CN107785140A - Ferromagnetic material, permanent magnet, electric rotating machine and vehicle - Google Patents
Ferromagnetic material, permanent magnet, electric rotating machine and vehicle Download PDFInfo
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- CN107785140A CN107785140A CN201710730576.7A CN201710730576A CN107785140A CN 107785140 A CN107785140 A CN 107785140A CN 201710730576 A CN201710730576 A CN 201710730576A CN 107785140 A CN107785140 A CN 107785140A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K1/00—Details of the magnetic circuit
- H02K1/02—Details of the magnetic circuit characterised by the magnetic material
Abstract
The present invention improves the saturation magnetization of ferromagnetic material.Ferromagnetic material is with composition formula：(R1‑xYx)aMbTcAdThe ferromagnetic material of expression, have by ThMn12The principal phase that type crystalline phase is formed.30 atom % of the M element of composition formula are above is Fe.
Description
The application is with the Japanese patent application 2016-163797 (applyings date：And Japanese patent application 2017- 8/24/2016)
018622 (the applying date：And the Japanese patent application 2017-135371 (applyings date 2/3/2017)：7/11/2017) based on, enjoy
The priority of above-mentioned application.The application is by quoting above-mentioned application and comprising contents of these applications.
Technical field
The present invention relates to ferromagnetic material, permanent magnet, electric rotating machine and vehicle.
Background technology
Permanent magnet is applied to include the electrical equipment such as electric rotating machine, loudspeaker, metrical instrument such as motor, generator,
The product in the extensive field including the vehicles such as automobile, rolling stock.In recent years, it is desirable to the miniaturization of the said goods, it is desirable to open
Send the high performance permanent magnet with high magnetic intensity and high-coercive force.
As the example of high performance permanent magnet, the rare earth such as Sm-Co based magnets and Nd-Fe-B based magnets can be enumerated
Class magnet.In these magnet, Fe and Co are advantageous to the increase of saturation magnetization.In addition, to contain Nd and Sm etc. dilute for these magnet
Earth elements, larger magnetic anisotropy is brought by the behavior of the 4f electronics of the rare earth element in crystalline field.Thereby, can obtain larger
Coercivity.
The content of the invention
Problem to be solved by this invention is to improve the saturation magnetization of ferromagnetic material.
The ferromagnetic material of embodiment is with composition formula 1：(R1-xYx)aMbTc(in formula, R is more than one rare earth element, T
It is at least one element selected from Ti, V, Nb, Ta, Mo and W, M is that Fe either Fe and Co, x are satisfaction 0.01≤x≤0.8
Number, a are the atom % of 4≤a of satisfaction≤20 numbers, and b is the number for meeting b=100-a-c atoms %, and c is to meet the atom % of 0 ＜ c ＜ 7
Number) represent.Ferromagnetic material has by ThMn12The principal phase that type crystalline phase is formed.30 atom % of the M element of composition formula 1 above is
Fe。
Brief description of the drawings
Fig. 1 is represented with composition formula：(Sm0.82Y0.18)7.7(Fe0.70Co0.30)88.4Ti3.9The X ray of the ferromagnetic material of expression
The figure of the example of diffraction pattern.
Fig. 2 is represented with composition formula：(Sm0.68Zr0.32)7.8(Fe0.70Co0.30)88.2Ti4.0The X of the ferromagnetic material of expression is penetrated
The figure of the example of ray diffraction diagram case.
Fig. 3 is represented with Nd3(Fe,Ti)29The figure of the example of the X-ray diffraction pattern at the peak of type crystalline phase.
Fig. 4 is the figure for representing Permanent Magnet motor.
Fig. 5 is the figure for representing variable magnetic flux motor.
Fig. 6 is the figure for representing generator.
Fig. 7 is the schematic diagram for the configuration example for representing rolling stock.
Fig. 8 is the schematic diagram for the configuration example for representing automobile.
(symbol description)
1 ... Permanent Magnet motor, 2 ... turbines, 3 ... rotors, 4 ... iron cores, 5 ... permanent magnets, 11 ... variable magnetics are powered
Motivation, 13 ... rotors, 14 ... iron cores, 15 ... fixed magnets, 16 ... variable magnets, 21 ... generators, 22 ... stators, 23 ... turn
Son, 24 ... turbines, 25 ... axles, 26 ... brushes, 100 ... rolling stocks, 101 ... electric rotating machines, 200 ... automobiles, 201 ... electric rotatings
Machine.
Embodiment
Embodiment is illustrated with reference to the accompanying drawings.In addition, accompanying drawing is schematic diagram, such as thickness and planar dimension
Relation, the ratio of thickness of each layer etc. are sometimes different from actual conditions.In addition, in embodiment, for substantially the same structure
Identical symbol is marked with into key element, is omitted the description.
(first embodiment)
The ferromagnetic material of present embodiment contains rare earth element and M element (M is Fe either Fe and Co).Above-mentioned magnet material
Material, by improving the M element concentration in principal phase, can improve saturation magnetization with the metal structure using crystalline phase as principal phase.It is main
It is mutually volume occupation rate highest phase in each crystalline phase and amorphous phase in ferromagnetic material.
As the crystalline phase of the M element containing high concentration, such as ThMn can be enumerated12Type crystalline phase.ThMn12Type crystalline phase has just
The crystal structure of prismatic crystal system.With ThMn12Type crystalline phase for principal phase ferromagnetic material in because M element concentration is high, α-(Fe,
Co) mutually easily separate out.If the equal out-phase of α-(Fe, Co) separates out, then the M element concentration in principal phase reduces, and causes the full of principal phase
Reduced with the intensity of magnetization.In addition, the precipitation of α-(Fe, Co) phase causes the coercitive reduction of permanent magnet.Then, this embodiment party
In the ferromagnetic material of formula, each element concentration contained in principal phase is controlled, forms stable ThMn12Type crystalline phase, and reduce simultaneously
α-(Fe, Co) phase, the M element concentration in principal phase is improved, thereby suppress the reduction of saturation magnetization.
