R~Fe-B 8y9tem anlsotroplc magnets l - 26 of the presen~ invention and the ~-Fe-B system an~sotropic magnets 1 - 12 of the comparatlve R-Fe-B were obtained. The green compacts whlch wexe ~ormed in a magnetic field were arranged and subiected to hot pressi~g ln such a manner that the orienta~ion direct~on was identical to the dlrection of pressing at tne tlme o~
hot presslng.
On the other hand, the R-~e-B permanent magnetio powder which was produced from alloy ingots containing no Ga, Zr, or Hf was placed in a copper can in a.vacuum, thl~
was heated to a temperature of 720C, and rolling was conducted a number of times so that the rolling ratio re~ched a value of 80%~ and the convent~onal R-Fe B system anlsotrop~c magnet 1 was o~tained.
The component elements of the R-Fe-B system anisotropic magnets 1 - 26 of the present invention, the comparative R-Fe-B system anisotropic magnets 1 - 12, and ~' ' ' ' , ' 2~ ~ 3 ~ ~
the conventional R-Fe-B system anisotropic magnet 1 wh$ch were obtained in the above manner are shown ln Tables 1 -3.
Furthermore~ with respect to the R-Fe-B sy tem ani~otropic magnets 1 - 26, comparative R Fe-B ~y~t~m anisotropic magnets l -- 12 and the conventional ~Fe-B
system anlsotropic magnet 1 ha~ing the compo~ent element3 shown $n Tables 1 - 3, the a~erage crystallized grain dlametex, khe amount (volume %) of crystallized grain . :
present having a form such that the value of the largest grain diameter/smallest grain dlameter is less than 2, the coercive force temperature coefficient aiHc, and the magnetic characterl~tics were determined. These value~ are s~own $n Table~ 4 - 6.
The coerclve force ~c25 at ~5C and the coercive force iHCloo at 100C were measured, and ~he ~bo~e c~erc~ve for~e temperature coefficient aiHc has a value determined by the ~lYision of ~he proportional dlfference o the above coercive forces ~iHCloo - iHc2s~ / iHc2s divided by the temperature difference of 75C.
It was determined from the results of Tahles l - 6 that the R-~e-B system an~ sotropic magnets which were produced by the hot pressing of a green compact obtained by the press formation in a vacuum of R-Fe-B system permanent magnetic po~ders containing one or a plural I ty o~ Ga, Zr, and Hf, in accordance with the present inventlon, had superior magnetic characteristics, and in particular~ had superior maximum energy product ~8~)maX and residual magnetlc flux density Br, and had superior magnetic :~ ' ' ~' '' : ' 7 ~
anisotropy.
However, the comparative an~sotroplc magnets containing no Ga, ær, or Hf, and those comparati~e anisotropic magllets which did not fulflll the condlkion~ of the present invention, had poor magne~ic characterist~cs and magnetic anisotropy. Furthermore, in compari~on with the conventional anisotroplc magnet which was obtained by means of rolllng, the anisotropic magnets of the pxesent invent~on had magnetic characteristics which were essentially fdentical; however, the coerclve force temperature coefficient aiHc was clearly ~maller at a valu0 of approximately -0.5%/C.
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Nex~, vari.ous alloy in~ots having component compositlons containin~ one or a plurality of Al, V, and S1 in additlon to a R-Fe-~ syste~ alloy containing one or a plural~ty of Ga, Zr, and Hf, whlch were obta~ned by means of hlgh frequency lnduction melting and casting, were produced, these ~ngots were subjected to homogenizlng processing in an argon gas atmosphere under conditions such that the temperature was 1130C, and the time of processing was 30 hours, and then these h~mogeni7ing processed in~ot~
~re~e crushed to a fineness of approximately 20 mm to create a r~w material alloy.
The temperature of this raw material all~y was ralsed from room tcmperature to 850~C in an atmosphere of hydrogen gas at a pres~ure of 1 atmosphere, heat treatment was conducted in this hydrogen atmosphere at a temperat~re of 850C fo~ 30 minutes, hydrogen was desorped at a temperature of 850C so as to create a vacuum degree of less than 1 X 10 1 Torr, and immediately thereafter, Ar gas was introduced and rapid cooling was conducted. After this hydrogen treatment, the alloy was lightly crushed in a mortar and R-Fe-B sy~tem permanent magnetic powders havlng a mean partlcle s~ ze of ~0 ~m were obtaine~.
These R-Fe-B ~y~tem permanent magnetic powder~ were : r formed in a magnetic field so as to produce green compacts, these green compacts were vacuum filled and sealed in stainless steel vessels, an ~IP process was conducted under cond~tlon~ such that the temperature was 700C and the pressure was 1.8 Tonfcm2, and thereby, the R-Fe-B sys~em anisotropic magnets 27 - 36 of the present invention and the comparatlve R-Fe-B system anisotropic magnets 13 - 15 w~re pro~uced.
The component elements o~ the R-Fe-B system anl~otropic magnets 27 - 36 oE the present invention and the comparati~e R-Fe-B system anisotropic magnet 13 - 15 are shown ln Table 7. Furthermore, the average crystalltzed grain diametex, the amount (volume ~) of ~rystallized grains present for which the value of the ra~io of the largest grain diameter / smallest grain diameter was less than 2, the coercive force temperature coefflcient aiHc determined by the above method, and the magnetic characteri~tics of these anisotropic magnets were determined, and the results thereof are shown in Tablè 8.
