# Patent

## Title
Rare-earth magnet and manufacturing method thereof and magnet motor

## Abstract

The object of the present invention is to provide a rare earth magnet which enables to achieve a good balance between high coercive force and high residual magnetic flux density, and its manufacturing method. The present invention provides a rare earth magnet in which a layered grain boundary phase is formed on a surface or a potion of a grain boundary of Nd2Fe14B which is a main phase of an R—Fe—B (R is a rare-earth element) based magnet, and wherein the grain boundary phase contains a fluoride compound, and wherein a thickness of the fluoride compound is 10 μm or less, or a thickness of the fluoride compound is from 0.1 μm to 10 μm, and wherein the coverage of the fluoride compound over a main phase particle is 50% or more on average. Moreover, after layering fluoride compound powder, which is formed in plate-like shape, in the grain boundary phase, the rare earth magnet is manufactured by quenching the layered compound after melting it at a vacuum atmosphere at a predetermined temperature, or by heating and pressing the main phase and the fluoride compound to make the fluoride compound into a layered fluoride compound along the grain boundary phase.

## Background
This application is a Continuation application of Application No. 11/157,816, filed Jun. 22, 2005, now U.S. Pat. No. 7,179,340, issued Feb. 20, 2007, the contents of which application are incorporated herein by reference in their entirety.


FIELD OF THE INVENTION
The present invention relates to a rare-earth magnet and its manufacturing method, more particularly, relates to a rare-earth magnet having increased coercive force and high energy product and its manufacturing method, and further relates to a magnetic motor using the rare-earth magnet as a rotor.
BACKGROUND OF THE INVENTION
Conventional rare earth magnets including fluoride compounds are described, for example, in JP-A-2003-282312. In the technology described in JP-A-2003-282312, the grain boundary phase has a granular fluoride compound, and the size of the grain of the grain boundary phase is several μm. In such a rare earth magnet, if the coercive force is enhanced, the energy product decreases significantly.
Patent literature 1: JP-A-2003-282312
In the patent literature 1, the magnetic properties of a sintered magnet produced by adding NdFeB powder for sintered magnet and DyF3 that is a fluoride compound is described in table 3. Value of a residual magnetic flux density (Br) is 11.9 kG when DyF3 is added by 5 wt %. The value is decreased by about 9.8% as compared to a value (13.2 kG) of the case of no addition thereof. The energy product ((BH)max) also decreases significantly due to the decrease of the residual magnetic flux density. Therefore, though the coercive force is increased, it is difficult to use the magnet for a magnetic circuit requiring high magnetic flux or a rotating machine requiring high torque due to the small energy product.
In the patent literature 1, as for NdF3, it is used by mixing NdF3 powder having a mean particle diameter of 0.2 μm and NdFeB alloy powder using an automatic mortar, but there is no description in relation to the shape of the fluoride, and after sintering it is aggregated.
BRIEF SUMMERY OF THE INVENTION
The present invention is performed in view of above, and its object is to provide a rare earth magnet which enables to a good balance between high coercive force and high residual magnetic flux density, and its manufacturing method.
Also, the object of the present invention is to provide a magnetic motor using the rare earth magnet as a rotor of the magnet motors.
Other objects, features and advantages of the invention will become apparent from the following description of the embodiments of the invention taken in conjunction with the accompanying drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view illustrating the relationship between the magnetic properties of an NdFeB—NdF3 magnet and the NdF3 thickness.
FIG. 2 is a view illustrating the temperature coefficient of the coercive force of an NdFeB—NdF3 magnet.
FIG. 3 is a view illustrating the relationship between the magnetic properties of an NdFeB—(Nd,Dy)F3 magnet and the NdF3 thickness.
FIG. 4 is a view illustrating the relationship between the magnetic properties of an NdFeB—NdF3 magnet and the NdF3 thickness.
FIG. 5 is a view illustrating the temperature coefficient of the coercive force of an NdFeB—NdF3 magnet.
FIG. 6 is a view illustrating the relationship between the magnetic properties of an NdFeB—(Nd,Dy)F3 magnet and the NdF3 thickness.
FIG. 7 is a view illustrating a quenching apparatus for forming fluoride compound powder.
FIG. 8 is a view illustrating a rotor using a magnet including a fluoride compound.
FIG. 9 is a view illustrating a sectional texture of a magnet including a fluoride compound.
FIG. 10 is a view illustrating the relationship between the magnetic properties of an NdFeB—NdF3 magnet and the grain boundary coverage of NdF3.