The ferromagnetic material of present embodiment has with composition formula 1：(R1-xYx)aMbTc(in formula, R is more than one rare earth
Element, T are at least one elements selected from Ti, V, Nb, Ta, Mo and W, M be Fe either Fe and Co, x be 0.01≤x of satisfaction≤
0.8 number, a are the atom % of 4≤a of satisfaction≤20 numbers, and b is the number for meeting b=100-a-c atoms %, and c is to meet 0 ＜ c ＜ 7
Atom % number) represent composition.In addition, ferromagnetic material can contain inevitable impurity.
Yttrium (Y) contributes to ThMn12The stabilized element of type crystalline phase.That is, Y element mainly can by with principal phase
R element enters line replacement, lattice diminution etc. is improved ThMn12The stability of type crystalline phase.If the addition of Y element is very few,
It can not fully obtain and improve ThMn12The effect of the stability of type crystalline phase.If Y addition is excessive, ferromagnetic material it is each
Anisotropy magnetic field intensity is obviously reduced.X is preferably the number for meeting 0.01≤x≤0.8, more preferably meets 0.05≤x ＜'s 0.5
Number, more preferably meet the number of 0.1≤x≤0.4.
Below the 50 atom % of Y element can be by least one element substitution selected from zirconium (Zr) and hafnium (Hf).Zr elements
It is that larger coercitive element can be showed in the composition of high Fe concentration with Hf elements.By being replaced as Zr elements and Hf members
Element, coercivity can be improved.
R element is rare earth element, be can assign ferromagnetic material with larger magnetic anisotropy, can assign permanent magnet with compared with
High coercitive element.R element is specifically selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium
(Sm), at least the one of europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu)
Kind element, particularly preferably using Sm.Such as using the multiple element comprising Sm as R element in the case of, by making Sm concentration
Reach more than the 50 atom % for all elements that can be used as R element, performance, such as coercivity of ferromagnetic material can be improved.
The concentration a of R element and Y element is for example preferably the number for meeting the atom % of 4≤a≤20.Less than 4 atom % situation
Under, substantial amounts of α-(Fe, Co) is mutually separated out, and coercivity reduces.In the case of 20 atom %, Grain-Boundary Phase increase, saturated magnetization
Intensity decreases.The concentration a of R element and Y element is more preferably the number for meeting the atom % of 5≤a≤18, more preferably meets 7
The atom % of≤a≤15 number.
M element is Fe either Fe and Co, is the element for the high saturation and magnetic intensity for undertaking ferromagnetic material.In Fe and Co,
The Fe intensity of magnetization is higher, therefore Fe is indispensable element, and in the magnet of present embodiment, 30 atom % of M element are above is Fe.
By adding Co in M element, the Curie temperature of ferromagnetic material raises, and can suppress the drop of the saturation magnetization in high-temperature area
It is low.In addition, by adding a small amount of Co, compared with the situation for being individually added into Fe, saturation magnetization more can be improved.The opposing party
Face, if improving Co ratios, the decrease of anisotropic magnetic field intensity can be caused.Moreover, if Co ratios are too high, can also recruit
Cause the reduction of saturation magnetization.Therefore, by suitably controlling Fe and Co ratio, it can realize that high saturation is strong simultaneously
Degree, high anisotropy magnetic field intensity, high-curie temperature.If the M of composition formula 1 is denoted as (Fe1-yCoy), then preferable y value
For 0.01≤y ＜ 0.7, more preferably more preferably 0.01≤y ＜ 0.5,0.01≤y≤0.3.20 atom % of M element
Below can be by least one element selected from aluminium (Al), silicon (Si), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu) and gallium (Ga)
Displacement.Above-mentioned element is advantageous to for example form the growth of the crystal grain of principal phase.
T elements are, for example, at least one member selected from titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta), molybdenum (Mo) and tungsten (W)
Element.By adding T elements, ThMn can be made12Type crystalline phase is stable.However, due to the importing of T elements, M element concentration is reduced, and it is tied
Fruit is that the saturation magnetization of ferromagnetic material is easily reduced.In order to improve M element concentration, if T additions are reduced, but this
When, ThMn12The loss of stability of type crystalline phase, α-(Fe, Co) are mutually separated out, thus the coercivity of ferromagnetic material reduces.T elements add
Dosage c is preferably the number for meeting the atom % of 0 ＜ c ＜ 7.Thereby, can make while the precipitation of α-(Fe, Co) phase is suppressed
ThMn12Type crystalline phase is stable.More preferably 50 atom % of T elements are above is Ti or Nb.By using Ti or Nb, even if reducing T members
The content of element, can also make ThMn12The amount of precipitation of α-(Fe, Co) phase is greatly decreased in type crystalline phase while stable.
In order to further improve the saturation magnetization of ferromagnetic material, the addition of T elements is preferably less, but in T members
In the case that the addition of element is few, Nd3(Fe,Ti)29Type crystalline phase easily separates out, therefore saturation magnetization can drop on the contrary sometimes
It is low.In order to also suppress Nd in the case where the addition of T elements is few3(Fe,Ti)29The precipitation of type crystalline phase, effectively increases Y
Addition, can thereby realize high saturation and magnetic intensity.In composition formula 1 or composition formula 2, such as the addition c of T elements is to meet
In the case of the atom % of 0 ＜ c ＜ 4.5 number, x is preferably the number for meeting 0.1 ＜ x ＜ 0.6, and c is to meet the atom % of 1.5 ＜ c ＜ 4
Number in the case of, x is preferably the number for meeting 0.15 ＜ x≤0.55, in the case that c is the number for meeting the atom % of 3 ＜ c≤3.8,
X is preferably the number for meeting 0.3 ＜ x≤0.5.
