CN101142044B - Iron powder coated with mg-containing oxide film - Google Patents

Iron powder coated with mg-containing oxide film Download PDF

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CN101142044B
CN101142044B CN2005800491939A CN200580049193A CN101142044B CN 101142044 B CN101142044 B CN 101142044B CN 2005800491939 A CN2005800491939 A CN 2005800491939A CN 200580049193 A CN200580049193 A CN 200580049193A CN 101142044 B CN101142044 B CN 101142044B
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powder
iron
oxide
film
soft magnetic
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CN101142044A (en
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渡边宗明
中山亮治
鱼住学司
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Diamet Corp
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Diamet Corp
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Priority claimed from JP2005155206A external-priority patent/JP4761835B2/en
Priority claimed from JP2005155207A external-priority patent/JP4761836B2/en
Priority claimed from JP2005158892A external-priority patent/JP2006324612A/en
Priority claimed from JP2005158893A external-priority patent/JP5027390B2/en
Priority claimed from JP2005161480A external-priority patent/JP4480628B2/en
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Priority claimed from PCT/JP2005/020204 external-priority patent/WO2006080121A1/en
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Abstract

An oxide coated Fe powder for use to produce various electromagnetic circuit parts requiring high specific resistance. There is provided an Mg-containing oxide coated iron (Fe) powder comprising an iron powder having its surface coated with an Mg-Fe-O ternary oxide deposition film containing at least (Mg,Fe)O, wherein the (Mg,Fe)O is a crystalline wustite having MgO solid dissolved therein, and wherein the Mg-Fe-O ternary oxide deposition film in a region of interface with iron powder has a sulfur enriched layer containing sulfur in a concentration higher than in the center region of the iron powder, further having a microcrystalline structure of = 200 nm crystal grain diameter, the outermost surface of which consists essentially of MgO. Furthermore, there is provided a composite soft magnetic material making use of the Mg-containing oxide coated iron (Fe) powder.

Description

Contain the iron powder that the Mg oxide-film coats
Technical field
The present invention relates on the surface of iron powder, be formed with at least and contain (Mg, Fe) O or the atomic particle of metal Fe are dispersed in containing the iron powder that the Mg oxide-film coats and being used to make the iron powder that the deposited film of high resistance composite soft magnetic material coats of Mg-Fe-O ternary system oxide deposited film in the blank, contain the raw material that composite soft magnetic material that iron powder that the Mg oxide-film coats makes is used as various electromagnetic components such as various electromagnetic circuit parts that needs hang down iron loss, for example motor, actuator, yoke, iron core, reactor by this.
In addition, the Mg-Si-Fe-O quaternary system deposited oxide film that the present invention relates to be formed by Mg, Si, Fe and O is coated on the iron Si powder that deposited oxide film that the surface of iron Si powder forms coats, further, the present invention relates to the composite soft magnetic material that the press-powder fired body of the iron Si powder that coated by this deposited oxide film constitutes, further, the present invention relates to the iron core of the various electromagnetic components that constitute by described composite soft magnetic material, further, the present invention relates to be assembled with described iron core electric equipment, relate in particular to reactor.
In addition, the present invention relates to be coated on Fe-Si by the deposited oxide film that Mg, Si, Fe and O form is that the Fe-Si that the deposited oxide film that forms on the surface of iron-based soft magnetic powder coats is iron-based soft magnetic powder and manufacture method thereof, and the Fe-Si that uses this deposited oxide film to coat is that the composite soft magnetic material that iron-based soft magnetic powder is made is used as the raw material that needs hang down the various electromagnetic circuit parts as described above of iron loss.
In addition, the present invention relates to a kind of composite soft magnetic powder, this powder is further to coat MgO-SiO on the surface of the iron powder that contains the coating of Mg oxide-film 2The system complex oxide film (is preferably with mol ratio and calculates MgO/SiO 2Value be 2 forsterite) form, the iron powder that the wherein said Mg of containing oxide-film coats is by containing (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O is coated on and forms on the surface of iron powder, and relate to a kind of high strength that has that this composite soft magnetic powder makes of using, high magnetic flux density and the few composite soft magnetic material of high-resistance iron loss, and this has high strength, the composite soft magnetic material that high magnetic flux density and high-resistance iron loss are few can be as the various electromagnetic circuit parts that need low iron loss, motor for example, actuator, yoke, rotor, unshakable in one's determination, the raw material of various electromagnetic components such as reactor.
In addition, the present invention relates to a kind of composite soft magnetic powder, this powder is further to coat MgO-SiO on the surface of the iron powder that contains the coating of Mg oxide-film 2The system complex oxide film (is preferably with mol ratio and calculates MgO/SiO 2Value be 2 forsterite) form, the iron powder that the wherein said Mg of containing oxide-film coats is to be coated on the surface of iron powder by the Mg-Fe-O ternary system oxide deposited film of metal Fe microparticulate in blank to form, and, relate to a kind of high strength that has of using this composite soft magnetic powder making, high magnetic flux density and the few composite soft magnetic material of high-resistance iron loss, and this has high strength, the composite soft magnetic material that high magnetic flux density and high-resistance iron loss are few can be as the various electromagnetic circuit parts that need low iron loss, magnetic core for example, iron core of electric motor, generator core, solenoid plunger, the igniter iron core, reactor, transformer, choke core, the raw material of various electromagnetic circuit parts such as Magnetic Sensor iron core.
Background technology
Be well known that generally the soft magnetic material that uses in the various electromagnetic circuit parts is owing to require iron loss little, so will improve resistance, reduce eddy current losses, reduce coercive force, reduce magnetic hysteresis loss.And, in recent years, owing to pursue the miniaturization of electromagnetic circuit, high responseization, so the higher material of magnetic flux density also comes into one's own.
As an example of the material powder that is used to make soft magnetic material, be well known that having coated the Mg ferrite that contains with insulating properties on the surface of iron powder (knownly has (MgFe) with described high resistivity 3O 4, have spinel-type crystalline texture) film contain the iron powder (referring to Patent Document 1) that the Mg oxide-film coats.
In addition, as other a example known have to have coated on the surface of iron Si powder contain Mg and change into and handle changing into of film and handle the iron Si powder (referring to Patent Document 2) that film coats.
And then, as other a example, known have the Si:0.1 of containing～10 quality %, and all the other Fe-Si that are made of Fe and unavoidable impurities are iron-based soft magnetic powder, and then to it is also known at this Fe-Si be the soft magnetic powder that the surface of iron-based soft magnetic powder has coated the high resistance material.Also known a kind of method of making composite soft magnetic material, the soft magnetic powder that has formed the high resistance material on its surface is compressed shaping, the press-powder body that obtains is carried out sintering, obtain having the composite soft magnetic material (referring to Patent Document 3) that between the soft magnetism example, accompanies the tissue of high resistance material and have high resistivity.
Also known a kind of method of making press-powder magnetic material etc., to coat the iron powder and the low-melting glass powder that contain the coating of Mg iron oxide film that contain the Mg ferrite membrane by chemical method is mixed together, make mixed-powder, again this mixed-powder is carried out compression molding and heat-treat manufacturing press-powder magnetic material (referring to Patent Document 4 or 5).
Patent documentation 1:JP spy opens flat 11-1702 communique
Patent documentation 2:JP spy opens the 2003-142310 communique
Patent documentation 3:JP spy opens flat 5-258934 communique
Patent documentation 4:JP spy opens the 2004-253787 communique
Patent documentation 5:JP spy opens the 2004-297036 communique
But, the existing iron powder that the Mg oxide-film coats that contains that contains the Mg ferrite membrane that coated, owing to contain the Mg ferrite membrane in the coating of the surface of iron powder by chemical method, so the press-powder body after the drawing is carried out that the high temperature destressing is fired and the composite soft magnetic material that obtains, it is unstable that ferrite membrane becomes, insulating properties descends, and it is not enough with respect to the connecting airtight property on the surface of iron powder to contain the Mg ferrite membrane, even the iron powder that contains the coating of Mg iron oxide film is carried out firing after the drawing, also can't make the composite soft magnetic material of sufficient intensity, by the existing iron powder that the Mg oxide-film coats of containing that contains the Mg ferrite membrane that coated is carried out drawing and is fired, perhaps mix with the low-melting glass powder by having coated the iron powder that contains the coating of Mg iron oxide film that contains the Mg ferrite membrane, obtain mixed-powder, this mixed-powder is carried out drawing and heat-treats, the composite soft magnetic material of Zhi Zuoing is because of containing the Mg ferrite membrane and peel off or reason such as breakage in the stamping process like this, can't play enough insulation effect, therefore, existence can't obtain the shortcoming of enough high resistivities.