As ls clear from the results of Tables 7 and 8, wi~h respect to anisotropic magnets in which one or a plural~ty of Ga, Zr, and Hf were added in a total amount of 0.001 -S.0 atomic % and one or a plurality of Al, V, and Si were adde~ in a total amount of 0.1 - 2.0 atomic %, the maxlmum energy product was further increased, and mor~ striking magnetlc anisotropy wa~ obtained, while the coercive force temperature coefficient aiHc was also reduced to a value of approximately ~0.5%/C.
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2 ~ . 2 3 ~xamples of the Second Anisotroplc Magnet) Next, a second anisotropic magnet ln accordance with the present invention was produced in the mann~r descri.bed hereinbelow, and the characteristic~ thereof wer2 determined.
I~gots of varlous alloys contai~iny on~e or a plurallty of Ti, V, Nb, Ta, Al, and Si, and ingots of alloys contalning none of Ti, V, Nb, Ta, Al, or Si, which were :
obtalned by means of plasma melting and casting, were sub~ected to homogenizing processing in an atmosphere of Ar gas under oonditions such tha~ the temperature thereof was 1140C, and the processing time was 20 hours, and these homogeniæing processed ingots were then crushed to a 1nenes~ o approxlmately 20 mm to produce raw material alloys.
These raw material alloys were rais~d in temperature from roo~ temperature to 840~C in an atmosphere of hydrogen gas at a pres~ure of 1 atmosphere, heat treatment was conducted in th15 hydrogen atmosphere at a temperature of 840C for a period of 1 hour, and then, hydrogen was desorped at a temperature of 830C so as to produce a ~acuum degree of 1 X lo-l Torr, and direetly thereafter, argon gas was introduced, and rapid cooling was conducted.
~fter the concluaion of this hydrogen treatment, heat processing was conducted in a vacuum at a temperature of 620C Xor a period of 2 hours. The raw material alloys ob~ained were then slightly crushed in a mortar, and magnetic powders h~v~ng a mean particle size of gO ~m were obtained.
2a~9~2~
The magnetic powders thus obtained were press formed in a magnetic f~eld of 25 KOe to produce green compacts, ar~d the~e green compacts were subjected to hot pressing at a temperatux~ of 730C and pressure of 1O5 To~/cm2, vr were sub~ected to a HIP process at a temperature of 700C and a pres~ure of 1.6 Ton/cm2, and furthermore, heat processing was conducted in a vacuum at a temperatu~e of 630C for a perlod of 2 hours. The g~een compacts ~hich were formed in a magnetic field were arranged and hot pressed in such a manner that the orientation direction was in agreement with the pressed dixection at the time of hot pressing.
Among the anisotropic magnets 37 - 78 of the present invent~on and comparative anisotropic magnets 16 - 2~ which were produced ln thls manner, the anisotropic magnets 37 -60 accordlng to the pres~nt lnvention and the comparatlve anl~otroplc magnets 16 - 22 were produced by means of the above hot pres~ing, while the anisot~opic magnet~ 61 - 78 of the presen~ invention and the comparative anisotropic magnets 23 - 29 were produced by means of a HIP prooess.
The densities thereof were all sui~ably accurate, being in a range of 7.5 - 7.6 g/cm3.
Furthermore~ for the purposes of comparison, a R Fe-B
system permanent maqnet1c powder produced from an ingot o~
an alloy containing no Ti, V, Nb, Ta, Al, or S1 ~as placed in a copper can in a ~acuum, this was heated to a temperature of 700QC, rolling was conducted a number of t~mss so that the rolling ratio thereof was 80%, and a conventional a~isotropic magnet 2 was thereby obtained.
The component compositions of the anisotropic ~agnets :
2 ~
37 - 78 of th~ present invention, the comparative anisotroplc magnets 16 - 29 and the conventional an~sotropic ma~net 2 are shown in Tables 9 - 1~.
Fuxthermore, the average crystallized grain diameter, the amount ~volume %) of crystallized grains present having a form in whlch the value of the ra~io of the largest grain dlameter / smallest grain diameter was less than 2, the magnetic characteristics and the coercive force temperature coefficient ~iHc of the various anisotropic magnets was measured, and these values are shown in Tables 15 - 19.
The calculation method o the coercive force temperature coeff~cient ~lHc was identical to that given above.
From the results of Table 15 - 19, it is clear that the anisotropic magnets 37 - 78 of the present invention, whlch were produced by conductlng hot pressing or a ~IP
process on green compacts which were press formed in a magnetic field and con~ained one or a plurality of Ti~ V, Nb, Ta, A1, and S~ had superior magne~ic character~ic~, and in particular, had superior maximum energy product (~H)maX and residual magnetic flux density Br, and with respect to magnet~c anisotropy, had characteristics whlch were equiYalent or superior to those of the conventional anisotropic magnet 2 obtained by means of rolling, and furthermore, with respect to the coercive force temperature coef~lcient aiHc~ the value thereof was clearly smaller than in the case of the conventional anisotropic maqnet 2.
However~ as can be ~een from comparative anlsotropic magn~ts 16 ~ 29, if the contained amounts of one or a plurality of Ti, V, Nb, Ta, Al, and Si diverged from ~he ran~es of the present invention, magnetic anisotrop~
worse~edr so that this was not preferable.
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(Examples of the Third Anisotropic Magnet) Next, a third anisotropic magnet in accordance with the present invention was produced in the manner describçd herelnafter, and the characteristics thereo:f were determined.
Ingots of varlous R-Fe-Co-B system alloys contalning Co and one or a plurality of Ga, Zr, and Hf~ and lngot~ ~f R-Fe-Co-B system alloys containing ~o Ga, Zr, or H~ which ~;
were obtained by means of plasma melting and castingr were prepared, these alloy ingots were subjecte~ to homoge~&ing ~ :~
processing ln an argon gas atmosphere under condit~ons such that the temperature thereof was 1120C~ and the processi~g time was qO hours, and thexeafter, these homogenizing processed ingots were crushed to a fineness o~ 20 mm to form a raw materlal alloy.