The ferromagnetic material of present embodiment can also contain element A.Now, the composition of ferromagnetic material is with composition formula 2：(R1- xYx)aMbTcAd(in formula, R is more than one rare earth element, and T is at least one element selected from Ti, V, Nb, Ta, Mo and W, M
It is that Fe either Fe and Co, A are at least one elements selected from N, C, B, H and P, x is the number of satisfaction 0.01≤x≤0.8, and a is
Meet the atom % of 4≤a≤20 number, c is the number for meeting the atom % of 0 ＜ c ＜ 7, and b is the number for meeting b=100-a-c atoms %, d
It is the number for meeting the atom % of 0 ＜ d≤18) represent.
Element A is at least one element selected from nitrogen (N), carbon (C), boron (B), hydrogen (H) and phosphorus (P).Element A has intrusion
ThMn12The lattice of type crystalline phase is interior, triggers the work(of at least one of the expansion of such as lattice and the change of electronic structure phenomenon
Energy.Thereby, Curie temperature, magnetic anisotropy, saturation magnetization can be changed.In addition to inevitable impurity, element A may not
It must add.
50 atom % of R element are above is in the case of Sm (in the case that the principal component of R element is Sm), due to element A
Intrusion, ThMn12The magnetic anisotropy of type crystalline phase changes out of c-axis direction court the face vertical with c-axis, reduces coercivity.Cause
This, does not preferably add element A in addition to inevitable impurity.In contrast, R element 50 atom % above is selected from Ce,
(principal component of R element is at least one selected from Ce, Pr, Nd, Tb and Dy in the case of Pr, Nd, Tb and Dy at least one element
In the case of kind element), due to the intrusion of element A, ThMn12The magnetic anisotropy of type crystalline phase is out of vertical with c-axis face towards c-axis
Direction change, increase coercivity.It is therefore preferable that addition element A.In the case of adding element A, element A concentration d is preferably full
Foot 0 ＜ d≤18 atom % number.If greater than 18 atom %, then ThMn12The stability of type crystalline phase reduces.Element A concentration d is more
Preferably meet the atom % of 0 ＜ d≤14 number.
Fig. 1 is represented with composition formula：(Sm0.82Y0.18)7.7(Fe0.70Co0.30)88.4Ti3.9The X ray of the ferromagnetic material of expression
The figure of the example of diffraction pattern, Fig. 2 are represented with composition formula：(Sm0.68Zr0.32)7.8(Fe0.70Co0.30)88.2Ti4.0The magnetic of expression
The figure of the example of the X-ray diffraction pattern of iron material.Fig. 1, the X-ray diffraction pattern shown in 2 are penetrated by carrying out X to ferromagnetic material
Line diffraction (X-ray Diffraction：XRD) determine and obtain.From the X-ray diffraction pattern shown in Fig. 1,2, ferromagnetic material
With with ThMn12Type crystalline phase is the metal structure of principal phase.
The maximum I of the peak intensity for coming from α-(Fe, Co) phase of X-ray diffraction pattern shown in Fig. 1α-(Fe,Co)Than Fig. 2 institute
The maximum I of the peak intensity for coming from α-(Fe, Co) phase of the X-ray diffraction pattern shownα-(Fe,Co)It is small.This represents present embodiment
Ferromagnetic material α-(Fe, Co) phase amount of precipitation it is few.In the X-ray diffraction pattern of the ferromagnetic material of present embodiment, relatively
In coming from ThMn12The maximum I of the peak intensity of type crystalline phaseThMn12With the maximum for the peak intensity for coming from α-(Fe, Co) phase
Iα-(Fe,Co)Sum, come from α-ratio (I of the maximum of the peak intensity of (Fe, Co) phaseα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) excellent
Choosing is less than 0.20, more preferably less than 0.15, is further preferably no larger than 0.10.
Fig. 3 is represented with Nd3(Fe,Ti)29The figure of the example of the X-ray diffraction pattern at the peak of type crystalline phase.Such as Fig. 3 institutes
Show, Nd3(Fe,Ti)29Separating out for type crystalline phase can go out according in the position that 2 θ of X-ray diffraction pattern are less than more than 39 degree 40 degree
Existing peak judges., can be according to relative to coming from ThMn in the X-ray diffraction pattern of the ferromagnetic material of present embodiment12Type is brilliant
The maximum I of the peak intensity of phaseThMn12With coming from Nd3(Fe,Ti)29The maximum I of the peak intensity of type crystalline phase3-29Sum, come from
Nd3(Fe,Ti)29The maximum I of the peak intensity of type crystalline phase3-29Ratio (I3-29/(I3-29+IThMn12)) evaluate Nd3(Fe,
Ti)29The amount of precipitation of type crystalline phase.I3-29/(I3-29+IThMn12) it is preferably less than 0.070, more preferably less than 0.050, it is further excellent
Choosing is less than 0.040.
In the ferromagnetic material of present embodiment, the M element concentration in principal phase is higher, can more improve the saturation magnetic of ferromagnetic material
Change intensity.M element concentration in the principal phase of ferromagnetic material is preferably element (R element, Y element, the M members in principal phase in addition to element A
Element and T elements) total amount more than 85 atom %, more preferably more than 87.4 atom %, more preferably 87.6 atom %
More than, it is even more preferably more than 88.0 atom %.
In the ferromagnetic material of present embodiment, by making the M element concentration in principal phase reach the member in principal phase in addition to element A
More than the 87.4 atom % of the total amount of plain (R element, Y element, M element and T elements), it is possible to provide there is saturation higher than ever
The ferromagnetic material of the intensity of magnetization.The overall saturation magnetization of ferromagnetic material is for example higher than 1.48T, more preferably more than 1.52T.
