CN101552061A - High resistivity compressed magnetic core - Google Patents

High resistivity compressed magnetic core Download PDF

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Publication number
CN101552061A
CN101552061A CNA2008101843269A CN200810184326A CN101552061A CN 101552061 A CN101552061 A CN 101552061A CN A2008101843269 A CNA2008101843269 A CN A2008101843269A CN 200810184326 A CN200810184326 A CN 200810184326A CN 101552061 A CN101552061 A CN 101552061A
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fluoride
powder
compressed
mentioned
iron
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CN101552061B (en
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今川尊雄
佐通祐一
小室又洋
铃木启幸
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Hitachi Ltd
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Hitachi Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/20—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/22—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
    • H01F1/24—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 soft-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together the particles being insulated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Soft Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention cheaply provides magnetic powder with a heat-resistant insulation film, and a compressed powder formed body with high specific resistance and small iron loss and the like. The compressed powder formed body is the compressed powder formed body that has the magnetic powder of the fluoride layer formed on the surface of the alloy powder using iron powder or iron as a main component, and the coating property of the fluoride film is improved by forming a substrate layer between the fluoride layer and the iron powder, so as to obtain the compressed magnetic core using the cheap iron powder.

Description

High resistivity compressed magnetic core
Technical field
The present invention relates to contain the compressed-core that the Magnaglo of ferro element is made, particularly relate to the compressed-core of the motor component that is suitable for electric rotating machine, reactor etc. by compression molding.
Background technology
In recent years, the viewpoint electric automobile from environmental problem receives much concern.Power source as such electric automobile possesses electric rotating machine (motor), in addition, possesses level and smooth transformer (reactor) in phase inverter output, requires to improve the efficient of these parts.Much less, wherein used magnetic core is low iron loss and is high magnetic flux density that their magnetic characteristic requires all can not reduce at high-frequency region even from low frequency.
Iron loss has with the eddy current loss in close relations of the ratio resistance of magnetic core and the magnetic hysteresis loss of the strain influence in the iron powder that is subjected to being taken place by the manufacture process of iron powder and process magnetic hysteresis thereafter.And shown in following (formula 1), iron loss (W) can by eddy current loss (We) and magnetic hysteresis loss (Wh) and the expression.In (formula 1), f is a frequency, and Bm is a magnetic flux density, and ρ is than resistance, and t is the thickness of material, k 1, k 2It is coefficient.
W=We+Wh=(k 1Bm 2t 2/ ρ) f 2+ k 2Bm 1.6F (formula 1)
According to (formula 1), owing to square proportional increase of eddy current loss (We), so particularly for the magnetic characteristic under the high frequency is not reduced, suppressing this eddy current loss (We) can not lack with frequency f.In order to suppress compressed-core eddy generation electricity, the size optimization of magnetic that must use, and on the surface of magnetic one by one, form dielectric film, use compressed-core by this magnetic compression molding.
Such compressed-core insulate when insufficient, reduces than resistance ρ, and it is big that eddy current loss (We) becomes.On the other hand, when in order to improve insulating properties dielectric film being thickened, the ratio of the volume that the soft magnetism powder in the magnetic core is occupied reduces, and magnetic flux density reduces.In addition, in order to improve that magnetic flux density is carried out the compression molding of soft magnetism powder with high pressure and when increasing the density of soft magnetism powder, magnetic hysteresis loss (Wh) increases because the distortion of the soft magnetism powder when being shaped is inevitable, so be difficult to suppress iron loss (W) as its result.Particularly owing to little, so the influence of the magnetic hysteresis loss (Wh) in the iron loss (W) increases in low frequency region eddy current loss (We).
