FIELD OF THE INVENTION
[0001] The present invention relates to a R (where R represents at least one type of rare
earth element including Y)-Fe-B system and a R-Fe-Co-B system anisotropic magnet possessing
superior magnetic anisotropy and a small coercive force temperature coefficient, and
relates more particularly to an anisotropic magnet comprising a hot press molded body
or a hot isostatic press molded body.
PRIOR ART
[0002] In Japanese Patent Application, First Publication, Laid-Open no. Hei 1-132106, a
R-Fe-B system permanent magnetic powder obtained by means of the hydrogen treatment
of a R-Fe-B system 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.
[0003] The above R-Fe-B system permanent magnetic powder utilizes R-Fe-B system mother alloy
as a raw material for the main phase of a R
2Fe
14B type intermetallic compound phase (hereinbelow termed the "R
2Fe
14B type phase") which is a ferromagnetic phase; after the heat treatment of this mother
alloy raw material in a H
2 atmosphere within a specified temperature range and the fostering of a phase-changed
state in each of the RH
X, Fe
2B, and the remaining Fe phases, the H
2 is removed from the raw material by means of an H
2-desorption process, and the R
2Fe
14B type phase, which is the ferromagnetic phase, is recreated; the R
2Fe
14B system permanent magnetic powder obtained as a result has an aggregate structure
such that the main phase thereof is an extremely fine R
2Fe
14B type phase having a recrystallized structure and an average grain diameter of 0.05
- 3 µm.
[0004] Furthermore, in the same manner, the above R-Fe-Co-B system permanent magnetic powder
uses R-Fe-Co-B system mother alloy having as a main phase thereof R
2(Fe, C
O)
14B type intermetallic compound (hereinbelow termed R
2(Fe, C
O)
14B type phase), which is a ferromagnetic phase, as a raw material thereof, and this
is processed in a manner identical to the case of the above R-Fe-B system; this has
an aggregate structure having as a main phase thereof an extremely fine R
2(Fe, C
O)
14B type phase with a recrystallized structure and an average grain diameter of 0.05
- 3 µm.
[0005] EP-A-0 274 034 discloses magnetically anisotropic magnetic powders including R-Fe-B-Ga
alloys which may optionally contain further elements such as V, Si and Al. The process
of manufacturing these powders comprises inter alia the steps of hot pressing and
plastic working of the material.
[0006] The above R-Fe-B system and R-Fe-Co-B system permanent magnetic powders are unable
to achieve sufficient magnetic anisotropy simply as a result of being formed as hot
press molded bodies, so that, as disclosed in Japanese Patent Application, First Publication,
Laid-Open No. Hei 2-39503, by carrying out a hot rolling process such as hot rolling
or the like on the above hot press molded bodies and thus creating a rolled structure,
the C axes of the crystal grains of the R
2Fe
14B phase or the R
2(Fe, C
O)
14B type phase are oriented, and the magnetic anisotropy thereof is increased.
[0007] However, R-Fe-B system and R-Fe-Co-B system rolled magnets obtained by the further
hot rolling of a hot press molded body possess superior magnetic anisotropy; but in
comparison with magnets which are produced by the hot pressing of the above R-Fe-B
system and R-Fe-Co-B system permanent magnetic powders obtained by means of hydrogen
treatment, the temperature coefficient of the coercive force increases in an undesirable
manner, and in the case in which such a rolled magnet is incorporated in a motor or
the like, the performance of such a motor or the like varies based on temperature,
and there is a problem in that the stability thereof is lacking.
[0008] Furthermore, in the above R-Fe-B system and R-Fe-Co-B system rolled magnets, positional
variation in the degree of working causes variations in magnetic anisotropy, so that
in order to prevent this, it is impossible to avoid an increase in the complexity
of the hot plastic working processes.
[0009] Believing that the above increase in the temperature coefficient of the coercive
force was caused as a result of the hot rolling of a hot press molded body, and based
on the conviction that if a magnet having superior magnetic anisotropy could be obtained
without the use of hot rolling, this increase in the temperature coefficient of the
coercive force would not occur, the present inventors have conducted research, and
have obtained the R-Fe-B system and R-Fe-Co-B system anisotropic magnets of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The first anisotropic magnet in accordance with the present invention is a R-Fe-B
system anisotropic magnet which is a hot press molded body or a hot isostatic press
molded body (hereinafter termed an "HIP molded body") having a composition comprising
10 - 20 atomic % of R, 3 - 20 atomic % of B, and 0.001 - 5.0 atomic % of one or the
total amount of a plurality of Ga, Zr, and Hf, the remainder comprising Fe and unavoidable
impurities; the above hot press molded body or HIP molded body has an aggregate structure
of crystal grains having dimensions such that the average grain diameter is 0.05 -
20 f..lm and having as a main phase thereof a R
2Fe
14B type intermetallic compound with a tetragonal structure; in addition, 50 volume
% or more of the total individual crystal grains comprising the above aggregate structure
have a value of less than 2 for b/a, a for the smallest grain diameter and b for the
largest grain diameter.
[0011] This first anisotropic magnet has a small coercive force temperature coefficient,
does not exhibit the localized variations in magnetic anisotropy when compared with
conventional molded magnets, and also possesses superior corrosion resistance.
[0012] Furthermore, as this first R-Fe-B system anisotropic magnet possesses a crystal grain
aggregate structure, it possesses superior magnetic anisotropy and a high coercive
force in the vicinity of a R
2Fe
14B type compound composition, that is to say, in the vicinity of a R,
1.
8Fe
baIB
5.
9 (atomic %) composition.
[0013] It is acceptable to add, to the first R-Fe-B system anisotropic magnet composition,
one or a plurality of a group comprising Al, V, and Si, in a total amount of 0.01
- 2.0 atomic %. In such a case, the maximum energy product is further increased, more
striking magnetic anisotropy is displayed, and the coercive force temperature coefficient
is also small.