In addition, the saturation magnetization of the principal phase after rejecting the contribution of the saturation magnetization of α-(Fe, Co) phase is for example higher than 1.41T,
More preferably more than 1.50T.Saturation magnetization equimagnetic physical property is for example with vibrating specimen magnetometer (Vibrating Sample
Magnetometer：VSM) calculate.
The composition of ferromagnetic material is for example, by ICP-AES (high-frequency inductive coupling plasma bodies-emission spectrometry：
Inductively Coupled Plasma-Atomic Emission Spectroscopy), SEM-EDX (scanning electron microscopies
Mirror-energy dispersion type x-ray spectrometry：Scanning Electron Microscope-Energy Dispersive X-ray
Spectroscopy), TEM-EDX (transmission electron microscopes-energy dispersion type x-ray spectrometry：Transmission
Electron Microscope-Energy Dispersive X-ray Spectroscopy) etc. determine.The volume of each phase
Ratio by electron microscope, the observation of light microscope and X-ray diffraction etc. and for comprehensively judging.
The concentration of each element of principal phase is for example determined with SEM-EDX.For example, can be according to SEM observation image and SEM-
The distribution image of each element for the ferromagnetic material determination sample that EDX is measured determines principal phase.
Then, manufacturer's rule of the ferromagnetic material of present embodiment is illustrated.First, manufacture contains ferromagnetic material
The alloy of required regulation element.Such as can use arc melting process, high frequency fusion method, mold castings, mechanical alloying method,
Mechanical milling method, gas atomization, reduction-diffusion process etc. manufacture alloy.If there is α-(Fe, Co) interpromoting relation in five elements in obtained alloy
Into can then cause the coercitive reduction of the permanent magnet manufactured by the alloy.
Then, by above-mentioned alloy melting, quenching.Thereby, the amount of precipitation of α-(Fe, Co) phase can be reduced.The alloy example of fusing
Such as it is quenched with thin strap continuous casting method.In thin strap continuous casting method, by pouring into alloy molten solution to chill roll, alloy thin band can be manufactured.Now,
By controlling the rotary speed of roller, the cooling velocity of liquation can control.Roller can be that single roll shape can also be double roller type.
Above-mentioned alloy thin band can be implemented to be heat-treated.Thereby, the material can be made to homogenize.Such as at 800~1300 DEG C
Lower heating 2~120 hours.Thereby, ThMn can be improved12The stability of type crystalline phase, further improve saturation magnetization, respectively to different
Both characteristics of property magnetic field intensity.
Element A can be made to invade above-mentioned alloy thin band.Before the process of element A intrusion alloy is made, preferably in advance by alloy
It is ground into powder.In the case that element A is nitrogen, can in the atmosphere such as the nitrogen of about 0.1~100 atmospheric pressure or ammonia,
Alloy thin band is heated 1~100 hour within the temperature range of 200~700 DEG C, so that alloy thin band nitrogenizes, invades N element
Alloy thin band., can be in the C of about 0.1~100 atmospheric pressure in the case that element A is carbon2H2、CH4、C3H8Or CO gases or
In the heat resolve gas atmosphere of methanol, alloy thin band is heated 1~100 hour within the temperature range of 300~900 DEG C, from
And alloy thin band is carbonized, C element is invaded alloy thin band., can be in about 0.1~100 air in the case that element A is hydrogen
In the atmosphere such as the hydrogen or ammonia of pressure, alloy thin band is heated 1~100 hour within the temperature range of 200~700 DEG C, so as to
Alloy thin band is hydrogenated, H element is invaded alloy thin band.In the case that element A is boron, it can make when manufacturing alloy in raw material
Containing boron, so that containing boron in alloy thin band.In the case that element A is phosphorus, alloy thin band phosphatization can be made, invade P element
Enter alloy thin band.
Ferromagnetic material is manufactured by above-mentioned operation.Then, permanent magnet is manufactured with above-mentioned ferromagnetic material.For example, will
Above-mentioned ferromagnetic material crushes, and the heat treatment such as is then sintered, so as to manufacture the sintering of the sintered body containing above-mentioned ferromagnetic material
Magnet.In addition, above-mentioned ferromagnetic material is crushed, solidified with resin etc., so as to manufacture the binding magnet containing above-mentioned ferromagnetic material.
(second embodiment)
The permanent magnet of the sintered body of ferromagnetic material with first embodiment can be used for various motor and generating
Machine.In addition, it also is used as the fixed magnet and variable magnet of variable magnetic flux motor and variable flux generator.By using
The permanent magnet of one embodiment, it may make up various motor and generator.The permanent magnet of first embodiment is applied to
In the case of variable magnetic flux motor, in the structure and drive system of variable magnetic flux motor, such as Japan can be applied special
Technology disclosed in sharp JP 2008-29148 publications or JP 2008-43172 publications.
Then, the motor with above-mentioned permanent magnet and generator are illustrated referring to the drawings.Fig. 4 is to represent permanent
The figure of magnetic motor.In Permanent Magnet motor 1 shown in Fig. 4, rotor (gyrator) is configured with stator (stator) 2
3.Permanent magnet 5 is configured with the iron core 4 of rotor 3, the permanent magnet 5 is the permanent magnet of first embodiment.By making
With the permanent magnet of first embodiment, the characteristic based on each permanent magnet etc., the high efficiency of Permanent Magnet motor 1 can be achieved
Change, miniaturization, cost degradation etc..
Fig. 5 is the figure for representing variable magnetic flux motor.It is (fixed in stator in variable magnetic flux motor 11 shown in Fig. 5
Son) rotor (gyrator) 13 is configured with 12.The permanent magnet that first embodiment is configured with the iron core 14 of rotor 13 is made
For fixed magnet 15 and variable magnet 16.The magnetic flux density (magnetic flux) of variable magnet 16 is variable.Variable magnet 16 due to
Its direction of magnetization is orthogonal with Q direction of principal axis, therefore is not influenceed by Q shaft currents, is magnetized using D shaft currents.On rotor 13
It is provided with magnetization winding (not shown).By making electric current flow to the magnetization winding from magnetization circuit, be formed as its magnetic field and directly make
Structure for variable magnet 16.