In addition, these existing coatings contain the iron Si powder of handling the film coating that changes into that Mg changes into the processing film, change into the processing film owing to contain Mg by the chemical method coating, so oxide-film is with respect to the weak strength of connecting airtight of iron Si powder, and the weak strength of oxide-film itself, therefore by the existing iron Si powder of handling the film coating that changes into is carried out drawing and is fired the composite soft magnetic material of making, handle that film is peeled off or breakage etc. because of in stamping process, changing into, and can't play enough insulation effect.In addition, by chemical method coated the described Mg of containing change into handle film change into the processing film, but also the time because of firing middle decomposition in the high temperature destressing, resistance descends, so existence can not get the shortcoming of the composite soft magnetic material of enough high resistivities.
In addition, one example of the high resistance material that forms as the surface that at described Fe-Si is iron-based soft magnetic powder, consider to contain Mg ferrite oxide-film, to having coated this Fe-Si that contains oxide-film coating of Mg ferrite oxide-film is that iron-based soft magnetic powder carries out drawing, make the press-powder body, fire even this press-powder body is carried out the high temperature destressing, also can not get enough high resistivities.As its reason, generally be to contain the Mg ferrite with respect to thermally labile, ferrite structure changes if heat then, and insulating properties descends easily, and therefore the insulating properties of the composite soft magnetic material that obtains descends.And then, the Fe-Si that has coated the existing Mg of containing ferrite oxide-film is an iron-based soft magnetic powder, coating contains Mg ferrite oxide-film on the surface because by chemical method, so it is not enough to contain Mg ferrite oxide-film and with respect to Fe-Si be the connecting airtight property on surface of iron-based soft magnetic powder, by being that iron-based soft magnetic powder carries out drawing and fires the composite soft magnetic material of making to the Fe-Si that has coated the existing Mg of containing ferrite oxide-film, in stamping process, because of containing that Mg ferrite oxide-film is peeled off or breakage etc., and can't play enough insulation effect.Therefore there is the shortcoming that can not get enough high resistivities.
Summary of the invention
Therefore, the inventor studies the iron powder that contains the coating of Mg oxide-film that will make, even iron powder drawing wherein, the high resistance oxide-film on iron powder surface can be not damaged yet when drawing, oxide-film connects airtight securely in the surface, fires even carry out the high temperature destressing after drawing, and the insulating properties on surface can not descend yet, the resistance height, eddy current losses is low, in addition, and when carrying out the firing of stress relief annealing, can further reduce coercive force, the magnetic hysteresis loss step-down.Consequently, by in the oxidizing gas environment, heating iron powder in advance, the surface that is produced on iron powder has formed the iron powder (hereinafter referred to as the oxidation processes iron powder) of iron oxide film, in this oxidation processes iron powder, add Mg powder and mixing, the mixed-powder that obtains is heated in inert gas environment or vacuum environment, further heating enforcement rear oxidation processing in the oxidizing gas environment afterwards then can obtain following opinion:
(1) at general known MgO-FeO-Fe 2O 3Representational in the system (Mg, Fe) O, (Mg, Fe) 3O 4Among the various oxides of MgO-Fe-O ternary system, at least contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O is formed on the surface of iron powder, and coated this on the surface of iron powder and contained (Mg at least, Fe) iron powder that contains the coating of Mg oxide-film of the Mg-Fe-O ternary system oxide deposited film of O, having formed the iron powder that contains the coating of Mg oxide-film that contains the Mg ferrite membrane with existing surface in iron powder compares, oxide-film is obviously superior with respect to the connecting airtight property of iron powder, therefore in stamping process, the situation that iron powder contacts with each other as the oxide-film of insulating coating is destroyed seldom appears, even carrying out the high temperature destressing after drawing fires, the insulating properties of oxide-film can not descend yet, can keep high resistance, so eddy current losses is low, and then when carrying out destressing and fire, owing to can further reduce coercive force, so can suppress magnetic hysteresis loss lower, therefore, can obtain having the composite soft magnetic material of low iron loss.
(2) more preferably, in the Mg-Fe-O ternary system oxide deposited film of the iron powder that the described Mg of containing oxide-film coats, contain (Mg, Fe) O is the MgO solid solution wustite (material of MgO solid solution in wustite (FeO)) of crystalline.
(3) in described iron powder with contain at least that (Mg, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O is formed with dense sulphur layer, the concentration height as the sulphur of unavoidable impurities that the concentration ratio of sulphur contains at the central part of iron powder in this dense sulphur layer.
(4) describedly contain at least that (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide deposited film of O.
(5) containing at least of forming on the surface of described iron powder, (amount of its most surperficial MgO that contains was The more the better for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and most preferably, it is the most surperficial to be made of MgO in fact.
The present invention just is being based on described opinion and is proposing, and it has following feature:
(1) a kind ofly contains the iron powder that the Mg oxide-film coats, be coated with at least on the surface of iron powder and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O;
(2) iron powder that contains the coating of Mg oxide-film of described (1) record, wherein, in the Mg-Fe-O ternary system oxide deposited film of the iron powder that the described Mg of containing oxide-film coats, contain (Mg, Fe) O is the MgO solid solution wustite of crystalline;
(3) iron powder that contains the coating of Mg oxide-film of described (1) or (2) record, wherein, the described iron powder that contains the coating of Mg oxide-film, at iron powder and the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer;
(4) described (1), (2) or (3) record contain the iron powder that the Mg oxide-film coats, wherein, describedly contain at least (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide deposited film of O;
(5) described (1), (2) or (3) record contain the iron powder that the Mg oxide-film coats, wherein, describedly contain (Mg, Fe) the most surperficial formation by MgO in fact of the Mg-Fe-O ternary system oxide deposited film of O at least.
The described iron powder that contains the coating of Mg oxide-film in described (1) of the present invention～(4), by in the oxidizing gas environment, heating iron powder in advance, be produced on the oxidation processes iron powder that has formed the iron oxide film on the surface of iron powder, in this oxidation processes iron powder, add Mg powder and mixing, the mixed-powder that obtains is heated in inert gas environment or vacuum environment, further heating enforcement rear oxidation processing in the oxidizing gas environment afterwards, can be made into thus, though be illustrated above, but, more particularly, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this oxidation processes iron powder, add the Mg powder and mix, with the mixed-powder that obtains 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1After heating in the inert gas environment of MPa or the vacuum environment, further in the oxidizing gas environment, heat for 50～350 ℃, implement rear oxidation and handle, make thus with temperature.
The most surperficial Mg-Fe-O ternary system oxide deposited film that contains MgO solid solution wustite phase that is made of MgO in fact of described (5) of the present invention record can be made as follows and obtain, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this oxidation processes iron powder, add more Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1After heating in the inert gas environment of MPa or the vacuum environment, further in the oxidizing gas environment, heat for more time, implement rear oxidation and handle, make thus.
The Mg-Fe-O ternary system oxide deposited film that forms on the surface of iron powder of the present invention contains (Mg, Fe) O at least.Preferably, in this Mg-Fe-O ternary system oxide deposited film, contain (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.Most preferably, this contains at least that (Mg, Fe) the most surperficial of the deposited film of O is made of MgO.Also can not be (Mg, Fe): O=1: 1, and O has the solid solution width.