[0014] Next, a manufacturing method for the above R-Fe-B system anisotropic magnet will
be explained. First, a R-Fe-B system mother alloy having a fixed component composition
containing Ga, Zr, and Hf, 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.
[0015] Next, the above R-Fe-B system mother alloy is heated in an atmosphere of hydrogen
gas, and is subjected to heat processing at a temperature of 500 - 1000°C in an atmosphere
of hydrogen gas or a mixed atmosphere of hydrogen gas and an inert gas; next, hydrogen
desorped processing is conducted at a temperature of 500 - 1000°C so as to create
a vacuum atmosphere in which the hydrogen gas pressure is below a level of 133 Pa
(1 Torr) or to create an inert gas atmosphere in which the hydrogen gas partial pressure
is less than 133 Pa (1 Torr), this is cooled, and thereby a R-Fe-B system permanent
magnetic powder possessing superior magnetic anisotropy and resistance to corrosion
is obtained.
[0016] By adding a homogenizing processing procedure in which the above R-Fe-B system mother
alloy is homogenized at a temperature of 600-1200°C prior to the conducting of the
above heat treatment, and by adding a heat processing procedure in which heat processing
is conducted at a temperature of 300 - 1000°C, 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 structure of the R-Fe-B
system permanent magnetic powder manufactured in the above manner comprises a recrystallized
aggregate structure in which recrystallized grains or a R
2Fe
14B type intermetallic compound phase which are free of impurities and strains within
the grains or at grain boundaries, are aggregated. It is sufficient if the average
crystallized grain diameter of the recrystallized grains comprising the recrystallized
aggregate structure is within a range of 0.05 - 20 µm; however, a mange of 0.05 -
3 µm, which is close to the dimensions of the simple magnetic domain grain diameter
(approximately 0.3 µm) is more preferable.
[0017] It is preferable that the individual recrystallized grains having the above dimensions
have a value of less than 2 for the ratio b/a, the ratio between the smallest grain
diameter a and the largest grain diameter b; it is necessary that recrystallized grains
having this form be present in an amount greater than 50 volume % of the total recrystallized
grains comprising the powder. By means of using recrystallized grains having a shape
such that the ratio b/a of the smallest grain diameter a and the largest grain diameter
b is less than 2, the coercive force of the R-Fe-B system permanent magnetic powder
is improved, and the temperature coefficient aiHc of the coercive force within the
temperature range of 25 - 100°C becomes smaller than -0.6%/°C.
[0018] Next, by pressing the above R-Fe-B system permanent magnetic powder to a green compact
in a magnetic field and then subjecting this green compact to hot pressing or an HIP
process at a temperature of 600°C - 900°C, it is possible to produce a R-Fe-B system
anisotropic magnet which preserves the superior characteristics of the above R-Fe-B
system permanent magnetic powder. Furthermore, after conducting hot pressing or an
HIP process, by conducting, where necessary, heat processing at a temperature of 300°C
- 1000°C, it is possible to improve the coercive force.
[0019] When the above green compact is sintered by means of a normal sintering method, as
the sintering temperature is, in general, high, the superfine recrystallized grains
of the R-Fe-B system permanent magnetic powder grow to large crystallized grains,
and as the magnetic characteristics, and in particular the coercive force, worsen,
such a method is not preferred. Accordingly, it is not preferable to utilize a normal
sintering method as a method for the manufacture of the R-Fe-B system anisotropic
magnets of the present invention; it is necessary, rather, to utilize a hot press
method or a HIP method which enables sintering at comparatively low temperatures,
and thus to control the growth of crystallized grains. Furthermore, as the imparting
of magnetic anisotropy is conducted in a magnetic field, there is no necessity to
conduct a thermoplastic process after hot pressing or the HIP process.
[0020] The reasons forthe limitation of the component composition, average crystallized
grain diameter, and crystallized grain form of the first R-Fe-B system anisotropic
magnet are as follows.
(a) R
[0021] R exhibits one or a plurality of Nd, Pr, Tb, Dy, La, Ce, Ho, Er, Eu, Sm, Gd, Tm,
Yb, Lu, and Y; in general, Nd is used as a main element, and to this are added other
rare earth elements, and in particular, Tb, Dy, and Pr have the effect of increasing
the coercive force iHc. If the amount of R contained is less than 10 atomic %, or
if this amount is greater than 20 atomic %, the coercive force of the anisotropic
magnet is reduced, and superior magnetic characteristics cannot be obtained. Accordingly,
the amount of R contained is set at a level of 10 - 20 atomic %.
(b) B
[0022] If the amount of B contained is less than 3 atomic %, or if this amount is greater
than 20 atomic %, the coercive force of the anisotropic magnet is reduced, and superior
magnetic characteristics cannot be obtained, so that the amount of B contained is
set at a level of 3 - 20 atomic %. It is possible to substitute one or a plurality
of C, N, O, P, and F for a portion of B; this is also the case with the second - fourth
anisotropic magnets described hereinafter.
(c) Ga, Zr, and Hf
[0023] Ga, Zr, and Hf have the function of increasing the coercive force and also stably
imparting superior magnetic anisotropy and resistance to corrosion; however, if one
or a plurality of Ga, Zr, and Hf are contained in a total amount of less than 0.001
atomic %, the desired effects cannot be obtained, while on the other hand, when the
total amount contained is greater than 5.0 atomic %, the magnetic characteristics
worsen. Accordingly, the total amount contained of 1 or a plurality of Ga, Zr, and
Hf is set to a level of 0.001 - 5.0 atomic %.