DESCRIPTION OF REFERENCE NUMERALS
101 . . . inert gas atmosphere, 102 . . . fluoride compound (raw material powder), 103 . . . tungsten electrode, 104 . . . nozzle hole, 105 . . . roll (rotates in an arrow direction), 107 . . . shutter, 201 . . . a magnet including a fluoride compound, 202 . . . shaft
DETAILED DESCRIPTION OF THE INVENTION
To achieve the above objects, the present invention intends to increase an interface between a fluoride compound and a main phase by forming a layered fluoride compound in a grain boundary, to thin the thickness of the fluoride compound, or to make the fluoride compound in a ferromagnetic phase.
In order to layer the shape of the fluoride compound powder after forming a magnet, the present invention also makes the particle shape of the fluoride compound powder to be used be plate-like. One example of such an approach is to melt and quench the fluoride compound to make it be plate-like. After being molten in a vacuum at a melting temperature of about 2000° C., it is quenched at a quench temperature of 105° C./sec. By quenching, it is possible to obtain plate-like powder having a thickness of 10 μm or less and an aspect ratio of 2 or more. Besides using such plate-like powder, an approach of heating and pressing the main phase and the fluoride compound to mold them such that the fluoride compound layers along the grain boundary, is also possible. If the fluoride compound is layered after molding, the area of the interface between the fluoride compound and the main phase is increased than that of the case that the fluoride compound is aggregated or granulated, and the area is formed along the grain boundary after molding. Since the fluoride is layered, even if less amount of the fluoride is mixed than that of it is aggregated, the increase of magnetic properties due to fluoride is achieved. For converting the fluoride compound into a ferromagnetic material, Fe or Co is added to the fluoride compound, and powder or thin strips are formed through a quenching process. A fluoride compound is paramagnetic and its magnetization at room temperature is small. Thereby, when fluoride compound is mixed with the main phase, the residual magnetic flux density decreases substantially in proportion to the mixing amount. The decrease of the residual magnetic flux density causes significant decrease of the energy product. Accordingly, in a magnetic circuit in which the magnetic flux density of a magnet is designed to be higher, though it was difficult to form a magnet including a conventional fluoride compound, when the fluoride compound could be converted into a ferromagnetic material, even if the added amount of the fluoride compound is equal to that of the conventional one, it is possible to increase the values of the saturated magnetic flux density and the residual magnetic flux density by adding the ferromagnetic fluoride compound. Even when the fluoride compound exhibits ferromagnetism, if the coercive force of the fluoride compound itself becomes not higher, the coercive force or the squareness property of the main phase is adversely affected. In order to ensure the squareness property and enhance the residual magnetic flux density while maintaining the coercive force of the main phase, the coercive force of the fluoride compound should be enhanced. It is possible to ensure the coercive force of the main phase or the squareness property to reduce the decrease of the residual magnetic flux density by making the coercive force of the fluoride compound itself 1 kOe or more. For forming the fluoride compound having such coercive force, an approach of melting and quenching the fluoride compound and the ferromagnetic, is applied. For quenching, a single-roll process or a twin-roll process may be used.
Now referring to drawings, embodiments according to the present invention will be described.
EXAMPLE 1
NdFeB alloy used was a powder having a particle size of about 100 μm subjected to a hydrogenation/dehydrogenation treatment, and the coercive force of this powder was 16 kOe. The fluoride compound to be mixed with the NdFeB powder was NdF3. NdF3 raw material powder was quenched using a quenching apparatus such as in FIG. 7 to form plate-like or ribbon-like powder. As shown in FIG. 7, raw material 102 was molten in an inert gas atmosphere 101 by arc melting using tungsten electrode 103, and by opening a shutter 107 of a nozzle hole 104, the molten NdF3 was atomized on a roll 105 from the nozzle hole 104. Ar gas was used as inert gas, and Cu or Fe based material was used for the roll 105, and the molten NdF3 was atomized on the roll 105 rotating at 500 to 5000 rpm by pressurizing it with Ar gas and utilizing the differential pressure. The resulting NdF3 powder was plate-like, and the NdF3 powder and NdFeB powder were mixed together such that NdF3 content became about 10 wt %. The mixed powder was oriented and compressed by a magnetic field of 10 kOe, and thermally compression molded in an Ar gas atmosphere. Under the molding condition of heating temperature at 700° C. and compression pressure of 3 to 5 t/cm2, an anisotropic magnet of 7 mm×7 mm×5 mm was made. The densities of the compacts made above were all 7.4 g/cm3 or more. Demagnetization curve of the molded anisotropic magnet was measured at 20° C. by applying a pulse magnetic field of 30 kOe or more in the anisotropic direction thereof.