Using the permanent magnet of first embodiment, fixed magnet 15 can obtain good coercivity.By the first embodiment party
In the case that the permanent magnet of formula is applied to variable magnet 16, exist by changing manufacturing condition, such as by coercivity control
In more than 100kA/m below 500kA/m scope.In addition, in variable magnetic flux motor 11 shown in Fig. 5, fixed magnet
15 and variable magnet 16 can use the permanent magnet of first embodiment, but can also the magnet of either one it is real using first
Apply the permanent magnet of mode.Variable magnetic flux motor 11 can export larger torque with less plant bulk, therefore be adapted to use
In the high-output power and the hybrid vehicle of miniaturization and the motor of electric automobile etc. that require motor.
Fig. 6 show generator.Generator 21 shown in Fig. 6 has the stator (stator) using above-mentioned permanent magnet
22.The rotor (gyrator) 23 of the inner side of stator (stator) 22 is configured at via axle 25 and the whirlpool of the one end for being arranged at generator 21
The connection of wheel 24.Turbine 24 for example rotates in the presence of the fluid being externally supplied.Alternatively, it is also possible to transmit the recovery energy of automobile
The dynamic rotaries such as amount replace the turbine 24 rotated under action of a fluid, so that axle 25 rotates.Stator 22 and rotor 23 can be adopted
With various known compositions.
The commutator (not shown) of opposite side of the axle 25 with being configured at turbine 24 relative to rotor 23 contacts, and passes through rotor 23
Rotation and caused electromotive force is boosted as the output of generator 21 via phase separation bus and main transformer (not shown)
To system voltage, then power.Generator 21 can be any of common generator and variable flux generator.Separately
Outside, rotor 23 occurs powered because of shaft current caused by the electrostatic from turbine 24 and adjoint generating.Therefore, generator 21 has
For the brush 26 for the powered release for making rotor 23.
To sum up, by the way that above-mentioned permanent magnet is applied into generator, high efficiency, miniaturization, cost degradation etc. can be obtained
Effect.
Above-mentioned electric rotating machine can for example be loaded into the rolling stock (one of vehicle) of railway traffic.Fig. 7 is to represent
The figure of one of the rolling stock 100 with electric rotating machine 101.As electric rotating machine 101, can be used above-mentioned Fig. 4,5 it is electronic
The generator etc. of machine, Fig. 6.In the case of loading above-mentioned electric rotating machine as electric rotating machine 101, electric rotating machine 101 for example can be with
Driven as using the electric power from the supply that installs electric wiring or the electric power supplied from the secondary cell for being loaded into rolling stock 100 to export
The motor (motor) of power uses, and can also change into electric power, the various loads into rolling stock 100 as by kinetic energy
The generator (generator) of supply electric power uses.By using efficient rotation as the electric rotating machine of embodiment
Motor, travel while rolling stock energy-conservation can be made.
Above-mentioned electric rotating machine can also be loaded into the automobiles such as hybrid vehicle and electric automobile (another example of vehicle).Figure
8 be the figure of one of the automobile 200 for representing to have electric rotating machine 201.As electric rotating machine 201, above-mentioned Fig. 4,5 electricity can be used
The generator etc. of motivation, Fig. 6.In the case of loading above-mentioned electric rotating machine as electric rotating machine 201, electric rotating machine 201 can be used
The generator of electric power is changed into as the motor of driving force of output automobile 200 or kinetic energy when automobile 200 is travelled.
Embodiment
(embodiment 1-38)
Appropriate raw material is weighed, alloy is made with arc-melting legal system.Then, by alloy melting, by gained liquation strip
Continuous metal cast process is quenched, and manufactures alloy thin band.Above-mentioned alloy thin band is heated 4 hours in 1100 DEG C under an ar atmosphere.Then, ICP- is used
The composition of alloy thin band after AES analysis heating.Table 1 is shown in the composition of the ICP-AES ferromagnetic materials tried to achieve.
Then, alloy thin band is crushed with mortar, alloy powder is made.Then, the XRD using CuK α as radiographic source is passed through
Determine to analyze the crystal structure of above-mentioned alloy powder.Fig. 1 is the X-ray diffraction pattern of the ferromagnetic material of embodiment 1.XRD is surveyed
It is fixed as a result, confirming that alloy powder has with ThMn12Type crystalline phase is the metal structure of principal phase.In addition, pass through calculating
Iα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) evaluate the amount of precipitation of α-(Fe, Co) phase.Also by calculating I3-29/(I3-29+IThMn12) come
Evaluate Nd3(Fe,Ti)29The amount of precipitation of type crystalline phase.