The temperature of this raw material alloy was ralsed from room temperature to a ~emperature of 830C i~ a ~ :
hydrogen a~mosphere at a pressure of 1 atmosphere, heat trea~ment was conducted in this hydrogen atmospher~ at a temperature of 830C for a period of 9 hour~, and then, hydrogen was desorped at a temperature of 830C so as to produce a vacuum degree of less than 1 X lo-l Torr, and directly there~fter, argon gas was introduced and rapid cooling conducted.
Af~er the conclusion of the above hydrogen treatment, the ingots were slightly crushed in mortars, and various ~-Fe-Co-s system perma~ent magnetic powders having a ~ean particle size of 50 ~m were obtained.
These R-Fe-Co-B sys~em permanent magne~ic powders were ~ ~ r7 9 ~ 2 press formed in a magnetic field so as to form gre~n compacts, and th~se green compacts were ~ub~ected to hot presslng under condit~ons such that the temperature was 700C and the pressure was l.S Ton/cm2. At this t1me, arrangement and hot pressing were conductedl in such a manner that the orientation direct~on was identical wi~
the press direction at the t~me of ho~ presslng.
By means of further sub~ect~ng the variou~ mold~d bodies to heat processing at a temperature o~ 6~0C and for a period of 2 hours, the anisotropic magnets 79 - 109 of ~:
the present 1nvention and the comparative anisotropic magnets 30 - 39 sh~wn ln Tables 20 - 23 were produced~ The densitles o~ these anisotropic magnets were su~fic1erltly accurate, being in a range of 7~5 to 7.6 g/cm3.
On the other han~, a R-Fe-Co-B system permanent magnetic powder p~oduced ~rom an ingot of an alloy ~
conta~ning no Ga, Zr, or Hf was placed in a copper can ~n a ~:
~acuum, this was heated to a temperature of ~/00C and rolling was conducted a number of times so that the roll~ng ratio reached 80%, and the conventional anisotropic magnet 3 shown ln Table 23 was obtained.
The varlou~ structures of the anisotroplc magnets i9 -109 of the present inven~ion, the comparative anisotropic magnets 30 - 39, and the conventional an1sstrop1c magn0t 3 having the componen~ composi~ions shown in Tables 20 - 22 were observed by means o~ a scanning electron microscope, and the avèrage crystallized grain diameter, the amount o~
crystallized grains present having a form in whlch the ratio of the largest grain diameter / smallest grain 2 ~ 7 ~ ~ ~ c~
diameter had a value of less than Z, the coercive force temperature coefficient aiHc and the ma~netic characteristics were determined. The values o~ta~ned thereby are shown in Tables 24 - 27. The Imethod o~
calculation of the coercive force temperature coe~icient iHc is as given above.
It is clear ~rom the results shown in Tables 20 - 27 that the anisotropic magnets 79 - 109 in accordance wlth the present invention which contaln one or a plurality of Ga, Zr, and Hf have superior magnetic characteristics, an~
~n partlcular, have superior maximum e~ergy product ~)~ax and resldual magnetic flux denslty Br, and ~urthermore~
have superior anisotropy. Furthermore, in comparl~on with the conventional an~sotropic m~gnet 3 obtained by meanY.of rolling, the anisotropic ma~net 79 - 109 of the present invention possess essentially identical magnetic characteristics; however, the coercive force temperature coeff~cient aiRc thereof is markedly smaller, having a value of approximately ~O.S~/C. In addi~ion, in the case , of the comparatlve anisotropic magnets 30 - 39, the compositions of which lie outside the ranges of the present inventlon, ~he ma~neti~ characteristics and magnetic anisotro~y worsen.
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(Examples of the Third Anisotropic Magnet) Next, a third anisotropic magnet in accordance with the present invention was produced in the manner describçd herelnafter, and the characteristics thereo:f were determined.
Ingots of varlous R-Fe-Co-B system alloys contalning Co and one or a plurality of Ga, Zr, and Hf~ and lngot~ ~f R-Fe-Co-B system alloys containing ~o Ga, Zr, or H~ which ~;
were obtained by means of plasma melting and castingr were prepared, these alloy ingots were subjecte~ to homoge~&ing ~ :~
processing ln an argon gas atmosphere under condit~ons such that the temperature thereof was 1120C~ and the processi~g time was qO hours, and thexeafter, these homogenizing processed ingots were crushed to a fineness o~ 20 mm to form a raw materlal alloy.
The temperature of this raw material alloy was ralsed from room temperature to a ~emperature of 830C i~ a ~ :
hydrogen a~mosphere at a pressure of 1 atmosphere, heat trea~ment was conducted in this hydrogen atmospher~ at a temperature of 830C for a period of 9 hour~, and then, hydrogen was desorped at a temperature of 830C so as to produce a vacuum degree of less than 1 X lo-l Torr, and directly there~fter, argon gas was introduced and rapid cooling conducted.
Af~er the conclusion of the above hydrogen treatment, the ingots were slightly crushed in mortars, and various ~-Fe-Co-s system perma~ent magnetic powders having a ~ean particle size of 50 ~m were obtained.
These R-Fe-Co-B sys~em permanent magne~ic powders were ~ ~ r7 9 ~ 2 press formed in a magnetic field so as to form gre~n compacts, and th~se green compacts were ~ub~ected to hot presslng under condit~ons such that the temperature was 700C and the pressure was l.S Ton/cm2. At this t1me, arrangement and hot pressing were conductedl in such a manner that the orientation direct~on was identical wi~
the press direction at the t~me of ho~ presslng.