The result is shown in FIG. 1. The NdF3 thickness is an average thickness of an NdF3 layer in the grain boundary of main phase of Nd2Fe14B grains. The NdF3 thickness is depends on molding condition and thermal compression molding condition of NdF3 powder, and the shape of NdFeB powder. As shown in FIG. 1, during making the NdF3 powder, the speed of revolution of a roll is changed from 500 to 5000 rpm to change the NdF3 thickness, the pulverized powder is further classified using such as a mesh. The higher of the speed of revolution, and the larger the pressure of compression molding, the thinner NdF3 thickness may be obtained. As shown in FIG. 1, as the NdF3 thickness increases from 0.01 μm, the values of Br (residual magnetic flux density), iHc (coercive force), and Bhmax (energy product) tend to increase. In the range of the NdF3 thickness of from 0.1 to 10 μm, the iHc increases significantly and Br also increases. Though the coercive force increases due to the presence of NdF3 in an interface, the reason of its decrease when the thickness is increased, is concluded that the ferromagnetic bonding between grains is weakened due to the NdF3 being paramagnetic. The reason of the increase of Br is due to the magnetic flux density at a low magnetic field being increased.
In FIG. 2, the result of the temperature dependence of the coercive force of a magnet having the NdF3 thickness of 1.0 μm, which is measured while the magnet being heated in the atmosphere, is shown. When the magnet is added with no NdF3, the temperature coefficient of its coercive force is 5.0%/° C. The temperature coefficient of the coercive force becomes smaller by increasing the NdF3 thickness. The effective range of the NdF3 thickness is from 1 nm to 10000 nm, and the temperature coefficient of the coercive force is 3.4%/° C. at minimum. It is concluded that this relates to the fact that NdF3 prevents the main phase from being oxidized and to the stabilization of the magnetic domain due to being high coercive force. FIG. 1 shows results in which the average coverage of fluoride over the main phase is about 50%; however, when the NdF3 thickness is from 0.1 to 10 μm, if the coverage changes, their coverage dependences are shown in FIG. 10. The coverage relates to the parameters and conditions such as mixing condition and particle size of the fluoride powder, particle size of the NdFeB powder, shape of the NdFeB powder, an orienting magnetic field, pressure during orientation, and heating condition. As the coverage increases, the coercive force tends to increase.
EXAMPLE 2
The NdFeB powder used in the example was intended for use of a bonded magnet or the like. The NdFeB powder used in the example 2 was powder of particle size of 5 μm diameter for use of sintering, in which main phase was Nd2Fe14B, and the grain boundary of the main phase was made of grown Nd rich phase. After being vacuumed to a degree of 1×10−5 Torr or less, (Nd, Dy)F3 powder was molten in an Ar atmosphere using arc melting, then the molten metal was pressurized and atomized on a surface of a single roll rotating in a vacuum atmosphere. The cooling rate of this processing was 104 to 106° C./sec. The NdF3-5 wt % DyF3 powder (i.e. (Nd, Dy) F3 powder) formed by quenching, included powder having thickness of 10 μm or less and aspect ratio (the ration of vertical length and horizontal length) of 2 or more. By removing thick powder from such (Nd, Dy)F3 powder, NdF3 powder being as possible as thin was selected to be mixed with Nd—Fe—B alloy powder. The mixing amount of the (Nd, Dy)F3 powder was about 10 wt %. The mixed powder was pressed (1 t/cm2) in a magnetic field (10 kOe) and sintered at 1100° C. in a vacuum atmosphere. The sintered body was 10×10×5 mm, the anisotropic direction was the direction of 5 mm. After being magnetized in the anisotropic direction in a magnetic field of 30 kOe, the sintered magnet was measured its demagnetization curve at 20° C. The average grain boundary coverage was about 50%.
The results are shown in FIG. 3. The relationships between the magnetic properties and the NdF3 thickness are qualitatively equal to those of the tendency of FIG. 1. Thus, Br, iHc, and Bhmax are all higher than those of a magnet without NdF3 in a range of the thickness of (Nd, Dy)F3 from 0.1 μm to 10 μm. This indicates that (Nd, Dy)F3 allows to make coercive force more higher and to increase the squareness property of the demagnetization curve and Br, resulting in the increase of (BH)max. From these results, it is possible to attain the high performance of the sintered magnet by controlling the grain boundary coverage and its fluoride thickness.
EXAMPLE 3
The NdFeB alloy was hydride dehydrated powder having a particle size of 150 μm, and the coercive force of the powder was 12 kOe. The fluoride compound added to the NdFeB powder was NdF3. The raw material powder of NdF3 was pulverized into powder having a mean particle diameter of 0.1 μm. It was mixed with the NdFeB powder such that the content of NdF3 became to 10%. The mixed powder was oriented and compressed using a magnetic field of 10 kOe, and thermally compression molded in a vacuum atmosphere (1×10−5 Torr) by energization. Under the molding condition of heating temperature at 700° C. and compression pressure of 3 t/cm2, an anisotropic magnet of 7 mm×7 mm×5 mm was made. The densities of the compacts made above were all 7.4 g/cm3 or more. Demagnetization curve of the molded anisotropic magnet was measured at 20° C. by applying a pulse magnetic field of 30 kOe or more in the anisotropic direction thereof.