In addition, the magnetic physical property of ferromagnetic material is evaluated with VSM devices.Apply 5.0T magnetic to direction in the face of alloy thin band
After, by field scan to -5.0T, magnetic field intensity H and magnetization M are determined.4.5T mistake is reduced to from 5.0T to application magnetic field
The intensity H of magnetization M and magnetic field in journey relation applies mechanically being approached to saturation calmly with what following formula (1) represented for regular crystal
Rule, so as to calculate ferromagnetic material overall saturation magnetization Ms and anisotropic magnetic field intensity HA。
M=Ms (1-HA 2/15H2) (Ms represents saturation magnetization, HARepresent anisotropic magnetic field intensity) (1)
Based on coming from the peak intensity of the α in X-ray diffraction pattern-(Fe, Co) phase, evaluation α-(Fe, Co) is relatively full
With the contribution of the intensity of magnetization, the overall saturation magnetization of ferromagnetic material is subtracted into the value, so as to obtain the saturated magnetization of principal phase
Intensity.Specifically, the powdered sample without the peak intensity for coming from α-(Fe, Co) phase in X-ray diffraction pattern is manufactured,
Wherein powdered sample of the addition with α-(Fe, Co) phase, is sufficiently mixed, more parts of samples is made.There is α-Fe in more parts of samples
The mass ratio of the powdered sample of phase is different in the scope more than 0 mass % below 21 mass %.By XRD determining come
The crystal structure of said sample is analyzed, as a result, confirming the mass ratio and peak intensity of the powdered sample with α-(Fe, Co) phase
The ratio I of the maximum of degreeα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) relation it is linear.Based on the conclusion, by X-ray diffractogram
The peak intensity of the α of case-(Fe, Co) phase obtains the mass ratio of α-(Fe, Co) phase, is converted into α-(Fe, Co) relative saturation
The contribution of the intensity of magnetization.
Then, determine the concentration of element of the principal phase of 5 points respectively in 3 field of view by SEM-EDX measure, calculate
The simple average value of this 15 points, so as to calculate the M element concentration in principal phase.As measuring point, select in SEM image in radius
The point of α-(Fe, Co) phase is not present within 5 μm.In SEM observations, with new and high technology Co., Ltd. of Hitach (Hitachi Ha イ テ Network ノ
ロ ジ ー ズ societies) SU8020 processed observed with accelerating potential 30kV.In addition, in SEM-EDX measure, Yi Da Ces Co., Ltd is used
(エ ダ ッ Network ス societies) Octan-super (semiconductor element size 60mm processed2), operating distance is set to 15mm, by live time
(live time) is set to 100 seconds to be measured.In the calculating of concentration of element, only using the constitution element of each sample as calculating
Object, L alpha rays are used for Sm, Zr, Y, and K alpha rays are used for Fe, Co, Ti.
(embodiment 39-41)
Appropriate raw material is weighed, alloy is made with arc-melting legal system.Then, by alloy melting, by gained liquation strip
Continuous metal cast process is quenched, and manufactures alloy thin band.Above-mentioned alloy thin band is heated 4 hours in 1100 DEG C under an ar atmosphere.Then, by alloy
Strip is crushed with mortar, and gained powder is heated 4 hours in nitrogen atmosphere in 450 DEG C.Then, alloy is analyzed with ICP-AES
The composition of powder.Table 1 is shown in the composition of the ICP-AES ferromagnetic materials tried to achieve.
Then, the crystal structure of above-mentioned alloy powder is analyzed by the XRD determining using CuK α as radiographic source.XRD is surveyed
It is fixed as a result, confirming that alloy powder has with ThMn12Type crystalline phase is the metal structure of principal phase.In addition, pass through calculating
Iα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) evaluate the amount of precipitation of α-(Fe, Co) phase.Also by calculating I3-29/(I3-29+IThMn12) come
Evaluate Nd3(Fe,Ti)29The amount of precipitation of type crystalline phase.
In addition, alloy powder is fixed in acrylic resin square sample pond with paraffin, ferromagnetic material is evaluated with VSM
Magnetic physical property.The computational methods of condition determination and saturation magnetization and anisotropic magnetic field intensity and the phase of embodiment 1~30
Together.
Then, determine each element concentration of the principal phase of 5 points respectively in 3 field of view by SEM-EDX measure, calculate
Go out the simple average value of this 15 points, so as to calculate the M element concentration in principal phase.
(embodiment 42,43)
Appropriate raw material is weighed, alloy is made with arc-melting legal system.Then, by alloy melting and quenching, under an ar atmosphere
Heated 4 hours in 1100 DEG C.Then, with the composition of the alloy after ICP-AES analysis heating.The magnet material tried to achieve with ICP-AES
The composition of material is shown in table 1.
Then, alloy thin band is crushed with mortar, alloy powder is made.Then, penetrated by the X using CuK α as radiographic source
Line diffraction analyzes the crystal structure of above-mentioned alloy powder.XRD determining as a result, confirm alloy powder have with
ThMn12Type crystalline phase is the metal structure of principal phase.In addition, by calculating Iα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) come evaluate α-(Fe,
Co) the amount of precipitation of phase.Also by calculating I3-29/(I3-29+IThMn12) evaluate Nd3(Fe,Ti)29The amount of precipitation of type crystalline phase.
In addition, the magnetic physical property of ferromagnetic material is evaluated with VSM.Condition determination and saturation magnetization and anisotropic magnetic
The computational methods of field intensity are identical with embodiment 1~41.
Then, determine each element concentration of the principal phase of 5 points respectively in 3 field of view by SEM-EDX measure, calculate
Go out the simple average value of this 15 points, so as to calculate the M element concentration in principal phase.
(comparative example 1~5)
Appropriate raw material is weighed, alloy is made with arc-melting legal system.Then, by alloy melting, by gained liquation strip
Continuous metal cast process is quenched, and manufactures alloy thin band.Above-mentioned alloy thin band is heated 4 hours in 1100 DEG C under an ar atmosphere.Then, ICP- is used
The composition of alloy thin band after AES analysis heating.Table 1 is shown in the composition of the ICP-AES ferromagnetic materials tried to achieve.
Then, alloy thin band is crushed with mortar, alloy powder is made.Then, penetrated by the X using CuK α as radiographic source
Line diffraction analyzes the crystal structure of above-mentioned alloy powder.Fig. 2 is the X-ray diffraction pattern of the ferromagnetic material of comparative example 1.
XRD determining as a result, confirm alloy powder have with ThMn12Type crystalline phase is the metal structure of principal phase.In addition, pass through calculating
Iα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) evaluate the amount of precipitation of α-(Fe, Co) phase.Also by calculating I3-29/(I3-29+IThMn12) come
Evaluate Nd3(Fe,Ti)29The amount of precipitation of type crystalline phase.