So-called " deposited film " this term ordinary representation for example is deposited on the epithelium that obtains on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, at least contain (Mg but the surface in iron powder of the present invention forms, Fe) the Mg-Fe-O ternary system oxide deposited film of O, the iron oxide (Fe-O) and the Mg on expression oxidation processes iron powder surface are deposited on the lip-deep epithelium of this iron powder along with reaction.And containing at least of forming on this iron powder surface, (Mg, the Fe) thickness of the Mg-Fe-O ternary system oxide deposited film of O was in order to obtain the high magnetic flux density and the high resistivity of the composite soft magnetic material after press-powder is shaped, preferably in the scope of 5nm～500nm.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, then the be shaped magnetic flux density of thick composite soft magnetic material of press-powder descends, and is not preferred.More preferably thickness is in the scope of 5nm～200nm.
Constitute the described (Mg that contains at least of the iron powder of the Mg of containing oxide-film coating of the present invention, Fe) the Mg-Fe-O ternary system oxide deposited film of O, at the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer.Having this dense sulphur layer can measure sulphur concentration by the auger electrons optical spectroscopy, and it is used graphical representation, confirms according to the sulphur concentration peak value.Owing to have so dense sulphur layer at borderline region, so contain (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O further improves with respect to the connecting airtight property on iron powder surface, deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, can keep high resistance, so eddy current losses reduces.The sulphur of dense sulphur layer contains the sulphur as unavoidable impurities in iron powder, most of sulphur that is contained by the surface portion in this iron powder is supplied with.
Surface in iron powder of the present invention forms describedly contains at least that (its crystal grain is fine more good more for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and preferably having the crystallization particle diameter is the following fine crystal tissue of 200nm.By having such fine crystal tissue, micro-crystallization Mg-Fe-O ternary system oxide deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, in addition, fire even carry out the high temperature destressing, oxide is also stable, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, then the thickness of Mg-Fe-O ternary system oxide deposited film becomes thicker than 500nm, and the magnetic flux density of the composite soft magnetic material that press-powder is shaped descends, and is therefore not preferred.
What in addition, constitute iron powder that the Mg of containing oxide-film of the present invention coats describedly contains at least that (amount of the MgO that it is the most surperficial is The more the better, most preferably is made of MgO in fact for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O.If the most surperficial MgO that comes down to, then when the firing of the press-powder body of drawing, also prevent the Fe diffusion, can prevent iron powder contact combination each other, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.
Constitute the described (Mg that contains at least of the iron powder of the Mg of containing oxide-film coating of the present invention, Fe) the Mg-Fe-O ternary system oxide deposited film of O, the part of Mg can be with replacing with respect to Mg more than one among the Al below 10%, Si, Ni, Mn, Zn, Cu, Co and are formed false ternary system oxide deposited film.
It is the interior powder of scope of 5～500 μ m that the iron powder that the Mg of containing oxide-film of the present invention coats is preferably used average grain diameter.Its reason is, if average grain diameter is more much smaller than 5 μ m, then the compressibility of powder descends, the volume ratio of powder reduces, so the decline of the value of magnetic flux density, and is therefore not preferred, on the other hand, if average grain diameter is more much bigger than 500 μ m, then the vortex flow of powder inside increases, and the permeability under the high frequency reduces.
The manufacture method of the composite soft magnetic material of the iron powder of using the Mg of containing oxide-film coating of the present invention then, is described.
The iron powder that the Mg of containing oxide-film of the present invention coats can be carried out press-powder by usual way and is shaped to fire and make.
The composite soft magnetic material with high resistivity that the iron powder that adopts the Mg of containing oxide-film of the present invention to coat is made preferably contains Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
In addition, with the average grain diameter that contains 0.05～1 quality % is silica, in the aluminium oxide one or both below the 0.5 μ m, the mode that all the other iron powder that coated by the Mg of containing oxide-film of the present invention constitute cooperates mixing, make mixed-powder, by usual way press-powder this mixed-powder that is shaped, can make by firing.According to this manufacture method, what constitute iron powder that the Mg of containing oxide-film of the present invention coats contains (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O and silica or aluminium oxide reaction, form composite oxides, can obtain sandwiching composite soft magnetic material with high resistivity with high-resistance composite oxides at the crystal boundary of iron powder, and owing to fire via silica or aluminium oxide, so but the superior composite soft magnetic material of manufacturing machine intensity.In this case, owing to being that main body is fired,, therefore, can make the few composite soft magnetic material of magnetic hysteresis loss so can guarantee less coercive force with silica or aluminium oxide.Described firing preferably in inert gas environment or oxidizing gas environment carried out under 400～1300 ℃ of temperature.
In addition, adding collosol and gel (silicate) solution of silica or the wet type solution such as sol gel solution of aluminium oxide in the iron powder that the Mg of containing oxide-film of the present invention coats mixes dry afterwards, this dried mixture is being carried out compression molding, afterwards in inert gas environment or oxidizing gas environment, by under 400～1300 ℃ of temperature, firing, can make composite soft magnetic material thus.The composite soft magnetic material with high resistivity that these iron powder that adopt the Mg of containing oxide-film of the present invention to coat are made preferably contains Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
And then, the composite material that mixes organic insulation, inorganic insulating material or organic insulation and inorganic insulating material in the iron powder that the Mg of containing oxide-film of the present invention coats forms to be fired, and then can make the composite soft magnetic material that resistivity and intensity further improve.At this moment, in organic insulation, can use epoxy resin or fluororesin, phenolic resins, polyurethane resin, silicone resin, mylar, phenoxy resin, Lauxite, isocyanate resin, acrylic resin, polyimide resin etc.In addition, in inorganic insulating material, can use phosphate such as ferric phosphate, various glassy insulant, be the waterglass of principal component, insulating properties oxide etc. with sodium metasilicate.
In addition, contain in the iron powder that the Mg oxide-film coats, of the present invention with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, in boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide of cooperation 0.05～1 quality % one or more, mix the back press-powder and be shaped, the press-powder formed body that obtains is fired under 500～1000 ℃ of temperature, can make composite soft magnetic material thus.So the composite soft magnetic material of making has following composition: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3In boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide that contains 0.05～1 quality % one or more convert, all the other are made of the iron powder that the Mg of containing oxide-film of the present invention coats, form and contain (Mg, Fe) epithelium of the Mg-Fe-O ternary system oxide deposited film of O and one or more reactions in boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide at least.
In addition, this composite soft magnetic material can followingly obtain: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert with the sol solution or the powder of the boron oxide that contains 0.05～1 quality %, the sol solution of vanadium oxide or powder, the sol solution of bismuth oxide or powder, the sol solution of the sol solution of antimony oxide or powder and molybdenum oxide or among the powder one or more, forming that all the other iron powder that coated by the Mg of containing oxide-film of the present invention constitute cooperates, mix, dry, the mixed oxide that making is made of oxide desiccant gel or powder coats the iron powder that mixed oxide that iron powder that the described Mg of containing oxide-film of the present invention coats forms coats, carry out press-powder in the iron powder that this mixed oxide is coated, after the shaping, by under 500～1000 ℃ of temperature, firing and can obtain.The composite soft magnetic material that the iron powder that adopts these Mg of containing oxide-films of the present invention to coat is made with high resistivity, preferably contain Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
The composite soft magnetic material that the iron powder that adopts the Mg of containing oxide-film of the present invention to coat is made has high density, high resistivity and high magnetic flux density, this composite soft magnetic material is owing to the feature with high magnetic flux density, the low iron loss of high frequency, so can be as the material of the various electromagnetic circuit parts that this feature is played a role.Described electromagnetic circuit parts have magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, reactor, transformer, choke core or magnetic sensor iron core etc.And, the electromagnetic circuit parts with high-resistance composite soft magnetic material formation that are assembled with the iron powder that adopts the Mg of containing oxide-film coating of the present invention have motor, generator, solenoid, injector, Electromagnetically driven valve, inverter (inverter), transverter (converter), transformer, relay, biosensor systems etc., can realize high efficiency, high-performance and the small-sized light weight of electric equipment.
In addition, the inventor studies in order to make such iron powder that contains the coating of Mg oxide-film, even this iron powder that contains the coating of Mg oxide-film is drawing, the high resistance oxide-film on iron powder surface can be not damaged yet when drawing, oxide-film connects airtight the iron powder in the surface securely, even carrying out the high temperature destressing after drawing fires, the insulating properties on surface can not descend yet, the resistance height, eddy current losses is low, in addition, and when carrying out the firing of stress relief annealing, can further reduce coercive force, the magnetic hysteresis loss step-down.