The results are shown in FIG. 4. The NdF3 thickness is the average thickness of an NdF3 layer in the grain boundary of main phase of Nd2Fe14B grains. The NdF3 thickness is depends on pulverizing condition and thermal compression molding condition of NdF3 powder. As shown in FIG. 4, Br, iHc, and Bhmax are all higher than those of a magnet without NdF3 in a range of the thickness of (Nd, Dy)F3 from 0.1 μm to 10 μm. iHc significantly increases at the NdF3 thickness of 1 μm or more, and Br also keeps the value being equal to or higher than that of a magnet without NdF3 in the thickness range of NdF3 from 1 μm to 10 μm. The texture of the cross section of the magnet when the NdF3 thickness is 1 μm is shown in FIG. 9. Analysis of the SEM results in allowing the NdF3 thickness to be identified, it is found that the NdF3 is formed with coverage of 50% or more along the grain boundary of the main phase. The result of the temperature coefficient of the coercive force of the magnet in FIG. 4, which is heated in the atmosphere and measured, is shown in FIG. 5. The temperature coefficient of the coercive force decreases by increasing the NdF3 thickness. It is concluded that, similarly to the case in FIG. 2, this relates to the fact that NdF3 prevents the main phase from being oxidized and to the stabilization of the magnetic domain due to being high coercive force.
EXAMPLE 4
NdFeB powder was a powder for use of sintering, and the particle size of main phase Nd2Fe14B powder was 5 μm. After being vacuumed to a degree of 1×10−2 Torr or less, the mixed powder of (Nd, Dy)F3 and Fe was heated and quenched and formed by rolling using a twin roll in an Ar atmosphere. The cooling rate was 103° C./sec at that time. The NdF3-5 wt % DyF3—Fe 1 wt % powder (Fe—(Nd, Dy)F3 powder) formed by quenching includes powder having a thickness of 30 μm or less, and an aspect ratio (the ration of vertical length and horizontal length) of 2 or more. Such Fe—(Nd, Dy)F3 powder was mixed with Nd—Fe—B powder. The Fe—(Nd, Dy)F3 powder exhibited ferromagnetism at room temperature, because it contained Fe. Its Curie temperature was 400° C. and was higher than that of the NdFeB main phase. Moreover, the coercive force of Fe—(Nd, Dy)F3 powder at 20° C. was 3 to 10 kOe, and higher coercive force than that of using fluoride without Fe could be obtained. The mixing amount of Fe—(Nd, Dy)F3 was 10 wt %. The mixed powder was pressed (1 t/cm2) in a magnetic field (10 kOe) and sintered at 1100° C. in a vacuum atmosphere. The sintered body was 10×10×5 mm, the anisotropic direction was the direction of 5 mm. After being magnetized in the anisotropic direction in a magnetic field of 30 kOe, the sintered magnet was measured its demagnetization curve at 20° C. The average grain boundary coverage was about 50%. The results are shown in FIG. 6. The relationships between Br and Bhmax in FIG. 6 and the NdF3 thickness are qualitatively equal to those of the tendency of FIG. 3. Br, iHc, and Bhmax are all higher than those of a magnet without NdF3 in a range of the thickness of (Nd, Dy)F3 of from 0.05 μm to 10 μm. This indicates that (Nd, Dy)F3 allows making coercive force more higher and increases the squareness property of the demagnetization curve and Br resulting in the increase of (BH)max. From these results, it is possible to attain the high performance of the sintered magnet by controlling the grain boundary coverage (50% or more) and its fluoride thickness.
EXAMPLE 5
An example of production of a rotor for a motor is shown below. In FIG. 8, the schematic view of the produced rotor is shown. For an inner rotor, a magnet was arranged to the periphery of a shaft 202, thereby, a magnet 201 including the above fluoride was arranged to the periphery of a shaft 202. The thermal demagnetization of the rotor in FIG. 8 was hardly done, thereby, by applying a hard magnetic material with small temperature dependence of coercive force, it is possible to obtain an output which has resistance against an inverse magnetic field, small temperature dependence of its induced voltage, and high temperature stability.
EXAMPLE 6
Powder having a main phase of Nd2Fe14B and particle size of 1 to 100 μm was used as a magnetic material, and a film based of crystalline or amorphous NdF3-based film was formed on a portion or whole of the surface of the magnetic powder using a solution containing NdF3. The NdF3 thickness was 1 to 100 nm on average. Even if NdF2 was mixed into NdF3, the magnetic properties of the magnetic powder were not affected. An oxide containing an rare earth element and a small amount of impurity, i.e. carbon-containing compound, may exist adjacent to the interface between these fluoride layers and the magnetic powder. Fluorides that may be used as similar solution are BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, or PmF3. By forming at least one kind of these crystalline or amorphous component containing fluoride compound on the surface of the powder of which main phase being Nd2Fe14B, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density, and increase the squareness property of the demagnetization curve was obtained. By producing a compound that is a mixture-of magnetic powder in which the above fluorides being formed and organic resin such as PPS (polyphenylene sulfide) and molding it in a magnetic field, it may be molded into a bonded magnet. The magnetic properties of the produced bonded magnet are shown in Table 1.