(d) Al, V, and Si
[0024] Where necessary, Al, V, and Si may be added as components of the R-Fe-B system anisotropic
magnet. These exhibit the effect of increasing the coercive force; however, if one
or a plurality of AI, V, and Si are contained in a total amount of less than 0.01
atomic %, the desired effects cannot be obtained, while on the other hand, when this
amount exceeds 2.0 atomic %, the magnetic characteristics worsen. Accordingly, it
is preferable that one or a plurality of Al, V, and Si be contained in a total amount
of 0.01 - 2.0 atomic %.
(e) Average Crystallized Grain Diameter and Form Thereof
[0025] If the average crystallized grain diameter of the crystallized grains comprising
the structure of the anisotropic magnet is smaller than 0.05 µm, magnetization becomes
a problem, so that this is not desirable, while on the other hand, at a value of more
than 20 µm, the coercive force and the angularity of the hysteresis loop is reduced,
and furthermore, the temperature coefficient of the coercive force increases, so that
this is also not desirable. Accordingly, the average crystallized grain diameter is
set to a value of 0.05 - 20 µm. It is more preferable that the average crystallized
grain diameter be within the range of 0.05 - 3 µm, which is close to the dimensions
of the simple magnetic domain grain diameter (0.3 pm). It is preferable that the individual
crystallized grains have a value of less than 2 for the ratio b/a, the ratio of the
smallest grain diameter a and the largest grain diameter b; it is necessary that crystallized
grains having such a form be present in an amount of greater than 50 volume % of the
total crystallized grains. By means of so setting the form of the crystallized grains
so that a value of less than 2 is obtained for the ratio b/a between the smallest
grain diameter a and the largest grain diameter b, the coercive force of the R-Fe-B
system anisotropic magnet is improved, the resistance to corrosion increases, and
the temperature coefficient of the coercive force is reduced. Accordingly, the value
of b/a of the individual crystallized grains is set to less than 2.
[0026] The second anisotropic magnet in accordance with the present invention is a R-Fe-B
system anisotropic magnet which is a hot press molded body or a HIP molded body having
a composition comprising 10-20 atomic % of R, 3 - 20 atomic % of B, and one or a plurality
of Ti, V, Nb, Ta, Al, and Si in a total amount of 0.001 - 5.0 atomic %, wherein the
remainder comprises Fe or unavoidable impurities; the hot press molded body or HIP
molded body above has an aggregate structure of crystallized grains having as a main
phase thereof an R
2Fe
14B type intermetallic compound with a tetragonal structure, the crystallized grains
having an average grain diameter of 0.05 - 20 µm, and 50 volume % or more of the individual
crystallized grains 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 of less
than 2. In this second R-Fe-B system anisotropic magnet, as well, superior effects
which are identical to those of the above first anisotropic magnet can be obtained.
[0027] In manufacturing this second anisotropic magnet, first, a R-Fe-B system mother alloy
having a fixed component composition containing one or a plurality of Ti, V, Nb, Ta,
Al, and Si is subjected to melt casting, and it is then acceptable, using this as
a raw material, to conduct processing in exactly the same manner as that of the first
anisotropic magnet above.
[0028] With respect to Ti, V, Nb, Ta, Al, and Si, by means of adding one or a plurality
of these elements to the components of the R-Fe-B system anisotropic magnet, the effects
of an increase in the coercive force and the stable imparting of superior magnetic
anisotropy and resistance to corrosion can be obtained; however, when the total amount
of these elements which is contained is less than 0.001 atomic %, the desired effects
cannot be obtained, while on the other hand, when this amount exceeds 5.0 atomic %,
the magnetic characteristics worsen. Accordingly, the total amount of one or a plurality
of Ti, V, Nb, Ta, Al , and Si which is contained is set to a value in the range of
0.001 - 5.0 atomic %.
[0029] Furthermore, in the case of this second anisotropic magnet, even in the case in which
at least one of Co, Ni, Cu, Zn, Ga, Ge, Zr, Mo, Hf, and W is contained in an amount
of 0.001 - 5.0 atomic % in addition to the above composition, superior magnetic anisotropy
and resistance to corrosion can be obtained.
[0030] The third anisotropic magnet in accordance with the present invention is a R-Fe-Co-B
system anisotropic magnet comprising a hot press molded body or an HIP molded body
having a composition comprising 10 - 20 atomic % of R, 0.1 - 50 atomic % of Co, 3
- 20 atomic % of B, and one or a plurality of Ga, Zr, and Hf in a total amount of
0.001 - 5.0 atomic %, wherein the remainder comprises Fe or unavoidable impurities;
the hot press molded body or HIP molded body above has an aggregate structure of crystallized
grains having as a main phase thereof a R
2(Fe, C
O)
14B type intermetallic compound having a tetragonal structure, the crystallized grains
possessing an average grain diameter of 0.05 - 20 µm, and more than 50 volume % of
the individual crystallized grains comprising the above aggregate structure have a
ratio b/a of the smallest grain diameter a and the largest grain diameter b having
a value less than 2.
[0031] This third anisotropic magnet, as in the cases of the first and second anisotropic
magnets above, also has a temperature coefficient of the coercive force which is small,
and in comparison with the conventional rolled magnets, has almost no localized variations
in magnetic anisotropy and also possesses superior resistance to corrosion. Furthermore,
as the magnet has crystallized grain aggregate structure, it has superior magnetic
anisotropy and a high coercive force in the vicinity of a R
2(Fe, C
O)
14B type compound composition, that is to say, in the vicinity of a R,
1.
8(Fe, C
O)
baIB
5.
9 (atomic %) composition.
[0032] It is acceptable to add one or a plurality of Al, V, and Si in a total amount of
0.01 - 2.0 atomic % to the composition of this third anisotropic magnet. In such a
case, the maximum energy product will be further increased.