Consequently, by implementing the oxidation processes of heating iron powder in the oxidizing gas environment in advance, be produced on the iron powder (hereinafter referred to as the oxidation processes iron powder) that has formed the iron oxide film on the surface of iron powder, in this oxidation processes iron powder, add Mg powder and mixing, the mixed-powder that obtains is implemented heat treated while rotating in inert gas environment or vacuum environment, then can obtain following opinion:
(6) form the atomic particle of metal Fe on the surface of iron powder and be distributed to Mg-Fe-O ternary system oxide deposited film in the blank, the Mg-Fe-O ternary system oxide deposited film that the atomic particle of this metal Fe is distributed in the blank is distributed in the blank owing to the atomic particle of metal Fe, so have very strong toughness, compare with the existing Mg of containing ferrite membrane, morphotropism is superior, in addition, be coated with the atomic particle of metal Fe and be distributed to the iron powder that the Mg oxide-film coats that contains of Mg-Fe-O ternary system oxide deposited film in the blank, having formed the iron powder that contains the coating of Mg oxide-film that contains the Mg ferrite membrane with existing surface in iron powder compares, because the atomic particle of metal Fe is distributed to and contains in the Mg oxide-film blank, so have very strong toughness, can fully follow the distortion of iron powder, and then oxide-film is very good with respect to the connecting airtight property of iron powder, therefore, in stamping process, situation that iron powder contacts with each other is few as the oxide-film of insulating coating is destroyed, even carrying out the high temperature destressing after drawing fires, the insulating properties of oxide-film can not descend yet, can keep high resistance, eddy current losses is low, and then when carrying out destressing and fire, owing to can further reduce coercive force, so can suppress magnetic hysteresis loss lower, therefore, can obtain having the composite soft magnetic material of low iron loss
(7) the atomic particle of described metal Fe is distributed to Mg-Fe-O ternary system oxide deposited film in the blank and has the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside;
(8) the Mg-Fe-O ternary system oxide deposited film that is distributed in the blank of the atomic particle of described metal Fe contains MgO solid solution wustite phase (material of MgO solid solution in wustite (FeO));
(9) the MgO solid solution wustite of described (eight) record is more preferably crystalline;
(10) borderline region that is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank at described iron powder and the atomic particle of metal Fe is formed with dense sulphur layer, the concentration height as the sulphur of unavoidable impurities that sulphur concentration contains than the central part in iron powder in this dense sulphur layer;
The atomic particle of (11) described metal Fe is distributed to Mg-Fe-O ternary system oxide deposited film in the blank, and to have the crystallization particle diameter be the following fine crystal tissue of 200nm;
The atomic particle of metal Fe that (12) form on the surface of described iron powder is distributed to the most surperficial in fact more preferably the formation MgO of the Mg-Fe-O ternary system oxide deposited film in the blank.
The present invention just is being based on described opinion and is proposing, and it has following feature:
(8) a kind ofly contain the iron powder that the Mg oxide-film coats, wherein, be coated with the atomic particle of metal Fe on the surface of iron powder and be distributed to Mg-Fe-O ternary system oxide deposited film in the blank.
(9) iron powder that contains the coating of Mg oxide-film of described (8) record, wherein, the atomic particle of described metal Fe is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, has the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside.
(10) iron powder that contains the coating of Mg oxide-film of described (8) or (9) record, wherein, the atomic particle of described metal Fe is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, has MgO solid solution wustite phase in blank.
(11) iron powder that contains the coating of Mg oxide-film of described (10) record, wherein, the MgO solid solution wustite phase that described MgO solid solution wustite is crystalline mutually.
(12) iron powder that contains the coating of Mg oxide-film of described (8), (9), (10) or (11) record, wherein, be distributed to Mg-Fe-O ternary system oxide deposited film in the blank and the borderline region of iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer at the atomic particle of described metal Fe.
(13) iron powder that contains the coating of Mg oxide-film of described (8), (9), (10), (11) or (12) record, wherein, the atomic particle of described metal Fe is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and having the crystallization particle diameter is the following fine crystal tissue of 200nm.
(14) iron powder that contains the coating of Mg oxide-film of described (8), (9), (10), (11), (12) or (13) record, wherein, the atomic particle of described metal Fe is distributed to the most surperficial of Mg-Fe-O ternary system oxide deposited film in the blank, is made of MgO in fact.
The described following making of iron powder that contains the coating of Mg oxide-film in described (8) of the present invention～(13), make the oxidation processes iron powder by in the oxidizing gas environment, heating iron powder in advance, in this oxidation processes iron powder, add the Mg powder and mix, make while the mixed-powder that obtains rotated to heat in inert gas environment or vacuum environment.
More particularly, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this oxidation processes iron powder, add the Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1Make while rotating to heat in the inert gas environment of MPa or the vacuum environment.
The Mg-Fe-O ternary system oxide deposited film that the most surperficial atomic particle of metal Fe that is made of MgO in fact of described (14) of the present invention record is distributed in the blank can following such making obtain, by in the oxidizing gas environment, iron powder being heated to for more time 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of thicker iron oxide film, formed at this and to have added more Mg powder in oxidation processes iron powder of thicker iron oxide film and mix, with the mixed-powder that obtains 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1Heat and obtain while rotating in the inert gas environment of MPa or the vacuum environment.
Usually, so-called " deposited film " this term ordinary representation for example is deposited on epithelium on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, but among the present invention, the atomic particle of metal Fe that surface in iron powder of the present invention forms is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and expression is accompanied by the iron oxide (Fe-O) on oxidation processes iron powder surface and Mg and reacts and be deposited on the lip-deep epithelium of this iron powder.And the atomic particle of metal Fe of the present invention is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, because the atomic particle of metal Fe is distributed to containing in the Mg oxide-film blank of Mg-Fe-O ternary system oxide deposited film, so have very strong toughness.Therefore, the distortion of the iron powder in the time of can fully following drawing, and oxide-film is obviously good with respect to the connecting airtight property of iron powder.And then the Mg-Fe-O ternary system oxide deposited film that the atomic particle of metal Fe of the present invention is distributed in the blank preferably contains MgO solid solution wustite, and this MgO solid solution wustite is crystalline preferably.
The atomic particle of metal Fe that forms on the surface of iron powder of the present invention is distributed to the thickness of the Mg-Fe-O ternary system oxide deposited film in the blank, preferably in the scope of 5～500nm, to obtain the high magnetic flux density and the high resistivity of the composite soft magnetic material after press-powder is shaped.If Film Thickness Ratio 5nm approaches, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, and is therefore not preferred, and on the other hand, if Film Thickness Ratio 500nm is thick, then the magnetic flux density of the composite soft magnetic material of press-powder shaping descends, and is not preferred.More preferably thickness is 5～200nm.
The atomic particle of described metal Fe that constitutes the iron powder that the Mg of containing oxide-film of the present invention coats is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, has Mg and O reduces to inside from the surface, and the concentration slope that Fe increases to inside, owing to have such concentration slope, so oxide-film is more superior with respect to the connecting airtight property of iron particle, therefore the situation that iron powder contacts with each other as the oxide-film of insulating coating is destroyed seldom appears in stamping process, even carrying out the high temperature destressing after drawing fires, the insulating properties of oxide-film can not descend yet, can keep high resistance, so eddy current losses is low.
In addition, be distributed to Mg-Fe-O ternary system oxide deposited film in the blank and the borderline region of iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer at the atomic particle of described metal Fe.Owing to have so dense sulphur layer at borderline region, so oxide-film is more superior with respect to the connecting airtight property of iron particle, deposited film can follow the distortion of powder and prevent to destroy coating when therefore press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, can keep high resistance, so eddy current losses reduces.Think that in addition the sulphur of dense sulphur layer supplied with by the unavoidable impurities of iron powder.