TABLE 1







bonded magnet



















tem-



aver-




perature



age



tem-
coefficient



film

residual

perature
of



thick-

mag-

coefficient
residual



ness

netic

of
magnetic



of
coercive
flux
energy
coercive
flux



flouride
force
density
product
force
density


flouride
(nm)
(kOe)
(T)
(MGOe)
(%/° C.)
(%/° C.)





BaF2
10
15.0
1.00
19.5
−0.41
−0.09


CaF2
10
15.0
1.01
19.6
−0.41
−0.09


MgF2
10
15.0
1.01
19.5
−0.41
−0.09


SrF2
10
15.0
1.01
19.5
−0.41
−0.09


LiF
10
15.0
1.01
19.5
−0.41
−0.09


LaF3
10
15.0
1.01
19.6
−0.41
−0.09


NdF3
10
16.0
1.03
19.8
−0.39
−0.08


PrF3
10
22.0
1.02
19.7
−0.37
−0.09


SmF3
10
17.0
1.02
19.4
−0.39
−0.08


EuF3
10
16.0
1.01
19.5
−0.40
−0.09


GdF3
10
16.0
1.02
19.5
−0.40
−0.09


TbF3
10
32.0
1.01
20.1
−0.35
−0.08


DyF3
10
25.0
1.01
20.0
−0.34
−0.08


CeF3
10
16.0
1.00
19.3
−0.40
−0.09


HoF3
10
17.0
1.02
19.4
−0.40
−0.09


ErF3
10
15.5
1.02
19.4
−0.40
−0.09


TmF3
10
15.5
1.00
19.4
−0.41
−0.09


YbF3
10
16.0
1.00
19.2
−0.41
−0.09









EXAMPLE 7
Magnetic powder having a main phase of Nd2Fe14B and particle size of 1 to 100 μm was used, and a crystalline or amorphous fluoride-based film was formed on a portion or whole of the surface of the magnetic powder using a solution containing fluoride. The fluoride thickness was 1 to 100 nm on average. The magnetic powder was heated to 1100° C. and further annealed at 500 to 600° C. to increase the coercive force of the magnetic powder. Coercive force of 10 kOe or more was obtained by the annealing. A rare earth rich phase was formed adjacent to the surface of the magnetic powder by the above annealing, and at its outer side there was a crystalline or amorphous fluoride-based film. As for fluorides, BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, or PmF3 might be formed, and by forming these fluoride, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, and decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density was obtained. Oxide on the surface of the magnetic powder and a portion of fluoride reacted to mix oxygen into the fluoride by the above annealing, and oxygen-containing fluoride was formed. Formation of the oxyfluoride may decrease the oxygen concentration of the main phase, thereby providing in the increase of residual magnetic flux density and increase of squareness property. The powder may be used as highly heat resistance magnetic powder for bonded magnet because the oxidation of the surface of the magnetic powder may be suppressed by fluoride even without surface oxide. The magnetic properties of the produced bonded magnet are shown in Table 2.







TABLE 2







bonded magnet



















tem-



aver-




perature



age



tem-
coefficient



film

residual

perature
of



thick-

mag-

coefficient
residual



ness

netic

of
magnetic



of
coercive
flux
energy
coercive
flux



flouride
force
density
product
force
density


flouride
(nm)
(kOe)
(T)
(MGOe)
(%/° C.)
(%/° C.)
















BaF2
50
25.0
1.05
27
−0.39
−0.09


CaF2
100
25.0
1.04
27.1
−0.39
−0.09


MgF2
100
25.0
1.04
27.1
−0.38
−0.09


SrF2
100
25.0
1.03
26.7
−0.37
−0.09


LiF
100
25.0
1.02
26.6
−0.38
−0.09


LaF3
100
25.0
1.02
26.8
−0.39
−0.09


NdF3
100
27.0
1.07
27.8
−0.32
−0.09


PrF3
100
29.0
1.06
27.1
−0.38
−0.09


SmF3
100
25.0
1.05
27.5
−0.39
−0.09


EuF3
100
26.0
1.05
27
−0.39
−0.09


GdF3
100
26.0
1.05
27.8
−0.38
−0.09


TbF3
100
40.0
1.04
29.5
−0.31
−0.08


DyF3
100
35.0
1.05
28.5
−0.3
−0.08


CeF3
100
25.1
1.02
26.4
−0.38
−0.09


HoF3
100
25.0
1.01
26.3
−0.39
−0.09


ErF3
100
25.2
1.02
26.4
−0.39
−0.09


TmF3
100
25.0
1.01
26.4
−0.39
−0.09


YbF3
100
25.2
1.02
26.4
−0.39
−0.09









EXAMPLE 8
Magnetic powder having a main phase of Nd2Fe14B and particle size of 1 to 100 μm was used, and a crystalline or amorphous fluoride-based film was formed on a portion or whole of the surface of the magnetic powder using a solution containing fluoride. The fluoride thickness was 1 to 100 nm on average. If the crystalline or amorphous fluoride-based film would be formed or not could be identified by analysis such as X-ray diffraction, SEM composition analysis, and TEM. The magnetic powder coated with the crystalline or amorphous fluoride-based film was applied a magnetic field, and a compact was made using a pressing machine. The compact was heated to 900 to 1100° C. and further annealed at 500 to 700° C. to increase the coercive force of the body. Coercive force of 10 kOe or more was obtained by the annealing. If the thickness of the crystalline or amorphous fluoride-based film would be thin, in the above heat treating of 1100° C., the body was sintered by the partial aggregation or breaking of the fluoride layer. By the above heat treating, a rare earth rich phase was formed adjacent to the surface of the magnetic powder, and at its outer side there was a crystalline or amorphous fluoride-based layer. As for fluorides, BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, or PmF3 might be formed, and these fluorides would either form an interface between itself and the rare earth rich phase or the rare earth oxide, or become a mixed layer of the rare earth oxide and itself. Formation of the mixed layer of the rare earth oxide and the fluoride results in forming a fluoride with low fluorine concentration, however, similar effect might be obtained. By forming such a fluorine-containing periphery layer, it was possible to prevent the inside from being oxidized, thereby any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, and decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density was obtained. The magnetic properties of the produced bonded magnet are shown in Table 3.