By means of further sub~ect~ng the variou~ mold~d bodies to heat processing at a temperature o~ 6~0C and for a period of 2 hours, the anisotropic magnets 79 - 109 of ~:
the present 1nvention and the comparative anisotropic magnets 30 - 39 sh~wn ln Tables 20 - 23 were produced~ The densitles o~ these anisotropic magnets were su~fic1erltly accurate, being in a range of 7~5 to 7.6 g/cm3.
On the other han~, a R-Fe-Co-B system permanent magnetic powder p~oduced ~rom an ingot of an alloy ~
conta~ning no Ga, Zr, or Hf was placed in a copper can ~n a ~:
~acuum, this was heated to a temperature of ~/00C and rolling was conducted a number of times so that the roll~ng ratio reached 80%, and the conventional anisotropic magnet 3 shown ln Table 23 was obtained.
The varlou~ structures of the anisotroplc magnets i9 -109 of the present inven~ion, the comparative anisotropic magnets 30 - 39, and the conventional an1sstrop1c magn0t 3 having the componen~ composi~ions shown in Tables 20 - 22 were observed by means o~ a scanning electron microscope, and the avèrage crystallized grain diameter, the amount o~
crystallized grains present having a form in whlch the ratio of the largest grain diameter / smallest grain 2 ~ 7 ~ ~ ~ c~
diameter had a value of less than Z, the coercive force temperature coefficient aiHc and the ma~netic characteristics were determined. The values o~ta~ned thereby are shown in Tables 24 - 27. The Imethod o~
calculation of the coercive force temperature coe~icient iHc is as given above.
It is clear ~rom the results shown in Tables 20 - 27 that the anisotropic magnets 79 - 109 in accordance wlth the present invention which contaln one or a plurality of Ga, Zr, and Hf have superior magnetic characteristics, an~
~n partlcular, have superior maximum e~ergy product ~)~ax and resldual magnetic flux denslty Br, and ~urthermore~
have superior anisotropy. Furthermore, in comparl~on with the conventional an~sotropic m~gnet 3 obtained by meanY.of rolling, the anisotropic ma~net 79 - 109 of the present invention possess essentially identical magnetic characteristics; however, the coercive force temperature coeff~cient aiRc thereof is markedly smaller, having a value of approximately ~O.S~/C. In addi~ion, in the case , of the comparatlve anisotropic magnets 30 - 39, the compositions of which lie outside the ranges of the present inventlon, ~he ma~neti~ characteristics and magnetic anisotro~y worsen.
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~Other Examples of the Third ~niso~ropic Magnet) Next, ingo cs of ~ari~us alloys hav~ng componentcomposltions co ltainlng vne or ~ plurality of Al, V, and S~
~n addi~i.on to ~ R-Fe-Co-B system ~lloy conta~nlng one or a plurality of Ga ~r~ and ~f obtain~d ~y means of h~gh frequency induc ~ion melting and ca$ting, were prepar~d, these ingots we re processed by a method identical to t~at of the anisotro pic magnets 79 - 10~ and the comparati~e aniso~ropic mag nets 30 - 39 above, and ~-Fe-Co-B system permanent magne tic powders having ~ mean par~icle s~ze of 40 ~m were pro uced. These permanent magnetic powder~ were press formed in the presence or ab~ence of a magnetic ~ield to form green c ~mpacts, these gxeen compacts were ~ubje~ted to hot isostati c presSing un~er condit~ons such th~t th~
temperature th reof was 710C, and the pressure thereof was 1.7 Ton/cm2, an the anisotropic m~gnets 110 - 119 o the present inventil n and the comparati~e a~isotropic magnets :~
qO - 42 compri~ing the component c~mpositi~ns shown in Table 28 were btained.
The avera e crystallized grain diame~er, the amou~t (volume %) of rys~allized grains present fo~ ~hich the value of the r tio of the largest grain diamete~ / ~malle~t grain dlameter was less than 2, the coercive ~orce ~: :
temperat~re co ff~clent ai~c and the magnetic charac~eristic of these anisotroplc magnets were determined in ma~ner identical t~ that akove. The results thèreo are shown in Table 29.
As can be ~een ~rom the resul~s of Table~ ~8 and 29, by mean~ of adc ing 0.1 - 2.0 atomlc ~ of one or a plurality ' ' ' , , ~ 7J'~
of Al, V, and S: . to 0.01 -5.0 atomic % of 1 or ~ plu~ality of Ga, Zr, aAd ~ ~f, the maximum ene~gy product ls further increased. Fur¦hermore, it is cle~r that the crys~allized grain diame~er nd the form of ~he crystal]Lized ~rains have a large effect n the reduction o the coercive ~or~e temperature coe ficient. -~
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~Other Examples of the Third ~niso~ropic Magnet) Next, ingo cs of ~ari~us alloys hav~ng componentcomposltions co ltainlng vne or ~ plurality of Al, V, and S~
~n addi~i.on to ~ R-Fe-Co-B system ~lloy conta~nlng one or a plurality of Ga ~r~ and ~f obtain~d ~y means of h~gh frequency induc ~ion melting and ca$ting, were prepar~d, these ingots we re processed by a method identical to t~at of the anisotro pic magnets 79 - 10~ and the comparati~e aniso~ropic mag nets 30 - 39 above, and ~-Fe-Co-B system permanent magne tic powders having ~ mean par~icle s~ze of 40 ~m were pro uced. These permanent magnetic powder~ were press formed in the presence or ab~ence of a magnetic ~ield to form green c ~mpacts, these gxeen compacts were ~ubje~ted to hot isostati c presSing un~er condit~ons such th~t th~
temperature th reof was 710C, and the pressure thereof was 1.7 Ton/cm2, an the anisotropic m~gnets 110 - 119 o the present inventil n and the comparati~e a~isotropic magnets :~
qO - 42 compri~ing the component c~mpositi~ns shown in Table 28 were btained.