[0033] In manufacturing this third R-Fe-Co-B system anisotropic magnet, first, a R-Fe-Co-B
system mother alloy having a fixed component composition possessing Ga, Zr, and Hf,
or a R-Fe-Co-B system mother alloy having a fixed component composition in which Al,
V, and Si are added to the above alloy, is manufactured.
[0034] Next, this R-Fe-Co-B system mother alloy is heated in an atmosphere of hydrogen gas,
is subjected to heat treatment at a temperature of 500 - 1000°C in an atmosphere of
hydrogen gas or a mixed atmosphere of hydrogen gas and an inert gas, and then hydrogen
removal processing is carried out at a temperature of 500 - 1000°C so as to produce
a vacuum atmosphere having a hydrogen gas pressure of less than 1 Torr or an inert
gas atmosphere in which the partial pressure of hydrogen gas is less than 1 Torr,
and by cooling this, a R-Fe-Co-B system permanent magnetic powder is obtained.
[0035] By means of the addition of a procedure for homogenizing processing at a temperature
of 600 - 1200°C prior to the conducting of the above heat treatment of the R-Fe-Co-B
system mother alloy above, and by means of the addition of a procedure for heat treatment
at a temperature of 300 - 1000°C after the hydrogen desorped processing above, it
is possible to create a R-Fe-Co-B system permanent magnetic powder having more superior
magnetic anisotropy and resistance to corrosion.
[0036] The structure of the R-Fe-Co-B system permanent magnetic powder produced in the above
manner comprises a recrystallized aggregate structure in which R
2(Fe, C
O)
14B type intermetallic compound phase recrystallized grains, which are free of impurities
or strains within the grains or at the grain boundaries, are aggregated. The average
recrystallized grain diameter of the recrystallized grains comprising this recrystallized
aggregate structure is sufficiently within a range of 0.05 - 20 µm; however, a range
of 0.05 - 3 µm, which is close to the dimensions of a single magnetic domain grain
diameter (approximately 0.3 pm), is more preferable.
[0037] It is preferable that the individual recrystallized grains having the above dimensions
have a form such that the value of the ratio b/a of the smallest grain diameter a
and the largest grain diameter b be less than 2; it is necessary that recrystallized
grains having this form be present in an amount of more than 50 volume % of the total
recrystallized grains comprising the structure of the individual powders. By means
of setting the form of the recrystallised grains so that the ratio b/a of the smallest
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
the coercive force temperature coefficient aiHc in the temperature range of 25°C -
-100°C becomes smaller than 0.6%/°C.
[0038] Furthermore, as the recrystallized structure of the R-Fe-Co-B system permanent magnetic
powder produced in this manner has a recrystallised aggregate structure comprising
materially only R
2(Fe, C
O)
14B type intermetallic compound phase in which a grain boundary phase is almost nonexistent,
it is possible to raise the magnetization values of only the portion having no grain
boundary phase, corrosion proceeding along the grain boundary phase is halted, and
furthermore, as stress deformation resulting from thermoplastic processes does not
exists, the likelihood of stress corrosion is small, and the resistance to corrosion
thus increases.
[0039] Next, the R-Fe-Co-B system permanent magnetic powder above is pressed to a green
compact in a magnetic field, and by subjecting this green compact to hot pressing
or a HIP process at a temperature of 600°C - 900°C, it is possible to produce a R-Fe-Co-B
system anisotropic magnet which preserves the superior characteristics of the R-Fe-Co-B
system permanent magnetic powder above. Furthermore, by conducting heat processing
at 300°C - 1000°C where necessary, it is possible to increase the coercive force.
[0040] When the green compact above is sintered by a conventional method, as the sintering
temperature is normally high, the fine recrystallized grains of the R-Fe-Co-B system
permanent magnetic powder grow into large crystallized grains, and as the magnetic
characteristics, and particularly the coercive force, worsen, this is not preferable.
Furthermore, as the imparting of magnetic anisotropy is conducted in a magnetic field,
it is not necessary to conduct a thermoplastic process after hot pressing or the HIP
process.
[0041] Among the components comprising this third anisotropic magnet, the reasons for the
limitations of the contained amount of R, B, and one or a plurality of Ga, Zr, and
Hf, and the reasons for the limitation of the average crystallized grain diameter
and crystallized grain form, are the same as in the case of the first anisotropic
magnet which was discussed previously.
[0042] With respect to the amount of Co contained, by adding Co to the composition of the
anisotropic magnet, the coercive force and magnetic temperature characteristics (for
example, the Curie point) of the anisotropic magnet are improved, and moreover, the
effect of an increase in the resistance to corrosion is obtained; however, when the
amount contained 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 characteristics
worsen, so that this is not preferable. Accordingly, the amount of Co contained is
set to a range of 0.1 - 50 atomic %. When the amount of Co contained is in a range
of 0.1 - 20 atomic %, the coercive force increases to the greatest extent, so that
it is most preferable to set the amount of Co contained to 0.1 - 20 atomic %.
[0043] Furthermore, the reasons for the limitation of the preferable range of amounts of
Al, V, and Si, contained are the same as in the case of the first anisotropic magnet
which was discussed previously.
[0044] The fourth anisotropic magnet in accordance with the present invention is a R-Fe-Co-B
system anisotropic magnet which is a hot press molded body or a HIP molded body having
a composition containing 10-20 atomic % of R, 0.1 - 50 atomic % of Co, 3 - 20 atomic
% of B, 1 or a plurality of Ti, V, Nb, Ta, Al, and Si in a total amount of 0.001 -
5.0 atomic %, wherein the remainder comprises Fe and unavoidable impurities; the hot
press molded body or HIP molded body above has an aggregate structure of crystallized
grains having as a main phase thereof R
2(Fe, C
O)
14B type intermetallic compound having a tetragonal structure, the crystallized grains
having a average grain diameter of 0.05 - 20 µm, and more than 50 volume % of the
total crystallized grains comprising the above aggregate structure have a ratio b/a
of the smallest grain diameter a and the largest grain diameter b which has a value
of less than 2.