TABLE 3







bonded magnet



















tem-



aver-




perature



age



tem-
coefficient



film

residual

perature
of



thick-

mag-

coefficient
residual



ness

netic

of
magnetic



of
coercive
flux
energy
coercive
flux



flouride
force
density
product
force
density


flouride
(nm)
(kOe)
(T)
(MGOe)
(%/° C.)
(%/° C.)
















BaF2
50
30.0
1.2
32
−0.39
−0.09


CaF2
50
31.0
1.21
32.1
−0.38
−0.09


MgF2
50
31.0
1.22
32.2
−0.39
−0.09


SrF2
50
31.0
1.2
32.1
−0.38
−0.09


LiF
50
31.0
1.2
32.1
−0.39
−0.09


LaF3
50
30.0
1.2
32.1
−0.39
−0.09


NdF3
50
31.0
1.25
33.5
−0.34
−0.08


PrF3
50
33.0
1.22
32.5
−0.35
−0.09


SmF3
50
30.0
1.23
32.8
−0.37
−0.09


EuF3
50
30.0
1.21
32.3
−0.38
−0.09


GdF3
50
31.0
1.21
32.2
−0.36
−0.09


TbF3
50
38.0
1.22
32.5
−0.34
−0.08


DyF3
50
35.0
1.22
32.4
−0.33
−0.07


CeF3
50
30.0
1.2
31.5
−0.39
−0.09


HoF3
50
30.2
1.2
31.8
−0.39
−0.09


ErF3
50
30.1
1.2
31.8
−0.38
−0.09


TmF3
50
30.2
1.19
31.5
−0.39
−0.09


YbF3
50
30.3
1.18
31.4
−0.39
−0.09









EXAMPLE 9
Magnetic powder having a main phase of Nd2Fe14B and particle size of 1 to 100 μm was used, and a crystalline or amorphous fluoride-based film was formed on a portion or whole of the surface of the magnetic powder using a solution containing fluoride. The thickness of the fluoride was 1 to 100 nm on average. If the crystalline or amorphous fluoride-based film would be formed or not, could be identified by analysis such as X-ray diffraction, SEM composition analysis, and TEM. The magnetic powder coated with the crystalline or amorphous fluoride-based film was applied a magnetic field, and a compact was made using a pressing machine. The compact was heated to 1000° C. or more and further annealed at 500 to 600° C. to increase the coercive force of the body. Coercive force of 10 kOe or more was obtained by the annealing. The crystalline or amorphous fluoride-based layer remained present on the periphery of the magnetic powder in a continuous layer after the above heat treating. By the above heat treating, a rare earth rich phase was formed adjacent to the surface of the magnetic powder, and at its outer side there was the crystalline or amorphous fluoride-based layer. As for fluorides, BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, or PmF3 might be formed, and these fluorides would either form an interface between itself and the rare earth rich phase or the rare earth oxide, or become a mixed layer of the rare earth oxide and itself. Formation of the mixed layer of the rare earth oxide and the fluoride resulted in forming a fluoride with low fluorine concentration, however, similar effect might be obtained. By forming such a fluorine-containing periphery layer, it was possible to prevent the inside from being oxidized, thereby any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, and decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density was obtained. By pressurizing the above magnetic powder during the heat treating of 500 to 600° C., a sintered body was made. The magnetic properties of the produced sintered body are shown in Table 4.







TABLE 4







sintered magnet



















tem-



aver-




perature



age



tem-
coefficient



film

residual

perature
of



thick-

mag-

coefficient
residual



ness

netic

of
magnetic



of
coercive
flux
energy
coercive
flux



flouride
force
density
product
force
density


flouride
(nm)
(kOe)
(T)
(MGOe)
(%/° C.)
(%/° C.)
