The atomic particle of described metal Fe that formation of the present invention contains the iron powder that the Mg oxide coats is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and its crystal grain is fine more good more, and preferably the crystallization particle diameter has the following fine crystal tissue of 200nm.By having such fine crystal tissue, atomic fine crystallization deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, and then when firing, also can prevent the iron powder combination that contacts with each other, in addition, even carrying out the high temperature destressing fires, oxide is also stable, can prevent that insulating properties from descending, keeping high resistance, so eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, then the thickness of deposited film becomes thicker than 500nm, and the magnetic flux density of the composite soft magnetic material that press-powder is shaped descends, and is therefore not preferred.
In addition, the atomic particle of described metal Fe is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and the amount of the MgO that it is the most surperficial is The more the better, most preferably is made of MgO in fact.If the most surperficial MgO that comes down to, then when the firing of the press-powder body of drawing, also prevent the diffusion of Fe, can prevent iron powder contact combination each other, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.
The atomic particle of described metal Fe that constitutes the iron powder that the Mg of containing oxide-film of the present invention coats is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and the part of Mg can form false ternary system oxide deposited film with replacing with respect to Mg more than one among Al, Si below the 10 atom %, Ni, Mn, Zn, Cu, Co.
The iron powder that the Mg of containing oxide-film of the present invention coats is preferably used the powder in average grain diameter 5～500 mu m ranges.Its reason is, if average grain diameter is more much smaller than 5 μ m, then the compressibility of powder descends, the volume ratio of powder reduces, so the decline of the value of magnetic flux density, and is therefore not preferred, on the other hand, if average grain diameter is more much bigger than 500 μ m, then the vortex flow of powder inside increases, and the permeability under the high frequency reduces.
The iron powder that the Mg of containing oxide-film of the present invention coats can be carried out press-powder by usual way and is shaped to fire and make, and thus, compared with prior art, especially can make the composite soft magnetic material of the present invention with high resistivity.The tissue of the composite soft magnetic material of the present invention of Zhi Zuoing contains Mg-Fe-O ternary system oxide like this, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contain MgO solid solution wustite phase mutually at described crystal boundary, this MgO solid solution wustite is crystalline preferably mutually.
In addition, to contain silica 0.05～1 quality %, below the average grain diameter 0.5 μ m, in the aluminium oxide one or both, the mode that all the other iron powder that coated by the Mg of containing oxide-film of the present invention constitute cooperates mixing, make mixed-powder, by usual way press-powder this mixed-powder that is shaped, can make by firing.According to this manufacture method, constituting the Mg-Fe-O ternary system oxide deposited film that the atomic particle of metal Fe of the iron powder that the Mg of containing oxide-film of the present invention coats is distributed in the blank reacts with silica or aluminium oxide, form composite oxides, can obtain clipping composite soft magnetic material with high resistivity with high-resistance composite oxides at the crystal boundary of iron powder, and owing to fire via silica or aluminium oxide, so but the superior composite soft magnetic material of manufacturing machine intensity.At this moment, owing to being that main body is fired,, therefore, can make the few composite soft magnetic material of magnetic hysteresis loss so can keep less coercive force with silica or aluminium oxide.Described firing preferably in inert gas environment or oxidizing gas environment carried out under 400～1300 ℃ of temperature.
In addition, adding collosol and gel (silicate) solution of silica or the wet type solution such as sol gel solution of aluminium oxide in the iron powder that the Mg of containing oxide-film of the present invention coats mixes dry afterwards, this dried mixture is being carried out compression molding, afterwards in inert gas environment or oxidizing gas environment, by under 400～1300 ℃ of temperature, firing, can make composite soft magnetic material thus.The tissue of these composite soft magnetic materials of the present invention contains Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually the iron particle that iron powder generates, contain MgO solid solution wustite phase mutually at described crystal boundary, this MgO solid solution wustite is crystalline preferably mutually.
And then the composite material that mixes organic insulation, inorganic insulating material or organic insulation and inorganic insulating material in the iron powder that the Mg of containing oxide-film of the present invention coats can be made the composite soft magnetic material that resistivity and intensity have further improved.At this moment, can use epoxy resin or fluororesin, phenolic resins, polyurethane resin, silicone resin, mylar, phenoxy resin, Lauxite, isocyanate resin, acrylic resin, polyimide resin etc. in the organic insulation.Phosphate such as ferric phosphate, various glassy insulant be can use in addition in the inorganic insulating material, the waterglass of principal component, insulating properties oxide etc. are with sodium metasilicate.
In addition, contain in the iron powder that the Mg oxide-film coats, of the present invention with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, among boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide of cooperation 0.05～1 quality % one or more, mix the back press-powder and be shaped, the press-powder formed body that obtains is fired under 500～1000 ℃ of temperature, can make composite soft magnetic material thus.So the composite soft magnetic material of making has following composition: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, contain among boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide of 0.05～1 quality % one or more, all the other are made of iron powder that the Mg of containing oxide-film of the present invention coats, and have formed the atomic particle of metal Fe and be distributed to the Mg-Fe-O ternary system oxide deposited film in the blank and the epithelium of one or more reactions among boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide.
In addition, this composite soft magnetic material can followingly obtain: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3The sol solution or the powder of the boron oxide that cooperates 0.05～1 quality % convert, the sol solution of vanadium oxide or powder, the sol solution of bismuth oxide or powder, the sol solution of the sol solution of antimony oxide or powder and molybdenum oxide or among the powder one or more, all the other iron powder that coated by the described Mg of containing oxide-film of the present invention constitute, mix with such composition, dry, the mixed oxide that making is made of oxide desiccant gel or powder coats the iron powder that mixed oxide that iron powder that the described Mg of containing oxide-film of the present invention coats forms coats, carry out press-powder in the iron powder that this mixed oxide is coated, after the shaping, by under 500～1000 ℃ of temperature, firing and can obtain.
Use the iron powder that the Mg oxide-film coats that contains of the present invention, the composite soft magnetic material of making of described method of the present invention all contains Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually the iron particle that the iron powder in the iron powder that contains the coating of Mg oxide-film generates, and contains MgO solid solution wustite phase mutually at described crystal boundary.Described MgO solid solution wustite phase is crystalline preferably.
The composite soft magnetic material that the iron powder that adopts the Mg of containing oxide-film of the present invention to coat is made has high density, high strength, high resistivity and high magnetic flux density, this composite soft magnetic material is owing to the feature with high magnetic flux density, the low iron loss of high frequency, so can be as the material of the various electromagnetic circuit parts of bringing into play this characteristic action.Described electromagnetic circuit parts are: magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, reactor, transformer, choke core or magnetic sensor iron core etc.And, be assembled with the electromagnetic circuit parts with high-resistance composite soft magnetic material formation of the iron powder that adopts the Mg of containing oxide-film coating of the present invention, motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, transverter, transformer, relay, biosensor systems etc. are arranged, can realize high efficiency, high-performance and the small-sized light weight of electric equipment.
In addition, the inventor studies for the iron powder of making such high resistance membrane coating, even the iron powder that this high resistance membrane coats is drawing, the high resistance membrane on iron powder surface can be not damaged yet when drawing, high resistance membrane connects airtight the iron powder in the surface securely, even carrying out the high temperature destressing after drawing fires, the insulating properties on surface can not descend yet, the resistance height, eddy current losses is low, or when carrying out the firing of stress relief annealing, can further reduce coercive force, the magnetic hysteresis loss step-down.
Consequently, can obtain following opinion:
Handle by iron powder is implemented phosphoric acid (13), the surface that is produced on iron powder thus formed the iron powder of phosphate layer (below, be called the iron powder that phosphate coats), in the iron powder that this phosphate coats, add Mg powder and mixing, the mixed-powder that obtains is implemented heat treated while rotating in inert gas environment or vacuum environment, obtain being coated with by Mg on the surface of iron powder, Fe, the iron powder that the deposited film of the deposited film that P and O constitute coats, should be by Mg, Fe, the deposited film that P and O constitute contains by Mg, Fe, the Mg-Fe-P-O quaternary system phosphate compounds that P and O constitute and by Mg, the Mg-Fe-O ternary system oxide that Fe and O constitute, and in blank, be dispersed with the iron phosphide particulate.