At the method that has proposed to form insulating barrier in this problem patent documentation 1 with soft magnetism powder and insulating properties mix particles, on the surface of soft magnetism powder.In addition, disclose in the patent documentation 2 manufacture method as another kind of compressed-core, promptly be to form the method that the powder of the insulating coating of oxide scale film, phosphate coating etc. is made on the soft magnetic powder at Fe-Si by compression molding.In addition, disclose aqueous coating insulant in the patent documentation 3 and fixed, obtained high-resistance method by reprocessing.
In addition, the dielectric film that discloses the soft magnetism powder in the patent documentation 4 uses method of magnesium oxide.This method is by making the iron oxidation, magnesia powder is had an effect, and iron oxide is replaced as magnesium oxide and makes the method for surface insulation.But, have following problems with this method: can not make the MgO bed thickness to more than the oxidated layer thickness, in addition the MgO layer by more than 600 ℃ eliminate stress heat treatment its than the remarkable reduction of resistance.Relative therewith, even the heat treatment that the fluoride clad material has more than 600 ℃ reduces also little advantage than resistance.But, the iron powder shape that control is used, make the lining thickness of coating film evenly need labour and time, existing problems in use in purposes cheaply.
Patent documentation 1: the spy opens the 2003-332116 communique
Patent documentation 2: the spy opens the 2004-288983 communique
Patent documentation 3: specially permit communique No. 3475041
Patent documentation 4: the spy opens the 2006-233325 communique
The fluoride excellent heat resistance, also little with the iron reaction, be to solve the good method of above-mentioned problem, but must use processing gas atomized powder physically or water atomization powder to remove the iron powder of projection, wait for the Hybrid Vehicle magnetic core that requires the low-down a large amount of type of productions of price to be difficult to be suitable for.This is because the coating treatment fluid of fluoride based on alcohol, reacts with the raw material iron powder hardly, thereby can not successfully be overlayed on the concavo-convex complicated water atomization powder etc.Because general used phosphate treatment liquid is acid, institute is so that the iron powder surface oxidation forms the phosphoric acid covering simultaneously.Therefore, even the water atomization powder also can obtain high resistance.But because phosphoric acid undergoes phase transition about 500 ℃, thermal endurance can only be about 500 ℃.
The objective of the invention is to, clearly improve the method for the lining of fluoride coating layer, the magnetic core that goes for low price whirler soft magnetism powder is provided.
Summary of the invention
The invention provides high density, resistance value height, excellent in magnetic characteristics low price compressed-core and in order to obtain the suitable Magnaglo of this compressed-core.
According to compressed-core of the present invention, be will be formed with the iron powder of the fluoride layer that comprises terres rares fluoride or alkaline-earth metal fluoride from the teeth outwards or with iron as the alloy powder compression molding of principal component and the compressed-core that obtains, it is characterized in that, be provided with basalis in fluoride layer and iron powder or between with the alloy powder of iron as principal component.In addition, basalis is characterised in that, contains the oxide of alkaline-earth metal and alkaline-earth metal, contains at least a of MG, Ca, Ba or Sr.
In addition, according to compressed-core of the present invention, be will be formed with the iron powder of the fluoride layer that comprises fluoride or alkaline-earth metal fluoride from the teeth outwards or with iron as the alloy powder compression molding of principal component and the compressed-core that obtains, it is characterized in that, between fluoride layer and iron powder, has basalis, basalis contains the oxide of alkaline-earth metal and alkaline-earth metal, has oxygen containing layer between basalis and the iron powder, has the layer that contains oxygen and fluorine between basalis and the fluoride layer.
In addition, the press-powder formed body according to magnetic powder of the present invention is characterized in that, has in the raw material iron powder or the terres rares that forms on the alloy powder surface of iron as principal component or the combination of alkaline-earth metal fluoride coating film and basilar memebrane.