In addition, the magnetic physical property of ferromagnetic material is evaluated with VSM.Condition determination and saturation magnetization and anisotropic magnetic
The computational methods of field intensity are identical with embodiment 1~43.
Then, determine each element concentration of the principal phase of 5 points respectively in 3 field of view by SEM-EDX measure, calculate
Go out the simple average value of this 15 points, so as to calculate the M element concentration in principal phase.
As shown in Table 1, in the ferromagnetic material of embodiment 1~43,30 atom % of M element are above is Fe, has higher
Saturation magnetization.In addition, the M element concentration in the principal phase of the ferromagnetic material of embodiment 1~27,31~37 and 39~41 is R
Element, Y element, M element and T elements total amount more than 87.4 atom %, there is extra high saturation magnetization.It will implement
Example 21~26 and 28,29,31~38,41 ferromagnetic material are denoted as (Fe1-yCoy) when, y value for 0.01 less than 0.3,
With extra high anisotropic magnetic field intensity.In addition, the ferromagnetic material of embodiment 1~27,31~37 and 39~41
Iα-(Fe,Co)/(Iα-(Fe,Co)+IThMn12) it is less than 0.15.In addition, the I of the ferromagnetic material of embodiment 31~373-29/(I3-29+IThMn12)
Less than 0.020, the saturation magnetization of principal phase is in more than 1.52T.Moreover, the magnet of embodiment 1~27,31~37 and 39~41
The saturation magnetization of the principal phase of material is in more than 1.48T, and the anisotropic magnetic field intensity of embodiment 1~43 is all in 3MA/m
More than.
In contrast, it is known that in the ferromagnetic material of comparative example 5, Fe be less than M element 30 atom %, saturation magnetization and
Anisotropy field low intensity.In addition, in comparative example 1~4, Y addition outside the scope of the present invention, α-(Fe, Co) phase
Amount of precipitation is more.
The value of the saturation magnetization and anisotropic magnetic field intensity of above-described embodiment 1~43 and comparative example 1~5 depends on
The value in application magnetic field used in evaluation.
Above-mentioned embodiment is shown as an example, it is not intended to which the scope of invention is defined.These new realities
The mode of applying can be implemented by other various modes, and various provinces can be carried out in the range of the technological thought of invention is not departed from
Slightly, displacement, change.These embodiments and its deformation are included in the scope and technological thought of invention, and are also included within
In invention and its equivalent scope described in claims.
Above-mentioned embodiment can be summarized as following technical scheme.
(technical scheme 1)
A kind of ferromagnetic material, it is with composition formula 1：(R1-xYx)aMbTc(in formula, R is more than one rare earth element, and T is
At least one element selected from Ti, V, Nb, Ta, Mo and W, M are the numbers that Fe either Fe and Co, x are satisfaction 0.01≤x≤0.8,
A is the atom % of 4≤a of satisfaction≤20 number, and b is the number for meeting b=100-a-c atoms %, and c is to meet the atom % of 0 ＜ c ＜ 7
Number) represent ferromagnetic material, have by ThMn12The principal phase that type crystalline phase is formed, 30 atom % of the M element of the composition formula 1 with
On be Fe.
(technical scheme 2)
Ferromagnetic material as described in technical scheme 1, wherein, 50 atom % of the R element of the composition formula 1 are above is Sm.
(technical scheme 3)
A kind of ferromagnetic material, it is with composition formula 2：(R1-xYx)aMbTcAd(in formula, R is more than one rare earth element, T
It is at least one element selected from Ti, V, Nb, Ta, Mo and W, M is that Fe either Fe and Co, A are to be selected from N, C, B, H and P extremely
A kind of few element, x are the numbers of satisfaction 0.01≤x≤0.8, and a is the atom % of 4≤a of satisfaction≤20 number, and c is to meet that 0 ＜ c ＜ 7 are former
Sub- % number, b are the numbers for meeting b=100-a-c atoms %, and d is the number for meeting the atom % of 0 ＜ d≤18) the magnet material that represents
Material, have by ThMn12The principal phase that type crystalline phase is formed, 30 atom % of the M element of the composition formula 2 are above is Fe.
(technical scheme 4)
Ferromagnetic material as described in technical scheme 3, wherein, 50 atom % of the R element of the composition formula 2 are above is be selected from
Ce, Pr, Nd, Tb and Dy at least one element.
(technical scheme 5)
Such as the ferromagnetic material any one of technical scheme 1~4, wherein, the X-ray diffraction pattern of the ferromagnetic material
In, relative to coming from the ThMn12The maximum of peak intensity of the maximum of the peak intensity of type crystalline phase with coming from α-(Fe, Co) phase
The ratio of the maximum of sum, the described peak intensity for coming from α-(Fe, Co) phase is less than 0.20.
(technical scheme 6)
Such as the ferromagnetic material any one of technical scheme 1~5, wherein, the Y of the composition formula 1 or the composition formula 2
Below the 50 atom % of element are by least one element substitution selected from Zr and Hf.
(technical scheme 7)
Such as the ferromagnetic material any one of technical scheme 1~6, wherein, the T of the composition formula 1 or the composition formula 2
50 atom % of element are above is Ti or Nb.
(technical scheme 8)
Such as the ferromagnetic material any one of technical scheme 1~7, wherein, the M of the composition formula 1 or the composition formula 2
Below the 20 atom % of element are by least one element substitution selected from Al, Si, Cr, Mn, Ni, Cu and Ga.
(technical scheme 9)
Ferromagnetic material as described in any one of technical scheme 1~8, wherein, the concentration of the M element in the principal phase is described
More than the 87.4 atom % of the total amount of R element, Y element, M element and T elements in principal phase.