The avera e crystallized grain diame~er, the amou~t (volume %) of rys~allized grains present fo~ ~hich the value of the r tio of the largest grain diamete~ / ~malle~t grain dlameter was less than 2, the coercive ~orce ~: :
temperat~re co ff~clent ai~c and the magnetic charac~eristic of these anisotroplc magnets were determined in ma~ner identical t~ that akove. The results thèreo are shown in Table 29.
As can be ~een ~rom the resul~s of Table~ ~8 and 29, by mean~ of adc ing 0.1 - 2.0 atomlc ~ of one or a plurality ' ' ' , , ~ 7J'~
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(Example of a ourth Anisotropic M~gnet) Next, a f urth anisotropic ma~net in ,accordanGe with the present in ention ~as produced in the ,manner detailed hereinbelow, a d the characteristics thereof ~ere determined~
In~ots of a R-Fe-Co-B system ~lloy containing one or plurality of Ti , V, Nb, Ta, Al, an~ Sl, and ingot3 of a R
Fe-Co-B system alloy which contained no Tl, V, Nb, Ta~ Al, or Sl, which w re obtained by means of plasma melt$ng ~d oasting, were s b~ected to homogenizing processing ~ n an atmosphere of rgon gas under conditions such that the temperature th reof was 1130C, and the processing time thereof was 20 hours, and thereafter, ~hese homogen~zi~g ~ :
proce~sed ~ngo s were crushed to a fineness of approximately 5 mm to form ~w material alloys.
The tempe atuxe of these raw ~aterial alloys wa3 raised from ro m temperature to 830C in an atmosphere ~f hydrogen gas a a pressure of 1 atmosphere, heat treat~ent was carried ou in an atmosphere o~ hydrogen gas at a temperature of 830C for a period of 1 hour, hydrogen w~
desorped at a emperature of ~30~ in order ~o produce a vacuum degree f le~s than 1 X 10-a Torr, and ~mmediately thereafter, ar on gas was in~roduced and rapl~ cooli~g conducted. Af er the conclusion o~ this hydrogen treatmen~, heat processing was conducted in a vacuum at tempera~ure of¦630C for a period of 2 hours. The raw material alloy~ thus obtalned were sl~gh~ly cru~hed i~
mortars, and m~gnetic powders ha~i~g a mean partlcle si~e of 40 ~m were ~bt~ined.
' -~ 3 These magne ic powders were press formed in a ~5 KO~magnetic field o produce green compacts, and each gr~n compact was sub ected to hot presslQg under conditivn~ ~uch that the temper ture thereof was 7~0~C and t:he pre~sure thereo~ was l.S Ton/cm2, or was sub~jec~ed to a ~IP proce~
under condition such that the temperature ther~o wa~
710C and the p essure thereof was 1.5 Ton/om2, ~nd furthermore, ea h melted body was then sub~ected to heat processing a~ a temperature of 620~C fo~ a period of 2 h~urs. The gre n compacts which w~re formed in a magnet~c fleld were arra ged and hot pressed in a such a manner that the orientation direction was iden~ical with the presqln~
direction o~ th ~ hot pressing.
Among the ~nisQtropic magnets 12~ - 164 o~ the present invention and t ~e comparative anisOtropic magnet~ 43 - 5 which were prod Iced in the above m~nner, anisotropic magnets 120 - 1 4 o~ the present inventiOn and comparati~e anisotropio mag lets 43 - 49 were p~oduced by me~ns Gf hot : -pre~slng, while anisotropic magnet~ 1~5 - 1~4 of th~ ' present inventi ~n and comparative ~nisotropic ma~n~ts 50 -56 were produce 1 by ~eans of an HIP method. ~he den~ty thereof was ln ~11 cases s~fficien~ly accurate, being within a range ~f 7.5 - 7.6 g~cm3.
Furthermor ~, for the purposes of comparison~ a ~-~e-Co-B sy3tem per nanent magnetic pow~er produced from an ingot of an all ~y co~taining no Ti, V, Nb, Ta, Al~ vr Si was placed in a copper can in a va¢uum, this was he~ted ~o a temperature o f 720C, and rolling ~as conducted a number of t~mes so tha ~he rolling r~io reached a value of ~0~, , :
. ~5 ~ 2~
and thus a conv ntlonal a~lisotropic magnet 4 was obtained.
The compon nt compositions of the anisotropic magnets 120 - 164 of th 5 present invention, the comparative anisotropic mag ets ~3 - 56, and the conventional anisotropic mag let 4 obtained in the above manrler are sh~wn in Tables 30 - 5. In addition, t~e average crystallized grain diameter, the amount (vol~me %) of crystallized grains present laving a form in which the value of the :
ratio o the la -gest grain diameter / smallest graiD
dlameter is les than 2, the magne~ic characteristics, and ~he coercive fo ce temperature coe~ficient aiHc of these anisotropic maq lets were deterrnined by a method ldent~cal to that given a ~ove, and the resul~ing values are shown ln Tables 36 - 40.