The deposited film of the iron powder that (14) described deposited film coats is owing to be dispersed with the iron phosphide particulate in the blank of deposited film, so have very strong toughness, compare with the Mg ferrite membrane that contains that the surface of the existing iron powder that coats at oxide-film forms, because the distortion of iron powder when following drawing easily, and this deposited film obviously improves with respect to the connecting airtight property of iron powder, therefore, in stamping process, situation that iron powder contacts with each other is few as the deposited film of insulating coating is destroyed, even carrying out the high temperature destressing after the iron powder that described deposited film is coated is carried out drawing fires, the insulating properties of deposited film can not descend yet, can keep high resistance, eddy current losses is low, and then when carrying out destressing and fire, owing to can further reduce coercive force, so magnetic hysteresis loss is low, therefore, can obtain having the composite soft magnetic material of low iron loss
The MgO solid solution wustite phase that contains crystalline in described deposited film in Mg-Fe-P-O quaternary system phosphate compounds that (15) are contained and the Mg-Fe-O ternary system oxide.
It is fine crystal tissue below the 200nm that the deposited film of (16) described iron phosphide microparticulate in blank preferably has the crystallization particle diameter.
The present invention just is being based on described opinion and is proposing, and it has following feature:
(18) a kind of iron powder of deposited film coating wherein, is coated with the deposited film that is made of Mg, Fe, P and O on the surface of iron powder.
(19) iron powder of the deposited film coating of described (18) record, wherein, described deposited film contains Mg-Fe-P-O quaternary system phosphate compounds that is made of Mg, Fe, P and O and the Mg-Fe-O ternary system oxide that is made of Mg, Fe and O, and is dispersed with the iron phosphide particulate in blank.
(20) iron powder of the deposited film coating of described (18) or (19) record, wherein, the MgO solid solution wustite that contains crystalline in described deposited film in the Mg-Fe-P-O quaternary system phosphate compounds that contains and the Mg-Fe-O ternary system oxide that is made of Mg, Fe and O mutually.
(21) iron powder of the deposited film coating of described (18), (19) or (20) record, wherein, it is the following fine crystal tissue of 200nm that described deposited film has the crystallization particle diameter.
The iron powder that the described deposited film in described (18) of the present invention～(21) coats, as previously mentioned, by making as follows, adding the Mg powder in the iron powder that phosphate coats mixes, the mixed-powder that mixing obtains is implemented heat treated while rotating in inert gas environment or vacuum environment, further in the oxidizing gas environment, implement oxidation processes afterwards, make thus, more particularly, obtain mixed-powder by in the iron powder that phosphate coats, adding the Mg powder, with this mixed-powder 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1While rotating heat treated, further in the oxidizing gas environment, implement oxidation processes afterwards and make in the inert gas environment of MPa or the vacuum environment.
So-called " deposited film " this term ordinary representation for example is deposited on epithelium on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, but the deposited film that the surface in iron powder of the present invention forms, expression are accompanied by the ferric phosphate (Fe-P-O) on the iron powder surface that phosphate coats and Mg and react and be deposited on the lip-deep epithelium of this iron powder.The deposited film of the iron phosphide microparticulate that surface in iron powder of the present invention forms in the blank is because the iron phosphide microparticulate is in blank, so have very strong toughness.Therefore, the distortion of the iron powder in the time of can fully following drawing, and oxide-film is obviously good with respect to the connecting airtight property of iron powder.
The thickness of the deposited film that the surface of iron powder of the present invention forms is preferably in the scope of 5～500nm, with the high magnetic flux density and the high resistivity of the composite soft magnetic material that obtains obtaining after press-powder is shaped.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, then the be shaped magnetic flux density of thick composite soft magnetic material of press-powder descends, and is not preferred.More preferably thickness is in the scope of 5～200nm.
The MgO solid solution wustite phase that preferably contains crystalline in Mg-Fe-P-O quaternary system phosphate compounds that contains in the deposited film of the iron powder that formation deposited film of the present invention coats and the Mg-Fe-O ternary system oxide.Though the MgO solid solution wustite of described crystalline has been replaced the situation of a part of Fe or Mg mutually sometimes with P, most preferably have NaCl type crystalline texture.
The deposited film of the iron powder that formation deposited film of the present invention coats, its crystal grain is fine more good more, preferably has the following fine crystal tissue of crystallization particle diameter 200nm.By having such fine crystal tissue, atomic fine crystallization deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, and then when firing, also can prevent the iron powder combination that contacts with each other, in addition, even carrying out the high temperature destressing fires, oxide is also stable, can prevent that insulating properties from descending, can keep high resistance, so eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, then the thickness of deposited film becomes thicker than 500nm, and the magnetic flux density of the composite soft magnetic material that press-powder is shaped descends, and is therefore not preferred.
The powder of the preferred average grain diameter of iron powder in the scope of 5～500 μ m as the material powder that is used to make the iron powder that deposited film of the present invention coats.Its reason is, if average grain diameter is more much smaller than 5 μ m, then the compressibility of powder descends, the volume ratio of powder reduces, so the decline of the value of magnetic flux density, and is therefore not preferred, on the other hand, if average grain diameter is more much bigger than 500 μ m, then the vortex flow of powder inside increases, and the permeability under the high frequency reduces.
Constitute the Mg-Fe-P-O quaternary system phosphate compounds that is made of Mg, Fe, P and O of iron powder that deposited film of the present invention coats and the Mg-Fe-O ternary system oxide that is made of Mg, Fe and O, the part of Mg can form false ternary system oxide deposited film with replacing with respect to Mg more than one among the Al below 10%, Si, Ni, Mn, Zn, Cu, Co.
The manufacture method of the composite soft magnetic material of the iron powder of using deposited film coating of the present invention then, is described.
The iron powder that deposited film of the present invention coats can be carried out press-powder by usual way and is shaped to fire and make.In addition, can in the iron powder that deposited film of the present invention coats, add silica below the average grain diameter 0.5 μ m of 0.05～1 quality %, in the aluminium oxide one or both, make mixed-powder, with usual way this mixed-powder is carried out press-powder and be shaped, make by firing.
Composite soft magnetic material by this manufacture method making, contain by Mg, Fe, the Mg-Fe-P-O quaternary system phosphate compounds that P and O constitute and by Mg, the Mg-Fe-O ternary system oxide that Fe and O constitute, and has the tissue that combines the iron powder of deposited film coating by silica or aluminium oxide, the iron powder that this deposited film coats is that the deposited film encirclement iron powder of iron phosphide microparticulate in blank forms, and can obtain the composite soft magnetic material of high resistivity, owing to this composite soft magnetic material is fired via silicon or aluminium oxide, so can further improve mechanical strength.
At this moment, owing to being that main body is fired,, therefore, can make the few composite soft magnetic material of magnetic hysteresis loss so can keep less coercive force with silica or aluminium oxide.Described firing preferably in inert gas environment or oxidizing gas environment carried out under 400～1300 ℃ of temperature.
In addition, adding collosol and gel (silicate) solution of silica or the wet type solution such as sol gel solution of aluminium oxide in the iron powder that deposited film of the present invention coats mixes dry afterwards, this dried mixture is being carried out compression molding, afterwards in inert gas environment or oxidizing gas environment, by under 400～1300 ℃ of temperature, firing, can make composite soft magnetic material thus.
And then, in the iron powder that deposited film of the present invention coats, mix organic insulation not, the composite material of inorganic insulating material or organic insulation and inorganic insulating material forms and fires, and then can make the further composite soft magnetic material of raising of resistivity and intensity.At this moment, can use epoxy resin or fluororesin, phenolic resins, polyurethane resin, silicone resin, mylar, phenoxy resin, Lauxite, isocyanate resin, acrylic resin, polyimide resin etc. in the organic insulation.Phosphate such as ferric phosphate, various glassy insulant be can use in addition in the inorganic insulating material, the waterglass of principal component, insulating properties oxide etc. are with sodium metasilicate.