BaF2
100
30.0
1.14
28
−0.41
−0.09


CaF2
100
31.0
1.13
27.5
−0.4
−0.09


MgF2
100
31.0
1.13
27.4
−0.42
−0.09


SrF2
100
31.0
1.12
26.8
−0.39
−0.09


LiF
100
31.0
1.11
26.5
−0.38
−0.09


LaF3
100
31.0
1.12
26.8
−0.39
−0.09


NdF3
100
32.0
1.16
28.5
−0.35
−0.07


PrF3
100
32.0
1.15
28.3
−0.37
−0.08


SmF3
100
31.0
1.11
28.1
−0.39
−0.08


EuF3
100
31.0
1.12
27.6
−0.39
−0.08


GdF3
100
33.0
1.12
27.5
−0.38
−0.08


TbF3
100
39.0
1.14
28.9
−0.31
−0.08


DyF3
100
36.0
1.15
28.8
−0.29
−0.07


CeF3
100
30.0
1.13
27.4
−0.4
−0.09


HoF3
100
30.1
1.12
27
−0.41
−0.09


ErF3
100
30.0
1.12
27.1
−0.41
−0.09


TmF3
100
30.1
1.11
26.8
−0.41
−0.09


YbF3
100
30.2
1.12
26.9
−0.41
−0.09









EXAMPLE 10
It is possible to form a crystalline or amorphous fluoride-based film on a 2-17 phase (SmFeN-based, SmCo-based) that is another main phase other than 2-14 phase. By immersing Sm2Fe17N3 powder of particle size of 1 to 10 μm into a solution containing fluoride, the crystalline or amorphous fluoride-based film was formed on a portion or whole of the surface of the powder. The solvent on the surface of the magnetic powder can be removed by heating the powder at a temperature of 100° C. or more, thereby the crystalline or amorphous fluoride-based film was formed on a portion or whole of the surface of the magnetic powder. The thickness of the fluoride was 1 to 100 nm. As for fluorides, BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, or PmF3 might be formed. It is possible for the SmFeN or SmCo magnetic powder coated with these fluorides on a portion or whole of its surface of itself to be made a bonded magnet by mixing with a resin and by injection molding or compression molding.
EXAMPLE 11
Magnetic powder having a main phase of Nd2Fe14B and particle size of 1 to 100 μm was used, and a crystalline or amorphous NdF3-based film was formed on a portion or whole of the surface of the magnetic powder using a gelled NdF3 by the use of a solvent. During application to the magnetic powder, solvent that hardly damages the magnetic powder magnetically or structurally should be selected to be used. The NdF3 thickness formed by application was 1 to 10000 nm on average. Even if NdF2 was mixed into NdF3, the magnetic properties of the magnetic powder were not affected. Oxide containing rare earth element, and a small amount of impurity, i.e. carbon or oxygen-containing compound, might exist adjacent to the interface between these fluoride layers and the magnetic powder. Fluorides that might be used as similar gel material were BaF2, CaF2, MgF2, SrF2, LiF, LaF3, NdF3, PrF3, SmF3, EuF3, GdF3, TbF3, DyF3, CeF3, HoF3, ErF3, TmF3, YbF3, LuF3, LaF2, NdF2, PrF2, SmF2, EuF2, GdF2, TbF2, DyF2, CeF2, HoF2, ErF2, TmF2, YbF2, LuF2, YF3, ScF3, CrF3, MnF2, MnF3, FeF2, FeF3, CoF2, CoF3, NiF2, ZnF2, AgF, PbF4, AlF3, GaF3, SnF2, SnF4, InF3, PbF2, or BiF3. By forming at least one kind of these crystalline or equivalent composition amorphous component containing fluoride compound on the surface of the powder of which main phase being Nd2Fe14B, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density, increase the squareness property of the demagnetization curve, increase of corrosion resistance, and suppression of oxidation was obtained. These fluoride might be either ferromagnetic or paramagnetic at 20° C. The coverage of fluoride over the surface of the magnetic powder could be enhanced by applying the fluoride on the magnetic powder using gel than the case by mixing fluoride powder without using gel. Accordingly, the above effect appears more prominently in the case of the coating using gel than that of mixing with fluoride powder. Even if oxygen or constituent element of the main phase would be contained in the fluoride, the above effect would be sustained. It was possible for a bonded magnet to be molded by making a compound that is a mixture of the magnetic powder, on which the above fluoride being formed, and a simple body of polyphenylether or polyphenylenesulfide, or an organic resin such as epoxy resin, polyimide resin, polyamide resin, polyamide-imide resin, Kerimid resin, and maleimide resin, and molding it in a magnetic field or without the magnetic field. In the bonded magnet using Nd2Fe14B powder applied by the above gel, similar to the effect for magnetic powder, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density, increase of the squareness property of demagnetization curve, increase of corrosion resistance, and suppression of oxidation could be identified. These effects can be considered as the result of stabilizing the structure of the magnetic domain due to formation of a fluoride layer, increase of anisotropy of the magnet adjacent to fluoride, and the fact that fluoride prevents the magnetic powder from being oxidized.
EXAMPLE 12
Magnetic powder having a main phase of Nd2Fe14B, Sm2Fe17N3, or Sm2Co17 and particle size of 1 to 100 μm was used, and a crystalline or amorphous REF3-based film was formed on a portion or whole of the surface of the magnetic powder using a colloidal liquid or a solution containing a gel material containing REF3 (RE; rare earth element). The REF3 thickness was 1 to 1000 nm on average. Even if REF2 was mixed into REF3, the magnetic properties of the magnetic powder were not affected. After the formation, the solvent used for forming the gel material was removed. Oxide containing rare earth element, and a small amount of impurity, i.e. carbon or oxygen-containing compound, or a rare earth rich phase might exist adjacent to the interface between the fluoride compound layer and the magnetic powder. The composition of the fluoride could be changed by controlling the composition of the colloidal liquid or the solution containing the gel or the condition of application within the range of REFx (X=1 to 3). By forming at least one kind of these crystalline or equivalent composition amorphous component containing fluoride compound on the surface, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density, increase the squareness property of the demagnetization curve, increase of corrosion resistance, and suppression of oxidation was obtained. It was possible for a bonded magnet to be molded by making a compound that is a mixture of the magnetic powder, on which the above fluoride being formed, and a simple body of polyphenylether or polyphenylene sulfide, or organic resin such as epoxy resin, polyimide resin, polyamide resin, polyamide-imide resin, Kerimid resin, and maleimide resin, and molding it by compression molding or injection molding. Alternatively, a molded magnet having volume percentage of the magnetic powder of 80% to 99%, could be made by performing compression molding, thermal compression molding, or extruding of the magnetic powder in which above fluoride layer was formed, using a mold. Layered fluoride was formed in the grain boundary of the molded magnet. In a bonded magnet using powder of Nd2Fe14B, Sm2Fe17N3, or Sm2Co17 applied with the above gel, similar to the effect of magnetic powder, any effect of decrease of the temperature coefficient of the coercive force, increase the coercive force, decrease of the temperature coefficient or increase of Hk of the residual magnetic flux density, increase the squareness property of the demagnetization curve, increase of corrosion resistance, and suppression of oxidation may be identified. Though each of the powder of Nd2Fe14B, Sm2Fe7N3, or Sm2Co17 is added by various elements in application, even if any additive element would be used, fluoride might be formed and the above effect could be identified. The texture, the crystal structure, the grain boundary, and the particle size of the magnetic powder of Nd2Fe14B, Sm2Fe17N3, or Sm2Co17 were also controlled by adding metal based elements including rare earth elements. Thereby, beside of the main phase, other phases were formed by adding elements or by the manufacturing process of the magnet. As for NdFeB based powder, fluorides, a rare earth rich phase, or a Fe rich phase might be used, the surface of the powder in which these oxides were formed with such phases, was also possible to be applied by the above gel material, thereby resulting in the formation of layered fluorides. The magnetic properties of metal based magnetic powder containing at least one rare earth elements changed, because rare earth elements tended to be easily oxidized. Since fluoride is effective as a layer to prevent rare earth element from being oxidized, the fluoride layer used in the above example may be expected for all magnetic powders based of metal including rare earth element to have an effect to protect them from being oxidized, thereby being effective in suppression of corrosion and collapse, and stability of corrosion-potential.
INDUSTRIAL APPLICABILITY
The present invention is especially available to a magnet motor as a magnet for use in a high temperature of 100° C. or more, because the coercive force can be enhanced while suppressing the energy product of R—Fe—B (R; rare earth element) based magnet from being decreased. Such a magnet motor includes, for example, a driving motor of a hybrid vehicle, a starter motor, and an electrically controlled power steering motor.
It should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention, the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims.
ADVANTAGES OF THE INVENTION
As described above, the present invention enables to achieve a good balance between high coercive force and high residual magnetic flux density by forming a fluoride compound into a layered form at a grain boundary of NdFeB. The present invention may also provide a rare earth magnet available in a temperature range from 100° C. to 250° C., it may be applied for a rotor of a magnet motor.