From the r ~ult~ of Tables 36 - 40, it i clear that the R-Fe-Co-B s ~stem anlsotropic m~gnets 120 - 164 o~ t~e present inventi ~n containing one or a plurality o~ V~ :
Nb, Ta, Al, and Si, have essentially identical magnetic characteristics when compared wi~h the conventlonal anisotropic mag let 9, which doe~ n~t contain the~e elements; howev ~r, the coercive fo~ce temperatu~e coefficient is nar~edly smaller. ~urthermore, when the contained amoun of Ti, V, Nb, Ta, Al, and Si lies outs~de the range~ of t ~e present invention, as in the case of the comparative anl otropic magnets 43 - 56, the mag~e~lc anisotropy wors ~ns, and it is cleax that the crystallize~
grain diameter ~r~d cxystall ized gr~ form also have a large lnfluence on ~he magnetic ch~racteristicsv b/~ ~ .
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In accorda. Ice with the presen~ invent:Lon~ by mea~s of uslng a hydroge I treated powder of a R-~e-3 sy~tem or a h-Fe-Co-~ system ~ontaining one or a plurality of Ga, Zr, and ~f~ or containi lg one or a plurali~y of Ti, V, Nb, ~a, Al, and Si, i~ ls p ~sslble to obtain ad anisotropic ma~net ~r which the magne ic anisotropy is l~rge/ and moreover, the coercive force remperature coefficlent is small, so that there is no nee ~ to conduct a magn~tic anisotropizing proce~s such as a thermoplastic pr~cess or ~he l~e, as ln the conventiona 1 method, and produ~tion costs can be thereby reduce cons~der~bly. Acc~rdlngly, the invention contributes gre tly to the abllity to produce electronic machines such a motors and the like and to improvements ln ~ta~ility.
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(Example of a ourth Anisotropic M~gnet) Next, a f urth anisotropic ma~net in ,accordanGe with the present in ention ~as produced in the ,manner detailed hereinbelow, a d the characteristics thereof ~ere determined~
In~ots of a R-Fe-Co-B system ~lloy containing one or plurality of Ti , V, Nb, Ta, Al, an~ Sl, and ingot3 of a R
Fe-Co-B system alloy which contained no Tl, V, Nb, Ta~ Al, or Sl, which w re obtained by means of plasma melt$ng ~d oasting, were s b~ected to homogenizing processing ~ n an atmosphere of rgon gas under conditions such that the temperature th reof was 1130C, and the processing time thereof was 20 hours, and thereafter, ~hese homogen~zi~g ~ :
proce~sed ~ngo s were crushed to a fineness of approximately 5 mm to form ~w material alloys.
The tempe atuxe of these raw ~aterial alloys wa3 raised from ro m temperature to 830C in an atmosphere ~f hydrogen gas a a pressure of 1 atmosphere, heat treat~ent was carried ou in an atmosphere o~ hydrogen gas at a temperature of 830C for a period of 1 hour, hydrogen w~
desorped at a emperature of ~30~ in order ~o produce a vacuum degree f le~s than 1 X 10-a Torr, and ~mmediately thereafter, ar on gas was in~roduced and rapl~ cooli~g conducted. Af er the conclusion o~ this hydrogen treatmen~, heat processing was conducted in a vacuum at tempera~ure of¦630C for a period of 2 hours. The raw material alloy~ thus obtalned were sl~gh~ly cru~hed i~
mortars, and m~gnetic powders ha~i~g a mean partlcle si~e of 40 ~m were ~bt~ined.
' -~ 3 These magne ic powders were press formed in a ~5 KO~magnetic field o produce green compacts, and each gr~n compact was sub ected to hot presslQg under conditivn~ ~uch that the temper ture thereof was 7~0~C and t:he pre~sure thereo~ was l.S Ton/cm2, or was sub~jec~ed to a ~IP proce~
under condition such that the temperature ther~o wa~
710C and the p essure thereof was 1.5 Ton/om2, ~nd furthermore, ea h melted body was then sub~ected to heat processing a~ a temperature of 620~C fo~ a period of 2 h~urs. The gre n compacts which w~re formed in a magnet~c fleld were arra ged and hot pressed in a such a manner that the orientation direction was iden~ical with the presqln~
direction o~ th ~ hot pressing.
Among the ~nisQtropic magnets 12~ - 164 o~ the present invention and t ~e comparative anisOtropic magnet~ 43 - 5 which were prod Iced in the above m~nner, anisotropic magnets 120 - 1 4 o~ the present inventiOn and comparati~e anisotropio mag lets 43 - 49 were p~oduced by me~ns Gf hot : -pre~slng, while anisotropic magnet~ 1~5 - 1~4 of th~ ' present inventi ~n and comparative ~nisotropic ma~n~ts 50 -56 were produce 1 by ~eans of an HIP method. ~he den~ty thereof was ln ~11 cases s~fficien~ly accurate, being within a range ~f 7.5 - 7.6 g~cm3.
Furthermor ~, for the purposes of comparison~ a ~-~e-Co-B sy3tem per nanent magnetic pow~er produced from an ingot of an all ~y co~taining no Ti, V, Nb, Ta, Al~ vr Si was placed in a copper can in a va¢uum, this was he~ted ~o a temperature o f 720C, and rolling ~as conducted a number of t~mes so tha ~he rolling r~io reached a value of ~0~, , :
. ~5 ~ 2~
and thus a conv ntlonal a~lisotropic magnet 4 was obtained.
The compon nt compositions of the anisotropic magnets 120 - 164 of th 5 present invention, the comparative anisotropic mag ets ~3 - 56, and the conventional anisotropic mag let 4 obtained in the above manrler are sh~wn in Tables 30 - 5. In addition, t~e average crystallized grain diameter, the amount (vol~me %) of crystallized grains present laving a form in which the value of the :
ratio o the la -gest grain diameter / smallest graiD
dlameter is les than 2, the magne~ic characteristics, and ~he coercive fo ce temperature coe~ficient aiHc of these anisotropic maq lets were deterrnined by a method ldent~cal to that given a ~ove, and the resul~ing values are shown ln Tables 36 - 40.