[0045] As in the case of the first through third anisotropic magnets above, this fourth
anisotropic magnet has a small coercive force temperature coefficient, has almost
no localized variations in magnetic anisotropy in comparison with conventional rolled
magnets, has superior corrosion resistance, and as this magnet possesses a crystallized
grain aggregate structure, it has superior magnetic anisotropy and a high coercive
force even in the vicinity of a R
2(Fe, C
O)
14B type compound composition, that is to say, in the vicinity of a R,
1.
8(Fe, C
O)
baIB
5.
9 (atomic %) composition.
[0046] In order to produce this fourth anisotropic magnet, first, a R-Fe-Co-B system mother
alloy having a fixed component composition containing one or a plurality of Ti, V,
Nb, Ta, Al, and Si is subjected to melt casting, and using this as a raw material,
it is acceptable to conduct processing which is identical to that in the case of the
third anisotropic magnet above.
[0047] The reasons for the limitation of R, B, Co, the average crystallized grain diameter,
and the crystallized grain form in the component composition of the anisotropic magnet
of the present invention as given above are the same as in the case of the third anisotropic
magnet which was previously discussed. Furthermore, the reason for the limitation
of the numerical value of the total contained amount of Ti, V, Nb, Ta, Al, and Si
is the same as in the case of the second anisotropic magnet previously discussed.
[0048] Even if this fourth anisotropic magnet contains 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 magnetic
anisotropy and resistance to corrosion.
EXAMPLES
[0049] Next, the first through fourth anisotropic magnets in accordance with the present
invention were produced in the following manner, and the characteristics thereof were
determined.
(Examples of the First Anisotropic Magnet)
[0050] Ingots of various alloys containing one or a plurality of Ga, Zr, and Hf obtained
by plasma melting and casting, and ingots of alloys which contained no Ga, Zr, or
Hf were subjected to homogenizing processing in an atmosphere of argon gas at a temperature
of 1130°C for a period of 20 hours, and after this, these homogenized processed ingots
were crushed to a fineness of approximately 20 mm to create a raw material alloy.
[0051] The raw material alloy was taken from room temperature to a temperature of 830°C
in an atmosphere of hydrogen gas at 1 atmosphere, heat treatment was conducted in
a hydrogen atmosphere at a temperature of 830°C for a period of 4 hours, and next,
hydrogen was desorped so as to obtain a vacuum degree of less than 13 Pa (1 X 10-
1 Torr) at a temperature of 830°C, and immediately thereafter, argon gas was introduced
and rapid cooling conducted. After this, hydrogen treatment had been completed, heat
processing was conducted in argon gas at a temperature of 650°C. The raw material
alloy which was obtained was crushed slightly in a mortar, and a R-Fe-B system permanent
magnetic powder having a mean particle size of 50 f..lm was obtained.
[0052] A green compact was formed by press forming these R-Fe-B permanent magnetic powders
in a 2000 kA/m (25 KOe) magnetic field, and hot pressing these green compacts at a
temperature of 720°C and at a pressure of 1.5 t/cm
2. By further heat processing these molded bodies in a vacuum at a temperature of 620°C
for a period of 2 hours, the R-Fe-B system anisotropic magnets 1 - 26 of the present
invention and the R-Fe-B system anisotropic magnets 1 - 12 of the comparative R-Fe-B
were obtained. The green compacts which were formed in a magnetic field were arranged
and subjected to hot pressing in such a manner that the orientation direction was
identical to the direction of pressing at the time of hot pressing.
[0053] On the other hand, the R-Fe-B permanent magnetic powder which was produced from alloy
ingots containing no Ga, Zr, or Hf was placed in a copper can in a vacuum, this was
heated to a temperature of 720°C, and rolling was conducted a number of times so that
the rolling ratio reached a value of 80%, and the conventional R-Fe-B system anisotropic
magnet 1 was obtained.
[0054] 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 the conventional
R-Fe-B system anisotropic magnet 1 which were obtained in the above manner are shown
in Tables 1 - 3.
[0055] Furthermore, with respect to the R-Fe-B system anisotropic magnets 1 - 26, comparative
R-Fe-B system anisotropic magnets 1 - 12 and the conventional R-Fe-B system anisotropic
magnet 1 having the component elements shown in Tables 1 - 3, the average crystallized
grain diameter, the amount (volume %) of crystallized grains present having a form
such that the value of the largest grain diameter/smallest grain diameter is less
than 2, the coercive force temperature coefficient aiHc, and the magnetic characteristics
were determined. These values are shown in Tables 4 - 6.
[0056] The coercive force iHc
25 at 25°C and the coercive force iHc
100 at 100°C were measured, and the above coercive force temperature coefficient aiHc
has a value determined by the division of the proportional difference of the above
coercive forces (iHc
ioc - iHc
25) / iHc
25 divided by the temperature difference of 75°C.
[0057] It was determined from the results of Tables 1 - 6 that the R-Fe-B system anisotropic
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 powders containing
one or a plurality of Ga, Zr, and Hf, in accordance with the present invention, had
superior magnetic characteristics, and in particular, had superior maximum energy
product (BH)
max and residual magnetic flux density Br, and had superior magnetic anisotropy.
(Other Examples of the First Anisotropic Magnet)
[0059] Next, various alloy ingots having component compositions containing one or a plurality
of AI, V, and Si in addition to a R-Fe-B system alloy containing one or a plurality
of Ga, Zr, and Hf, which were obtained by means of high frequency induction melting
and casting, were produced, these ingots were subjected to homogenizing processing
in an argon gas atmosphere under conditions such that the temperature was 1130°C,
and the time of processing was 30 hours, and then these homogenizing processed ingots
were crushed to a fineness of approximately 20 mm to create a raw material alloy.