## Claims

1. A magnet comprising:
NdFeB based magnetic powder; and
a fluoride film formed on a portion or whole of a surface of said magnetic powder, wherein said fluoride film is mainly composed of at least one compound selected from the group consisting of TbF3 and DyF3, 
wherein said magnetic powder has an average particle size of 1 to 100 μm,
wherein a rare earth rich phase is formed on a surface of the magnetic powder, and said fluoride film is formed on an outer side of said rare earth rich phase, and
wherein said fluoride film has a thickness of 1 to 100 nm on average.

2. The magnet according to claim 1, wherein said fluoride film contains oxygen.

3. The magnet according to claim 1, wherein said magnetic powder has a main phase of Nd2Fe14B.

4. The magnet according to claim 1, which constitutes a bonded magnet.

5. The magnet according to claim 1, wherein said fluoride film is formed by using a solution containing a fluoride.

6. The magnet according to claim 1, wherein said fluoride film is an amorphous film.

7. The magnet according to claim 1, wherein said fluoride film is a crystalline film.

8. The magnet according to claim 1, wherein said magnetic powder has been subjected to annealing.

9. A magnet motor, including a rotor which has a magnet,
wherein the magnet comprises:
NdFeB based magnetic powder; and
a fluoride film formed on a portion or whole of a surface of said magnetic powder, wherein said fluoride film is mainly composed of at least one compound selected from the group consisting of TbF3 and DyF3,
wherein said magnetic powder has an average particle size of 1 to 100 μm, and
said fluoride film has a thickness of 1 to 100 μm on average.

10. The magnet according to claim 1, wherein the fluoride film is formed on the whole of the surface of the magnetic powder.

11. The magnet motor according to claim 9, wherein the fluoride film is formed on the whole of the surface of the magnetic powder.

12. The magnet motor according to claim 9, wherein a rare earth rich phase is formed on a surface of the magnetic powder, and said fluoride film is formed on an outer side of said rare earth rich phase.