From the r ~ult~ of Tables 36 - 40, it i clear that the R-Fe-Co-B s ~stem anlsotropic m~gnets 120 - 164 o~ t~e present inventi ~n containing one or a plurality o~ V~ :
Nb, Ta, Al, and Si, have essentially identical magnetic characteristics when compared wi~h the conventlonal anisotropic mag let 9, which doe~ n~t contain the~e elements; howev ~r, the coercive fo~ce temperatu~e coefficient is nar~edly smaller. ~urthermore, when the contained amoun of Ti, V, Nb, Ta, Al, and Si lies outs~de the range~ of t ~e present invention, as in the case of the comparative anl otropic magnets 43 - 56, the mag~e~lc anisotropy wors ~ns, and it is cleax that the crystallize~
grain diameter ~r~d cxystall ized gr~ form also have a large lnfluence on ~he magnetic ch~racteristicsv b/~ ~ .
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In accorda. Ice with the presen~ invent:Lon~ by mea~s of uslng a hydroge I treated powder of a R-~e-3 sy~tem or a h-Fe-Co-~ system ~ontaining one or a plurality of Ga, Zr, and ~f~ or containi lg one or a plurali~y of Ti, V, Nb, ~a, Al, and Si, i~ ls p ~sslble to obtain ad anisotropic ma~net ~r which the magne ic anisotropy is l~rge/ and moreover, the coercive force remperature coefficlent is small, so that there is no nee ~ to conduct a magn~tic anisotropizing proce~s such as a thermoplastic pr~cess or ~he l~e, as ln the conventiona 1 method, and produ~tion costs can be thereby reduce cons~der~bly. Acc~rdlngly, the invention contributes gre tly to the abllity to produce electronic machines such a motors and the like and to improvements ln ~ta~ility.
..7 ~ ~ !
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A rare earth-Fe-B system anisotropic magnet having as main components thereof at least 1 rare earth element including Y (hereinafter termed "R") and Fe and B, characterized in that this anisotropic magnet is a hot press molded body or a hot isostatic press molded body (hereinafter termed an "HIP molded body") having a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, and total amount of one or a plurality of Ga, Zr, and Hf:
0.001 - 5.0 atomic %, a remainder comprising Fe and unavoidable impurities;
said hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof a R2Fe14B type intermetallic compound having a tetragonal structure the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains comprising more than 50 volume % of total crystallized grains comprising the aggregate structure have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
0.001 - 5.0 atomic %, a remainder comprising Fe and unavoidable impurities;
said hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof a R2Fe14B type intermetallic compound having a tetragonal structure the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains comprising more than 50 volume % of total crystallized grains comprising the aggregate structure have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
2. A rare earth-Fe-B system anisotropic magnet having as main components thereof R and Fe and B, characterized in that the anisotropic magnet comprises a hot press molded body or HIP molded body having a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, total amount of one or a plurality of Ga, Zr, and Hf:
0.001 - 5.0 atomic %, and total amount of one or a plurality of Al, V, and Si:
0.01 - 2.0 atomic %, a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2Fe14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
0.001 - 5.0 atomic %, and total amount of one or a plurality of Al, V, and Si:
0.01 - 2.0 atomic %, a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2Fe14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
3. A rare earth element-Fe-B system anisotropic magnet having as main components thereof R and Fe and B, characterized in that the anisotropic magnet comprises a hot press molded body or HIP molded body having a composition comprising R: 10 - 20 atomic %, B: 3 - 20 atomic %, total amount of one or a plurality of Ti, V, Nb, Ta, Al, and Si: 0. 001 - 5.0 atomic %, and a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2Fe14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which having a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2Fe14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which having a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
4. A rare earth-Fe-B system anisotropic magnet in accordance with one of Claims 1, 2, and 3, characterized in that a crystallized grain aggregate structure in which the crystallized grains are aggregated, comprises materially essentially R2Fe14B type intermetallic compound.
5. A rare earth-Fe-B system anisotropic magnet in accordance with one of Claims 1, 2, and 3, characterized in that the average crystallized grain diameter is within a range of 0.05 - 3 µm.
6. A rare earth-Fe-Co-B system anisotropic magnet having as main components thereof R and Fe and Co and B, characterized in that the anisotropic magnet comprises a hot press molded body or HIP molded body having a composition comprising R: 10 - 20 atomic %, Co: 0.1 - 50 atomic %, B: 3 - 20 atomic %, total amount of one or a plurality of Ga, Zr, and Hf:
0.001 - 5.0 atomic %, and a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
0.001 - 5.0 atomic %, and a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
7. A rare earth-Fe-Co-B system anisotropic magnet having as main components thereof R and Fe and Co and B, characterized in that the anisotropic magnet comprises a hot press molded body or HIP molded body having a composition comprising R: 10 - 20 atomic %, Co: 0.1 - 50 atomic %, B: 3 - 20 atomic %, total amount of one or a plurality of Ga, Zr, and Hf:
0.001 - 5.0 atomic %, and total amount of one or a plurality of Al, V, and Si:
0.01 - 2.0 atomic %, a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
0.001 - 5.0 atomic %, and total amount of one or a plurality of Al, V, and Si:
0.01 - 2.0 atomic %, a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
8. A rare earth-Fe-Co-B system anisotropic magnet having as main components thereof R and Fe and Co and B, characterized in that the anisotropic magnet comprises a hot press molded body or HIP molded body having a composition comprising R: 10 - 20 atomic %, Co: 0.1 - 50 atomic %, B: 3 - 2 atomic %, and total amount of one or a plurality of Ti, V, Nb, Ta, Al, and Si: 0.001 - 5.0 atomic %, a remainder comprising Fe and unavoidable impurities;
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
the hot press molded body or HIP molded body has an aggregate structure of crystallized grains having as a main phase thereof R2(Fe, Co)14B type intermetallic compound having a tetragonal structure, the crystallized grains having dimensions of 0.05 - 20 µm; and individual crystallized grains are present in an amount of more than 50 volume % of the total crystallized grains comprising the aggregate structure which have a value of less than 2 of a ratio b/a of a smallest grain diameter a and a largest grain diameter b.