In addition, in the iron powder that deposited film of the present invention coats, with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, among boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide of cooperation 0.05～1 quality % one or more, mix the back press-powder and be shaped, the press-powder formed body that obtains is fired under 500～1000 ℃ of temperature, can make composite soft magnetic material thus.So the composite soft magnetic material of making has following composition: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, contain among boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide of 0.05～1 quality % one or more, all the other are made of the iron powder that deposited film of the present invention coats, and have formed one or more epitheliums that react among deposited film and boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide.
In addition, this composite soft magnetic material can followingly obtain: with B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, the sol solution or the powder that contain the boron oxide of 0.05～1 quality %, the sol solution of vanadium oxide or powder, the sol solution of bismuth oxide or powder, the sol solution of the sol solution of antimony oxide or powder and molybdenum oxide or among the powder one or more, what all the other iron powder that coated by deposited film of the present invention constituted forms, composition like this is cooperated, mix, dry, the mixed oxide that making is made of oxide desiccant gel or powder coats the iron powder that mixed deposit film that iron powder that described deposited film of the present invention coats forms coats, carry out press-powder in the iron powder that this mixed deposit film is coated, after the shaping, by under 500～1000 ℃ of temperature, firing and can obtain.
The composite soft magnetic material that these iron powder that adopt deposited film of the present invention to coat are made with high resistivity, preferably contain oxide, this oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.Though also there is the situation of having replaced a part of Fe or Mg with P in the MgO solid solution wustite of described crystalline mutually, most preferably has NaCl type crystalline texture.
The composite soft magnetic material that the iron powder that adopts deposited film of the present invention to coat is made has high density, high strength, high resistivity and high magnetic flux density, this composite soft magnetic material is owing to the feature with high magnetic flux density, the low iron loss of high frequency, so can be as the material of the various electromagnetic circuit parts of bringing into play this characteristic action.Described electromagnetic circuit parts are: magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, reactor, transformer, choke core or magnetic sensor iron core etc.And, be assembled with the electric equipment of the electromagnetic circuit parts with high-resistance composite soft magnetic material formation of the iron powder that adopts deposited film coating of the present invention, motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, transverter, transformer, relay, biosensor systems etc. are arranged, can realize high efficiency, high-performance and the small-sized light weight of electric equipment.
In addition, the inventor studies for the iron Si powder of making such dielectric film coating, even the iron Si powder that this dielectric film coats is drawing, being formed on the lip-deep dielectric film of iron Si powder when drawing can be not damaged yet, and dielectric film connects airtight securely in iron Si powder surface, even and then after drawing, fire, the insulating properties on iron Si powder surface can not descend yet.
Consequently, can obtain following opinion:
(17) at surface oxidation the iron Si powder (comprise surperficial autoxidation the iron Si powder and the iron Si powder that has formed oxide-film by oxidation processes on the surface.As follows) the middle Mg powder that adds, and mix, after the mixed-powder that obtains heated in inert gas environment or vacuum environment, further being implemented in the rear oxidation that heats in the oxidative environment as required handles, then obtain having formed by Mg on the surface of iron Si powder, Fe, the iron Si powder that the deposited oxide film of the Mg-Si-Fe-O quaternary system deposited oxide film that P and O constitute coats, the iron Si powder that this deposited oxide film coats, handle changing into of film and handle the iron Si powder that film coats and compare with on the surface of existing iron Si powder, having formed to change into, because Mg-Si-Fe-O quaternary system deposited oxide film is obviously superior with respect to the connecting airtight property of iron Si powder, so in stamping process, the situation that the iron Si powder contacts with each other as the Mg-Si-Fe-O quaternary system deposited oxide film of insulating coating is destroyed seldom appears, even carrying out the high temperature destressing after drawing fires, the insulating properties of Mg-Si-Fe-O quaternary system deposited oxide film can not descend yet, can keep high resistance, eddy current losses is low, and then when carrying out destressing and fire, owing to can further reduce coercive force, so can suppress magnetic hysteresis loss lower, therefore, can obtain having the composite soft magnetic material of low iron loss
(18) described Mg-Si-Fe-O quaternary system deposited oxide film has towards surperficial Mg and O amount to be increased and towards the concentration slope that surperficial Fe amount reduces, and also has the concentration slope of the Si that increases more near surface the most surperficial approaching more Si amount.
(19) described Mg-Si-Fe-O quaternary system deposited oxide film contains the MgO solid solution wustite phase of crystalline.
It is the following fine crystal tissue of 200nm that (20) described Mg-Si-Fe-O quaternary system deposited oxide film has the average crystallite particle diameter.
(21) described Mg-Si-Fe-O quaternary system deposited oxide film contains metal Fe or Fe-Si alloy.
The present invention just is being based on described opinion and is proposing, and it has following feature:
(24) a kind of iron Si powder of deposited oxide film coating wherein, is formed with the Mg-Si-Fe-O quaternary system deposited oxide film that is made of Mg, Si, Fe and O on the surface of iron Si powder.
(25) the iron Si powder of the deposited oxide film coating of described (24) record, wherein, described Mg-Si-Fe-O quaternary system deposited oxide film has towards surperficial Mg and O amount to be increased and towards the concentration slope that surperficial Fe amount reduces, and also has the concentration slope of the Si that increases more near surface the most surperficial approaching more Si amount.
(26) the iron Si powder of the deposited oxide film coating of described (24) or (25) record, wherein, described Mg-Si-Fe-O quaternary system deposited oxide film contains the MgO solid solution wustite phase of crystalline.
(27) the iron Si powder of the deposited oxide film coating of described (24), (25) or (26) record, wherein, described Mg-Si-Fe-O quaternary system deposited oxide film contains metal Fe or Fe-Si alloy.
(28) the iron Si powder of the deposited oxide film coating of described (24), (25), (26) or (27) record, wherein, it is the following fine crystal tissue of 200nm that described Mg-Si-Fe-O quaternary system deposited oxide film has the average crystallite particle diameter.
The iron Si powder of when making the iron Si powder of described (24), (25), (26), (27) or (28) described deposited oxide film coating of the present invention, using, use contains the iron Si powder that Si:0.1～10 quality %, one-tenth that all the other are Fe and unavoidable impurities constitute are grouped into, and it generally is that known one-tenth is grouped into that this one-tenth is grouped into.Thereby, have following feature among the present invention:
(29) the iron Si powder of the deposited oxide film coating of described (24), (25), (26), (27) or (28) record, wherein, described iron Si powder has: contain Si:0.1～10 quality %, one-tenth that all the other are Fe and unavoidable impurities constitute is grouped into.
The iron Si powder that the deposited oxide film of the present invention of described in order to make (24), (25), (26), (27), (28) and (29) record coats, in having the iron Si powder that surface that described one-tenth is grouped into has oxide-film, add the Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1After heating in the inert gas environment of MPa or the vacuum environment, further as required in the oxidizing gas environment, handle to obtain by the rear oxidation of implementing long-time heating.
Described surface has the iron Si powder of oxide-film, containing iron Si powder that Si:0.1～10 quality %, one-tenth that all the other are Fe and unavoidable impurities constitute are grouped into by having of will obtaining of water atomization, gas atomization or air water atomizing is placed in the atmosphere and obtains, though just obtain, also can obtain by oxidation processes by said method.The iron Si powder that obtains by the atomizing of gas atomization or air water is owing to approach sphere, so be suitable for obtaining having the composite soft magnetic material of high electrical resistance, on the other hand, the iron Si powder that obtains by water atomization, because it is concavo-convex that powder surface has, so be suitable for obtaining having the composite soft magnetic material of higher-strength.
At this, so-called " deposited oxide film " this term ordinary representation for example is deposited on oxide scale film on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, the epithelium that forms on this iron Si powder surface but the Mg-Si-Fe-O quaternary system deposited oxide film that forms on the surface of iron Si powder of the present invention, the surface film oxide of the iron Si powder that presentation surface is oxidized and Mg react.And the thickness of the deposited oxide film that forms on the surface of this iron Si powder is preferably in the scope at 5nm～500nm, to obtain the high magnetic flux density and the high resistivity of the composite soft magnetic material after press-powder is shaped.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, then the be shaped magnetic flux density of thick composite soft magnetic material of press-powder descends, and is not preferred.More preferably thickness is in the scope of 5～200nm.