In addition, the average thickness that fluoride layer and basalis amount to (coating layer total thickness) is below the 100nm, and the preferred substrate layer is the following thickness of 50nm, and preferred fluorinated thing material is magnesium fluoride MgF 2
According to the present invention the thermal endurance height can be provided, than the high high density press-powder formed body of resistance.
Description of drawings
Fig. 1 is the ideograph as the section of routine in the past fluoride cladding iron powder.
Fig. 2 is the ideograph as the section of the fluoride cladding iron powder of embodiments of the invention.
Fig. 3 is ratio resistance and the total graph of a relation that coats thickness in the embodiment of the invention.
Fig. 4 is magnetic flux density and the total graph of a relation that coats thickness in the embodiment of the invention.
Fig. 5 be in the embodiment of the invention basalis thickness and than the graph of a relation of resistance.
Fig. 6 is the basalis thickness in the embodiment of the invention and the graph of a relation of magnetic flux density.
Embodiment
Fig. 1 be represent in the past the fluoride coating layer and the ideograph of iron powder section.For example be MgF 2Fluoride forms the preceding oxide layer that exists on the iron powder surface about 20nm.Fluoride form to use with the fluoride colloidal sol of alcohol as solvent, and to remove temperature be 350 ℃ low temperature to the solvent of colloidal sol in addition, and heat treatment thereafter is the highest 600～700 ℃, forms compressed-core raw material iron powder under this state.The fusing point of fluoride is more than 1000 ℃, and interfacial structure does not change under such treatment temperature.Thereby, residual oxygen containing layer on the fluoride interface.This oxygen containing layer is the oxide of iron.Since more stable according to energy state figure fluoride than the oxide of iron, so can not react even heat-treat same as before yet.Because coating layer avalanche (Ga れ) so can take place in the concavo-convex big and surperficial big part of curvature of iron powder in not reaction.Its result compares resistance decreasing.
Fig. 2 represents concept map of the present invention.Form the Ca layer with methods such as evaporations on the iron powder surface in advance.Evaporation is that iron powder is contacted with calcium, can (550～600 ℃) heat below the fusing point of calcium.On the iron powder that takes out with this state cooling back, form and form CaO basilar memebrane and the Ca metal film that forms gradient.Carrying out fluoride thereon coats.On the calcium surface, form thin oxide layer, but because calcium is that the fluoride state is more stable, so by under the high temperature about 100 ℃, carrying out (2) of above-mentioned fluoride method for coating, can obtain the mixed interface of oxygen and fluorine.Its result is because fluoride is bigger than the adhesion at fluoride and iron powder interface with the adhesion at calcium interface, so even the big iron powder interface of curvature also is difficult to take place avalanche.Its result also just can use the iron powder of the like that concavo-convex big cheapness of water atomization powder.As long as at high temperature in atmosphere, add hot iron, just can obtain thick oxide layer before the Ca evaporation, use this method just can obtain thick basalis according to temperature conditions.Used calcium powder amount is few, and is little to the influence of the cost of integral body.In addition, even with Mg, Ba or the Sr of the low price of the same easy formation oxide layer of calcium, being used for the occasion of basalis, also can obtain same effect.
Below specifically describe embodiments of the invention.In addition, the present invention is not limited by following embodiment.
(embodiment 1)
(treatment fluid facture)
(1) will be in water the high salt of solubility, promptly magnesium acetate 3g imports in the water of 100mL, dissolves fully with oscillator or ultrasonic stirring device.
(2) to generate NdF 3The amount of the equivalent of chemical reaction slowly adds and is diluted to 10% hydrofluoric acid.
(3) for the MgF that generates colloidal sol shape precipitation 2Solution use the ultrasonic stirring device to stir more than 1 hour.
(4) after the rotary speed centrifugation with 4000～6000r.p.m, remove the top clarified solution, add substantially with the methyl alcohol of measuring.
(5) stirring contains colloidal sol shape MgF 2Methanol solution after become suspension fully, stir more than 1 hour with the ultrasonic stirring device.
(6) operation of 3～10 times (4) and (5) repeatedly is until the anion that can not detect acetic acid ion or hydrofluoric acid ion etc.