9. A rare earth-Fe-Co-B system anisotropic magnet in accordance with one of Claims 6, 7, and 8, characterized in that a crystallized grains aggregated, structure in which the crystallized grains are aggregated, comprises materially essentially R2(Fe, Co)14B type intermetallic compound.
10, A rare earth-Fe-Co-B system anisotropic magnet in accordance with one of Claims 6, 7, and 8, characterized in that the average crystallized grain diameter is within a range of 0.05 - 3 µm.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-060828 | 1991-01-28 | ||
| JP3060828A JP2773444B2 (en) | 1991-01-28 | 1991-01-28 | Rare earth-Fe-B based anisotropic magnet |
| JP3-060833 | 1991-01-30 | ||
| JP03060833A JP3092672B2 (en) | 1991-01-30 | 1991-01-30 | Rare earth-Fe-Co-B anisotropic magnet |
| JP3-060837 | 1991-01-31 | ||
| JP03060837A JP3092673B2 (en) | 1991-01-31 | 1991-01-31 | Rare earth-Fe-B based anisotropic magnet |
| JP3-060860 | 1991-02-01 | ||
| JP06086091A JP3196224B2 (en) | 1991-02-01 | 1991-02-01 | Rare earth-Fe-Co-B anisotropic magnet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2079223A1 true CA2079223A1 (en) | 1992-07-29 |
Family
ID=27463963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2079223 Abandoned CA2079223A1 (en) | 1991-01-28 | 1992-01-28 | Anisotropic rare earth-fe-b system and rare earth-fe-co-b system magnet |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0522177B2 (en) |
| CA (1) | CA2079223A1 (en) |
| DE (1) | DE69203405T3 (en) |
| WO (1) | WO1992013353A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352301A (en) * | 1992-11-20 | 1994-10-04 | General Motors Corporation | Hot pressed magnets formed from anisotropic powders |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1316375C (en) * | 1982-08-21 | 1993-04-20 | Masato Sagawa | Magnetic materials and permanent magnets |
| JPS61295342A (en) * | 1985-06-24 | 1986-12-26 | Hitachi Metals Ltd | Manufacture of permanent magnet alloy |
| JPS6217149A (en) * | 1985-07-16 | 1987-01-26 | Sumitomo Special Metals Co Ltd | Manufacture of sintered permanent magnet material |
| JPS62202506A (en) * | 1985-11-21 | 1987-09-07 | Tdk Corp | Permanent magnet and manufacture thereof |
| JPS63178505A (en) * | 1987-01-20 | 1988-07-22 | Hitachi Metals Ltd | Anisotropic r-fe-b-m system permanent magnet |
| JPS63211706A (en) * | 1987-02-27 | 1988-09-02 | Hitachi Metals Ltd | Manufacture of magnetic powder for bond magnet |
| JPS63211705A (en) * | 1987-02-27 | 1988-09-02 | Hitachi Metals Ltd | Anisotropic permanent magnet and manufacture thereof |
| JPS63235406A (en) * | 1987-03-24 | 1988-09-30 | Daido Steel Co Ltd | Production of radially anisotropic permanent magnet |
| DE3850001T2 (en) * | 1987-08-19 | 1994-11-03 | Mitsubishi Materials Corp | Magnetic rare earth iron boron powder and its manufacturing process. |
| JPH01257308A (en) * | 1987-09-09 | 1989-10-13 | Hitachi Metals Ltd | Magnet for voice coil motor |
| JPH07105301B2 (en) * | 1987-09-10 | 1995-11-13 | 日立金属株式会社 | Manufacturing method of magnetic anisotropy Nd-Fe-B magnet material |
| JP2803727B2 (en) * | 1987-09-14 | 1998-09-24 | 大同特殊鋼株式会社 | Manufacturing method of permanent magnet |
| JPH02138706A (en) * | 1988-11-18 | 1990-05-28 | Daido Steel Co Ltd | Anisotropic permanent magnet |
| JPH02263404A (en) * | 1989-04-04 | 1990-10-26 | Hitachi Metals Ltd | Rare earth group iron base permanent magnet |
-
1992
- 1992-01-28 EP EP92903728A patent/EP0522177B2/en not_active Expired - Lifetime
- 1992-01-28 CA CA 2079223 patent/CA2079223A1/en not_active Abandoned
- 1992-01-28 WO PCT/JP1992/000073 patent/WO1992013353A1/en active IP Right Grant
- 1992-01-28 DE DE69203405T patent/DE69203405T3/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0522177B1 (en) | 1995-07-12 |
| DE69203405D1 (en) | 1995-08-17 |
| DE69203405T2 (en) | 1996-02-15 |
| EP0522177A4 (en) | 1993-09-15 |
| DE69203405T3 (en) | 2004-05-06 |
| WO1992013353A1 (en) | 1992-08-06 |
| EP0522177B2 (en) | 2003-07-30 |
| EP0522177A1 (en) | 1993-01-13 |
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