(technical scheme 10)
Such as the ferromagnetic material any one of technical scheme 1~9, wherein, the composition formula 1 or the composition formula 2
The M is with Fe1-yCoyRepresent, the y is the number of satisfaction 0.01≤y≤0.3.
(technical scheme 11)
Such as the ferromagnetic material any one of technical scheme 1~10, wherein, the composition formula 1 or the composition formula 2
In, the x is the number for meeting 0.3 ＜ x≤0.6, and the c is the number for meeting the atom % of 3 ＜ c≤3.8.
(technical scheme 12)
Ferromagnetic material as described in technical scheme 11, wherein, in the X-ray diffraction pattern of the ferromagnetic material, relative to
Come from the ThMn12The maximum of the peak intensity of type crystalline phase is with coming from Nd3(Fe,Ti)29The maximum of the peak intensity of type crystalline phase it
It is sum, described to come from Nd3(Fe,Ti)29The ratio of the maximum of the peak intensity of type crystalline phase is less than 0.040.
(technical scheme 13)
A kind of permanent magnet, wherein, contain the ferromagnetic material any one of technical scheme 1~12.
(technical scheme 14)
A kind of permanent magnet, wherein, the sintered body with the ferromagnetic material any one of technical scheme 1~12.
(technical scheme 15)
A kind of electric rotating machine, wherein, there is stator and rotor, the stator or the rotor have described in technical scheme 14
Permanent magnet.
(technical scheme 16)
Electric rotating machine as described in technical scheme 15, wherein, the rotor is connected via axle with turbine.
(technical scheme 17)
A kind of vehicle, wherein, there is the electric rotating machine described in technical scheme 15.
(technical scheme 18)
Vehicle as described in technical scheme 17, wherein, the rotor and axis connection, rotation are delivered to the axle.
Claims (17)
1. a kind of ferromagnetic material, it is with composition formula：(R1-xYx)aMbTcAdThe ferromagnetic material of expression,
In formula, R is more than one rare earth element, and T is at least one element selected from Ti, V, Nb, Ta, Mo and W, M be Fe or
Person is Fe and Co, and A is at least one element selected from N, C, B, H and P, and x is the number of satisfaction 0.01≤x≤0.8, a be satisfaction 4≤
The atom % of a≤20 number, b are the numbers for meeting b=100-a-c atoms %, and c is the number for meeting the atom % of 0 ＜ c ＜ 7, and d is satisfaction 0
The atom % of≤d≤18 number；
The ferromagnetic material has by ThMn12The principal phase that type crystalline phase is formed；
30 atom % of the M element of the composition formula are above is Fe.
2. ferromagnetic material as claimed in claim 1, wherein,
The d is the number for meeting d=0 atoms %；
50 atom % of the R element of the composition formula are above is Sm.
3. ferromagnetic material as claimed in claim 1, wherein,
The d is the number for meeting the atom % of 0 ＜ d≤18；
50 atom % of the R element of the composition formula are above is at least one element selected from Ce, Pr, Nd, Tb and Dy.
4. such as ferromagnetic material according to any one of claims 1 to 3, wherein, the X-ray diffraction pattern of the ferromagnetic material
In, relative to coming from the ThMn12The maximum of peak intensity of the maximum of the peak intensity of type crystalline phase with coming from α-(Fe, Co) phase
The ratio of the maximum of sum, the described peak intensity for coming from α-(Fe, Co) phase is less than 0.20.
5. such as ferromagnetic material according to any one of claims 1 to 4, wherein, 50 atom % of the Y element of the composition formula with
It is lower by least one element substitution selected from Zr and Hf.
6. such as ferromagnetic material according to any one of claims 1 to 5, wherein, 50 atom % of the T elements of the composition formula with
On be Ti or Nb.
7. such as ferromagnetic material according to any one of claims 1 to 6, wherein, 20 atom % of the M element of the composition formula with
It is lower by least one element substitution selected from Al, Si, Cr, Mn, Ni, Cu and Ga.
8. such as ferromagnetic material according to any one of claims 1 to 7, wherein, the concentration of the M element in the principal phase is described
More than the 87.4 atom % of the total amount of R element, Y element, M element and T elements in principal phase.
9. such as ferromagnetic material according to any one of claims 1 to 8, wherein,
The M of the composition formula is with Fe1-yCoyRepresent,
The y is the number of satisfaction 0.01≤y≤0.3.
10. such as ferromagnetic material according to any one of claims 1 to 9, wherein, in the composition formula, the x is satisfaction 0.3
The number of ＜ x≤0.6, the c are the numbers for meeting the atom % of 3 ＜ c≤3.8.
11. ferromagnetic material as claimed in claim 10, wherein, in the X-ray diffraction pattern of the ferromagnetic material, relative to source
In the ThMn12The maximum of the peak intensity of type crystalline phase is with coming from Nd3(Fe,Ti)29The maximum sum of the peak intensity of type crystalline phase
, described come from Nd3(Fe,Ti)29The ratio of the maximum of the peak intensity of type crystalline phase is less than 0.040.
12. a kind of permanent magnet, wherein, contain the ferromagnetic material any one of claim 1~11.
13. a kind of permanent magnet, wherein, the sintered body with the ferromagnetic material any one of claim 1~11.
14. a kind of electric rotating machine, wherein, there is stator and rotor, the stator or the rotor have described in claim 13
Permanent magnet.
15. electric rotating machine as claimed in claim 14, wherein, the rotor is connected via axle with turbine.
16. a kind of vehicle, wherein, there is the electric rotating machine described in claim 14.
17. vehicle as claimed in claim 16, wherein, the rotor and axis connection, rotation are delivered to the axle.
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| CN111696741A (en) * | 2019-03-14 | 2020-09-22 | 株式会社东芝 | Magnet material, permanent magnet, rotating electrical machine, and vehicle |
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