(7) finally become colloidal sol shape MgF 2As the iron powder treatment fluid is until MgF with the methyl alcohol dilution 2The solution that becomes the relation of 1g/8mL and make.
(fluoride method for coating)
(1) adds the NdF of 8mL with respect to the gas atomization iron powder of 40g particle diameter 100 μ m 3Treatment fluid is mixed to and can confirms that whole iron powders are by moistening.
(2) under the decompressions of 2～5 holders to the MgF of (1) 2Handle iron powder and carry out removing of solvent methanol.
(3) with the carrying out of (2) iron powder removed of solvent move in the quartzy system boat, 5 * 10 -5Carry out 200 ℃ of 30 minutes and 350 ℃ of heat treatments of 30 minutes under the decompression of holder, making raw material iron powder.
(4) iron powder that is obtained by (3) is carried out conditioning treatment under 600 ℃.
(5) will carry out heat treated iron powder by (4) uses superhard mould to make the ring-shaped sample of external diameter 18mm, internal diameter 10mm as magnetic flux density and coercitive magnetic-measurement sample by compression.At this moment, compression pressure is 10t/cm 2
(6) will use the mould of 10 * 10mm to make the cuboid sample is measured usefulness as resistance value sample by the iron powder that (4) form by compression.It is 10t/cm that compression is pressed 2
(7) will pack in the stator system effect compression molding by the iron powder that (4) form, press 10t/cm to be shaped 2Compress.Form sample with (5) (6) and under 600 ℃, heat-treat, discharge strain.
(8) on the stator that forms by (7), implement coiling, make whirler.
Fig. 3 has represented to cover 20nm thickness, carry out MgF again at the water atomization pruinescence that makes average grain diameter 70 μ m with calcium (Ca) 2Total coating thickness and formed body are than the relation of resistance in the sample of the embodiment 1 that coats.Formed body is 10mm * 10mm * 2mm (thickness), is measured by 4 terminal methods than resistance.The pressure that is shaped is 1.2GPa.The heat treatment temperature that eliminates stress all is 600 ℃.By Fig. 3, even identical coating thickness, use calcium and form 2 layers embodiment than resistance height.Than resistance must be more than the 2m Ω cm, and comparative example is all insufficient in this scope.Relative therewith, among the embodiment when gross thickness 50nm is above, its than resistance more than 2m Ω cm.
Fig. 4 be with identical raw material form external diameter 50mm, internal diameter 40mm, thickness 5mm ring-shaped sample, carry out the dependence of total coating thickness of the magnetic flux densities that the coilings of 1 time 200 circle, 2 40 circles measure.The pressure that is shaped is 1.2GPa.The heat treatment temperature that eliminates stress is 600 ℃.Condition determination is that the D.C. magnetic field of excitation field 10000A/m is measured.Show that by Fig. 4 as long as coating thickness is identical, magnetic flux density does not just change.Show in addition, because necessary magnetic flux density is more than the 1.65T, so gross thickness must be below 100nm.
(comparative example 1)
Use is carried out MgF to the water atomization powder of average grain diameter 70 μ m 2The sample that coats is used with the same method of the foregoing description 1 and is measured than resistance and magnetic flux density.The results are shown among Fig. 3 and Fig. 4.
(comparative example 2)
Use is carried out the sample that Mg coats to the water atomization powder of average grain diameter 70 μ m, uses with the same method of the foregoing description 1 and measures than resistance and magnetic flux density.The results are shown among Fig. 3 and Fig. 4.
(embodiment 2)
The sample that use is made by the method identical with embodiment 1, MgF 2Coating thickness is 60nm, and the basalis thickness of calcium is changed from 20nm to 60nm, and research is than resistance and magnetic flux density, and it the results are shown in Fig. 5 and Fig. 6.Fig. 5 is than changes in resistance, in this scope, all is more than the 2m Ω cm than resistance, is good.On the other hand, Fig. 6 is the variation of magnetic flux density, is below the 50nm owing to become the above basalis thickness of 1.65T, so the preferred substrate layer thickness is below the 50nm.
Here, coating thickness is below the 60nm, if how the part of substrate Ca is formed, the basalis of keeping magnetic flux density just thickens.But, when the ratio 50nm of substrate Ca increases, because of not enough can not the keeping of thermal endurance of CaO layer compared resistance.Therefore, basalis is to be suitable below the 50nm.