[0060] The temperature of this raw material alloy was raised from room temperature to 850°C
in an atmosphere of hydrogen gas at a pressure of 1 atmosphere, heat treatment was
conducted in this hydrogen atmosphere at a temperature of 850°C for 30 minutes, hydrogen
was desorped at a temperature of 850°C so as to create a vacuum degree of less than
13 Pa (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
system permanent magnetic powders having a mean particle size of 60 µm were obtained.
[0061] These R-Fe-B system permanent magnetic powders were formed in a magnetic field so
as to produce green compacts, these green compacts were vacuum filled and sealed in
stainless steel vessels, an HIP process was conducted under conditions such that the
temperature was 700°C and the pressure was 1.8 t/cm
2, and thereby, the R-Fe-B system anisotropic magnets 27 - 36 of the present invention
and the comparative R-Fe-B system anisotropic magnets 13 - 15 were produced.
[0062] The component elements of the R-Fe-B system anisotropic magnets 27 - 36 of the present
invention and the comparative R-Fe-B system anisotropic magnet 13 - 15 are shown in
Table 7. Furthermore, the average crystallized grain diameter, the amount (volume
%) of crystallized grains present for which the value of the ratio of the largest
grain diameter / smallest grain diameter was less than 2, the coercive force, temperature
coefficient aiHc determined by the above method, and the magnetic characteristics
of these anisotropic magnets were determined, and the results thereof are shown in
Table 8.
[0063] As is dear from the results of Tables 7 and 8, with respect to anisotropic magnets
in which one or a plurality of Ga, Zr, and Hf were added in a total amount of 0.001
- 5.0 atomic % and one or a plurality of Al, V, and Si were added in a total amount
of 0.1 - 2.0 atomic %, the maximum energy product was further increased, and more
striking magnetic anisotropy was obtained, while the coercive force temperature coefficient
aiHc was also reduced to a value of approximately -0.5%/°C.

(Examples of the Second Anisotropic Magnet)
[0064] Next, a second anisotropic magnet in accordance with the present invention was produced
in the manner described hereinbelow, and the characteristics thereof were determined.
[0065] Ingots of various alloys containing one or a plurality of Ti, V, Nb, Ta, Al, and
Si, and ingots of alloys containing none of Ti, V, Nb, Ta, Al, or Si, which were obtained
by means of plasma melting and casting, were subjected to homogenizing processing
in an atmosphere of Ar gas under conditions such that the temperature thereof was
1140°C, and the processing time was 20 hours, and these homogenizing processed ingots
were then crushed to a fineness of approximately 20 mm to produce raw material alloys.
[0066] These raw material alloys were raised in temperature from room temperature to 840°C
in an atmosphere of hydrogen gas at a pressure of 1 atmosphere, heat treatment was
conducted in this hydrogen atmosphere at a temperature of 840°C for a period of 1
hour, and then, hydrogen was desorped at a temperature of 830°C so as to produce a
vacuum degree of 13 Pa (1 x 10-
1 Torr), and directly thereafter, argon gas was introduced, and rapid cooling was conducted.
After the conclusion of this hydrogen treatment, heat processing was conducted in
a vacuum at a temperature of 620°C for a period of 2 hours. The raw material alloys
obtained were then slightly crushed in a mortar, and magnetic powders having a mean
particle size of 40 f..lm were obtained.
[0067] The magnetic powders thus obtained were press formed in a magnetic field of 25 KOe
to produce green compacts, and these green compacts were subjected to hot pressing
at a temperature of 730°C and pressure of 1.5 t/cm
2, or were subjected to a HIP process at a temperature of 700°C and a pressure of 1.6
t/cm
2, and furthermore, heat processing was conducted in a vacuum at a temperature of 630°C
for a period of 2 hours. The green compacts which 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 direction at the time of hot pressing.
[0068] Among the anisotropic magnets 37 - 78 of the present invention and comparative anisotropic
magnets 16 - 29 which were produced in this manner, the anisotropic magnets 37 - 60
according to the present invention and the comparative anisotropic magnets 16 - 22
were produced by means of the above hot pressing, while the anisotropic magnets 61
- 78 of the present invention and the comparative anisotropic magnets 23 - 29 were
produced by means of a HIP process. The densities thereof were all suitably accurate,
being in a range of 7.5 - 7.6 g/cm
3.
[0069] Furthermore, for the purposes of comparison, a R-Fe-B system permanent magnetic powder
produced from an ingot of an alloy containing no Ti, V, Nb, Ta, AI, or Si was placed
in a copper can in a vacuum, this was heated to a temperature of 700°C, rolling was
conducted a number of times so that the rolling ratio thereof was 80%, and a conventional
anisotropic magnet 2 was thereby obtained.
[0070] The component compositions of the anisotropic magnets 37 - 78 of the present invention,
the comparative anisotropic magnets 16 - 29 and the conventional anisotropic magnet
2 are shown in Tables 9 - 14.
[0071] Furthermore, the average crystallized grain diameter, the amount (volume %) of crystallized
grains present having a form in which the value of the ratio of the largest grain
diameter / smallest grain diameter was less than 2, the magnetic characteristics and
the coercive force temperature coefficient aiHc of the various anisotropic magnets
was measured, and these values are shown in Tables 15 - 19. The calculation method
of the coercive force temperature coefficient aiHc was identical to that given above.