Claims (7)

1. compressed-core, be be formed with from the teeth outwards the fluoride layer that comprises terres rares fluoride or alkaline-earth metal fluoride iron powder or with iron as the alloy powder compression molding of principal component and the compressed-core that obtains it is characterized in that,
Be provided with basalis in above-mentioned fluoride layer and above-mentioned iron powder or between with the above-mentioned alloy powder of iron as principal component.
2. compressed-core according to claim 1 is characterized in that above-mentioned basalis contains the oxide of alkaline-earth metal and above-mentioned alkaline-earth metal.
3. compressed-core according to claim 1 is characterized in that above-mentioned basalis contains at least a of Mg, Ca, Ba or Sr.
4. compressed-core according to claim 1 is characterized in that,
The total thickness of above-mentioned basalis and above-mentioned fluoride layer is below the 100nm,
The thickness of above-mentioned basalis is below the 50nm.
5. compressed-core according to claim 1 is characterized in that above-mentioned fluoride is a magnesium fluoride.
6. compressed-core, be be formed with from the teeth outwards the fluoride layer that comprises terres rares fluoride or alkaline-earth metal fluoride iron powder or with iron as the alloy powder compression molding of principal component and the compressed-core that obtains it is characterized in that,
Between above-mentioned fluoride layer and iron powder, have basalis,
Above-mentioned basalis contains the oxide of alkaline-earth metal and above-mentioned alkaline-earth metal,
Have oxygen containing layer between above-mentioned basalis and the above-mentioned iron powder,
Has the layer that contains oxygen and fluorine between above-mentioned basalis and the above-mentioned fluoride layer.
7. compressed-core according to claim 6 is characterized in that above-mentioned alkaline-earth metal is a calcium.
CN2008101843269A 2007-12-10 2008-12-10 High resistivity compressed magnetic core Expired - Fee Related CN101552061B (en)

Applications Claiming Priority (3)

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JP2007317830A JP4576418B2 (en) 2007-12-10 2007-12-10 High resistance dust core
JP2007317830 2007-12-10
JP2007-317830 2007-12-10

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US6511552B1 (en) * 1998-03-23 2003-01-28 Sumitomo Special Metals Co., Ltd. Permanent magnets and R-TM-B based permanent magnets
EP1675136B1 (en) * 2003-10-15 2016-05-11 Sumitomo Electric Industries, Ltd. Soft magnetism material and powder magnetic core
JP4654709B2 (en) * 2004-07-28 2011-03-23 株式会社日立製作所 Rare earth magnets
CN100433204C (en) * 2004-07-28 2008-11-12 株式会社日立制作所 Rare-earth magnet
JP2006041203A (en) * 2004-07-28 2006-02-09 Hitachi Ltd Magnetic material for electrical device core, method for manufacturing the same, motor, motor for household electric appliance, electric generator, and motor for electric automobile
JP4863628B2 (en) * 2004-09-06 2012-01-25 株式会社ダイヤメット Method for producing Mg-containing oxide film-coated soft magnetic metal powder and method for producing composite soft magnetic material using this powder
TWI413137B (en) * 2005-03-23 2013-10-21 Shinetsu Chemical Co Functionally graded rare earth permanent magnet
JP4525425B2 (en) * 2005-03-31 2010-08-18 株式会社日立製作所 Fluoride coat film forming treatment liquid, fluoride coat film forming method and magnet
JP2007116088A (en) * 2005-09-26 2007-05-10 Hitachi Ltd Magnetic material, magnet and rotating machine
CN100565720C (en) * 2005-09-26 2009-12-02 株式会社日立制作所 Magnetic material, magnet and whirler
JP4719568B2 (en) * 2005-12-22 2011-07-06 日立オートモティブシステムズ株式会社 Powder magnet and rotating machine using the same

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