[0072] From the results of Table 15 - 19, it is clear that the anisotropic magnets 37 -
78 of the present invention, which were produced by conducting hot pressing or a HIP
process on green compacts which were press formed in a magnetic field and contained
one or a plurality of Ti, V, Nb, Ta, Al, and Si had superior magnetic characteristics,
and in particular, had superior maximum energy product (BH)
max and residual magnetic flux density Br, and with respect to magnetic anisotropy, had
characteristics which were equivalent or superior to those of the conventional anisotropic
magnet 2 obtained by means of rolling, and furthermore, with respect to the coercive
force temperature coefficient aiHc, the value thereof was clearly smaller than in
the case of the conventional anisotropic magnet 2. However, as can be seen from comparative
anisotropic magnets 16 - 29, if the contained amounts of one or a plurality of Ti,
V, Nb, Ta, Al, and Si diverged from the ranges of the present invention, magnetic
anisotropy worsened, so that this was not preferable.

(Examples of the Third Anisotropic Magnet)
[0073] Next, a third anisotropic magnet in accordance with the present invention was produced
in the manner described hereinafter, and the characteristics thereof were determined.
[0074] Ingots of various R-Fe-Co-B system alloys containing Co and one or a plurality of
Ga, Zr, and Hf, and ingots of R-Fe-Co-B system alloys containing no Ga, Zr, or Hf
which were obtained by means of plasma melting and casting, were prepared, these alloy
ingots were subjected to homogenizing processing in an argon gas atmosphere under
conditions such that the temperature thereof was 1120°C, and the processing time was
40 hours, and thereafter, these homogenizing processed ingots were crushed to a fineness
of 20 mm to form a raw material alloy.
[0075] The temperature of this raw material alloy was raised from room temperature to a
temperature of 830°C in a hydrogen atmosphere at a pressure of 101 kPa (1 atmosphere),
heat treatment was conducted in this hydrogen atmosphere at a temperature of 830°C
for a period of 4 hours, and then, hydrogen was desorped at a temperature of 830°C
so as to produce a vacuum degree of less than 13 Pa (1 X 10-
1 Torr), and directly thereafter, argon gas was introduced and rapid cooling conducted.
[0076] After the conclusion of the above hydrogen treatment, the ingots were slightly crushed
in mortars, and various R-Fe-Co-B system permanent magnetic powders having a mean
particle size of 50 µm were obtained.
[0077] These R-Fe-Co-B system permanent magnetic powders were press formed in a magnetic
field so as to form green compacts, and these green compacts were subjected to hot
pressing under conditions such that the temperature was 700°C and the pressure was
1.5 Ton/cm
2. At this time, arrangement and hot pressing were conducted in such a manner that
the orientation direction was identical with the press direction at the time of hot
pressing.
[0078] By means of further subjecting the various molded bodies to heat processing at a
temperature of 620°C and for a period of 2 hours, the anisotropic magnets 79-109 of
the present invention and the comparative anisotropic magnets 30 - 39 shown in Tables
20 - 23 were produced. The densities of these anisotropic magnets were sufficiently
accurate, being in a range of 7.5 to 7.6 g/cm
3.
[0079] On the other hand, a R-Fe-Co-B system permanent magnetic powder produced from an
ingot of an alloy containing no Ga, Zr, or Hf was placed in a copper can in a vacuum,
this was heated to a temperature of 700°C and rolling was conducted a number of times
so that the rolling ratio reached 80%, and the conventional anisotropic magnet 3 shown
in Table 23 was obtained.
[0080] The various structures of the anisotropic magnets 79-109 of the present invention,
the comparative anisotropic magnets 30 - 39, and the conventional anisotropic magnet
3 having the component compositions shown in Tables 20 - 22 were observed by means
of a scanning electron microscope, and the average crystallized grain diameter, the
amount of crystallized grains present having a form in which the ratio of the largest
grain diameter smallest grain diameter had a value of less than 2, the coercive force
temperature coefficient aiHc and the magnetic characteristics were determined. The
values obtained thereby are shown in Tables 24 - 27. The method of calculation of
the coercive force temperature coefficient aiHc is as given above.
[0081] It is clear from the results shown in Tables 20 - 27 that the anisotropic magnets
79 - 109 in accordance with the present invention which contain one or a plurality
of Ga, Zr, and Hf have superior magnetic characteristics, and in particular, have
superior maximum energy product (BH)
max and residual magnetic flux density Br, and furthermore, have superior anisotropy.
Furthermore, in comparison with the conventional anisotropic magnet 3 obtained by
means of rolling, the anisotropic magnet 79-109 of the present invention possess essentially
identical magnetic characteristics; however, the coercive force temperature coefficient
aiHc thereof is markedly smaller, having a value of approximately -0.5%/°C. In addition,
in the case of the comparative anisotropic magnets 30 - 39, the compositions of which
lie outside the ranges of the present invention, the magnetic characteristics and
magnetic anisotropy worsen.

(Other Examples of the Third Anisotropic Magnet)
[0082] Next, ingots of various alloys having component compositions containing one or a
plurality of AI, V, and Si in addition to a R-Fe-Co-B system alloy containing one
or a plurality of Ga, Zr, and Hf obtained by means of high frequency induction melting
and casting, were prepared; these ingots were processed by a method identical to that
of the anisotropic magnets 79 - 109 and the comparative anisotropic magnets 30 - 39
above, and R-Fe-Co-B system permanent magnetic powders having a mean particle size
of 40 µm were produced. These permanent magnetic powders were press formed in the
presence or absence of a magnetic field to form green compacts, these green compacts
were subjected to hot isostatic pressing under conditions such that the temperature
thereof was 710°C, and the pressure thereof was 1.7 Ton/cm
2, and the anisotropic magnets 110 - 119 of the present invention and the comparative
anisotropic magnets 40 - 42 comprising the component compositions shown in Table 28
were obtained.
[0083] The average crystallized grain diameter, the amount (volume %) of crystallized grains
present for which the value of the ratio of the largest grain diameter / smallest
grain diameter was less than 2, the coercive force temperature coefficient aiHc and
the magnetic characteristics of these anisotropic magnets were determined in a manner
identical to that above. The results thereof are shown in Table 29.
[0084] As can be seen from the results of Tables 28 and 29, by means of adding 0.1 - 2.0
atomic % of one or a plurality of AI, V, and Si to 0.01 -5.0 atomic % of 1 or a plurality
of Ga, Zr, and Hf, the maximum energy product is further increased. Furthermore, it
is clear that the crystallized grain diameter and the form of the crystallized grains
have a large effect in the reduction of the coercive force temperature coefficient.

(Example of a Fourth Anisotropic Magnet)
[0085] Next, a fourth anisotropic magnet in accordance with the present invention was produced
in the manner detailed hereinbelow, and the characteristics thereof were determined.
[0086] Ingots of a R-Fe-Co-B system alloy containing one or a plurality of Ti, V, Nb, Ta,
Al, and Si, and ingots of a R-Fe-Co-B system alloy which contained no Ti, V, Nb, Ta,
AI, or Si, which were obtained by means of plasma melting and casting, were subjected
to homogenizing processing in an atmosphere of argon gas under conditions such that
the temperature thereof was 1130°C, and the processing time thereof was 20 hours,
and thereafter, these homogenizing processed ingots were crushed to a fineness of
approximately 15 mm to form raw material alloys.
[0087] The temperature of these raw material alloys was raised from room temperature to
830°C in an atmosphere of hydrogen gas at a pressure of 101 kPa (1 atmosphere), heat
treatment was carried out in an atmosphere of hydrogen gas at a temperature of 830°C
for a period of 1 hour, hydrogen was desorped at a temperature of 830°C in order to
produce a vacuum degree of less than 13 Pa (1 X 10-
1 Torr), and immediately thereafter, argon gas was introduced and rapid cooling conducted.
After the conclusion of this hydrogen treatment, heat processing was conducted in
a vacuum at a temperature of 630°C for a period of 2 hours. The raw material alloys
thus obtained were slightly crushed in mortars, and magnetic powders having a mean
particle size of 40 f..lm were obtained.
[0088] These magnetic powders were press formed in a 25 KOe magnetic field to produce green
compacts, and each green compact was subjected to hot pressing under conditions such
that the temperature thereof was 720°C and the pressure thereof was 1.5 t/cm
2, or was subjected to a HIP process under conditions such that the temperature thereof
was 710°C and the pressure thereof was 1.5 t/cm
2, and furthermore, each melted body was then subjected to heat processing at a temperature
of 620°C for a period of 2 hours. The green compacts which were formed in a magnetic
field were arranged and hot pressed in a such a manner that the orientation direction
was identical with the pressing direction of the hot pressing.
[0089] Among the anisotropic magnets 120 - 164 of the present invention and the comparative
anisotropic magnets 43 - 56 which were produced in the above manner, anisotropic magnets
120 - 144 of the present invention and comparative anisotropic magnets 43 - 49 were
produced by means of hot pressing, while anisotropic magnets 145 -164 of the present
invention and comparative anisotropic magnets 50 - 56 were produced by means of an
HIP method. The density thereof was in all cases sufficiently accurate, being within
a range of 7.5 - 7.6
g/cm3
.
[0090] Furthermore, for the purposes of comparison, a R-Fe-Co-B system permanent magnetic
powder produced from an ingot of an alloy containing no Ti, V, Nb, Ta, AI, or Si was
placed in a copper can in a vacuum, this was heated to a temperature of 720°C, and
rolling was conducted a number of times so that the rolling ratio reached a value
of 80%, and thus a conventional anisotropic magnet 4 was obtained.
[0091] The component compositions of the anisotropic magnets 120 - 164 of the present invention,
the comparative anisotropic magnets 43 - 56, and the conventional anisotropic magnet
4 obtained in the above manner are shown in Tables 30 - 35. In addition, the average
crystallized grain diameter, the amount (volume %) of crystallized grains present
having a form in which the value of the ratio of the largest grain diameter / smallest
grain diameter is less than 2, the magnetic characteristics, and the coercive force
temperature coefficient aiHc of these anisotropic magnets were determined by a method
identical to that given above, and the resulting values are shown in Tables 36 - 40.
[0092] From the results of Tables 36 - 40, it is clear that the R-Fe-Co-B system anisotropic
magnets 120 - 164 of the present invention containing one or a plurality of Ti, V,
Nb, Ta, AI, and Si, have essentially identical magnetic characteristics when compared
with the conventional anisotropic magnet 4, which does not contain these elements;
however, the coercive force temperature coefficient is markedly smaller. Furthermore,
when the contained amount of Ti, V, Nb, Ta, Al, and Si lies outside the ranges of
the present invention, as in the case of the comparative anisotropic magnets 43 -
56, the magnetic anisotropy worsens, and it is clear that the crystallized grain diameter
and crystallized grain form also have a large influence on the magnetic characteristics.

POSSIBILITIES FOR USE IN INDUSTRY
[0093] In accordance with the present invention, by means of using a hydrogen treated powder
of a R-Fe-B system or a R-Fe-Co-B system containing one or a plurality of Ga, Zr,
and Hf, or containing one or a plurality of Ti, V, Nb, Ta, Al, and Si, it is possible
to obtain an anisotropic magnet for which the magnetic anisotropy is large, and moreover,
the coercive force temperature coefficient is small, so that there is no need to conduct
a magnetic anisotropizing process such as a thermoplastic process or the like, as
in the conventional method, and production costs can be thereby reduced considerably.
Accordingly, the invention contributes greatly to the ability to produce electronic
machines such as motors and the like and to improvements in stability.