The Mg-Si-Fe-O quaternary system deposited oxide film that the surface of the iron Si powder that coats at deposited oxide film of the present invention forms, has the concentration slope that increases and reduce towards surperficial Fe amount towards surperficial Mg and O amount, so described Mg-Si-Fe-O quaternary system deposited oxide film is with respect to the connecting airtight property raising of iron Si powder, and then owing to contain metal Fe or Fe-Si alloy, so described Mg-Si-Fe-O quaternary system deposited oxide film is with respect to the connecting airtight property raising of iron Si powder, therefore, think the iron Si powder that deposited oxide film of the present invention with described Mg-Si-Fe-O quaternary system deposited oxide film coats, in operations such as compression molding, film can be not damaged or be come off, and can obtain having high-resistance composite soft magnetic material.
The Mg-Si-Fe-O quaternary system deposited oxide film that the surface of the iron Si powder that coats at deposited oxide film of the present invention forms contains the MgO solid solution wustite phase of crystalline.The MgO solid solution wustite of described crystalline most preferably has NaCl type crystalline texture mutually.
The Mg-Si-Fe-O quaternary system deposited oxide film that the surface of the iron Si powder that coats at deposited oxide film of the present invention forms, its crystal grain is fine more good more, preferably has the following fine crystal tissue of crystallization particle diameter 200nm.By having such fine crystal tissue, the micro-crystallization deposited oxide film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the contact combination each other of iron Si powder, in addition, fire even carry out the high temperature destressing, oxide is also stable, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, the magnetic flux density of the composite soft magnetic material after then press-powder is shaped descends, and is therefore not preferred.Most preferably the crystallization particle diameter is below 50nm.
The average grain diameter of the iron Si powder of described (29) record of using when the iron Si powder that the deposited oxide film of making described (24)～(28) record coats is preferably used the powder in the scope of 5～500 μ m.Its reason is, if average grain diameter is more much smaller than 5 μ m, then the compressibility of powder descends, the volume ratio of powder reduces, so the decline of the value of magnetic flux density, and is therefore not preferred, on the other hand, if average grain diameter is more much bigger than 500 μ m, then the vortex flow of powder inside increases, and the permeability under the high frequency reduces.The preferred average grain diameter of the iron Si powder of using when the iron Si powder that the deposited oxide film of making described (20)～(27) coats is 5～100 μ m.
The iron Si powder that deposited oxide film of the present invention is coated is carried out press-powder and is shaped, and by fire the press-powder formed body that obtains under 500～1000 ℃ of temperature, can make composite soft magnetic material.
In addition, fire, can form the composite soft magnetic material that resistivity and intensity improve by iron Si powder that deposited oxide film of the present invention is coated and organic insulation or inorganic insulating material press-powder together.At this moment, can use epoxy resin or fluororesin, phenolic resins, polyurethane resin, silicone resin, mylar, phenoxy resin, Lauxite, isocyanate resin, acrylic resin, polyimide resin, polyphenylene sulfide (hereinafter referred to as the PPS resin) etc. in the organic insulation, in these organic insulations, especially preferred silicone resin, polyimide resin or PPS resin.Can also suitably add and be used to the coupling agent adjusting the softening agent of binding agent hardness or be used to improve the connecting airtight property of binding agent and powder.The sliding of the powder when improving densification, guarantee the insulation of deposited film, can also add lubricants such as stearic acid, various stearate.In addition, in order to improve the intensity of composite soft magnetic material, can also suitably add the glass binder of inorganic insulating material.
Therefore, the present invention has following feature:
(30) a kind of composite soft magnetic material, its press-powder fired body by the iron Si powder that the deposited oxide film of described (24) (25) (26) (27) (28) or (29) record coats constitutes.
(31) a kind of composite soft magnetic material, it is made of the press-powder fired body, and this press-powder fired body is that the insulating materials that sandwiches silicone resin, polyimide resin or PPS resin between the particle of the iron Si powder of the deposited oxide film coating of described (24) (25) (26) (27) (28) or (29) record forms.
The composite soft magnetic material that the iron Si powder that the deposited oxide film of being put down in writing by described (24) (25) (26) (27) (28) of the present invention or (29) coats is made preferably contains Mg-Si-Fe-O quaternary system oxide, this Mg-Si-Fe-O quaternary system oxide is made of with this iron silicon particle of encirclement crystal boundary mutually mutually mutually iron silicon particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.The MgO solid solution wustite of described crystalline most preferably has NaCl type crystalline texture mutually.Therefore, the invention is characterized in:
(32) composite soft magnetic material of described (30) or (31) record, wherein, contain Mg-Si-Fe-O quaternary system oxide, this Mg-Si-Fe-O quaternary system oxide is made of with this iron silicon particle of encirclement crystal boundary mutually mutually mutually iron silicon particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
The composite soft magnetic material that the iron Si powder that adopts deposited oxide film of the present invention to coat is made has high density, high strength, high resistivity and high magnetic flux density, this composite soft magnetic material is owing to the feature with high magnetic flux density, the low iron loss of high frequency, so can be as the material of the various electromagnetic circuit parts of bringing into play this characteristic action.Iron core memeber as described electromagnetic circuit parts has magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, iron core of electric reactor, transformer core, choke core or magnetic sensor iron core etc.And, the electric equipment that is assembled with the electromagnetic circuit parts with high-resistance composite soft magnetic material formation of the iron Si powder that adopts deposited oxide film coating of the present invention has motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, transverter, transformer, relay, biosensor systems etc., can realize high efficiency, high-performance and the small-sized light weight of electric equipment.
In recent years, field at general household electrical appliances or automobile, industrial machine, carrying out strategy of Saving Energy owing to environmental problem, wish to realize the high efficiency of circuit block, wherein, the power supply of using as automobile boost or the voltage transformation of step-down etc., impedance adjustment, wave filter have a reactor with power supply unit is known, small-sized in order to realize, the low loss of this reactor and adopt the soft magnetic material of high saturation and high resistance and low coercive force.In order to improve dc superposition characteristic, wish that permeability is stable, therefore be designed to: the iron core at this reactor is provided with the gap, even input current changes in the scope of application, also can obtain certain impedance.
The press-powder fired body of the iron Si powder that deposited oxide film of the present invention is coated or the composite soft magnetic material that is made of the press-powder fired body that accompanies the insulating materials of silicone resin, polyimide resin or PPS resin between the iron Si powder particle that coats at deposited oxide film of the present invention are as the reactor of core material, carry out the high temperature destressing and fire the feature of also guaranteeing to insulate and reducing coercive force simultaneously even have, therefore, in high-frequency region and low and medium frequency zone, loss reduces, and has superior AC characteristic.Therefore, can the automobile electrical source boost or the voltage transformation of step-down etc., impedance adjustment, wave filter are used as small-sized, low loss, low noise and the superior reactor of dc superposition characteristic with in the power supply etc.
In addition, the inventor is an iron-based soft magnetic powder and studying for the Fe-Si that obtains such oxide-film and coat, even it is that iron-based soft magnetic powder is drawing that this oxide-film coats Fe-Si, Fe-Si is that the high resistance oxide-film on iron-based soft magnetic powder surface also can be damaged when drawing, high resistance material film connects airtight securely in the surface, even and then after drawing, carry out the high temperature destressing and fire, the insulating properties on surface can not descend yet, the resistance height, eddy current losses is low, and then can further reduce coercive force, magnetic hysteresis loss step-down.
Consequently, by at Fe-Si being interpolation Si powder in iron-based soft magnetic powder or the Fe powder, mixing the back heats in non-oxidizable environment, making thus in advance at described Fe-Si is that the Fe-Si that the surface of iron-based soft magnetic powder or Fe powder has the diffusion layer of high concentration Si is an iron-based soft magnetic powder, the described Fe-Si of Si concentration ratio in the diffusion layer of described high concentration Si is the Si height that contains in iron-based soft magnetic powder or the Fe powder, by the Fe-Si to the diffusion layer with high concentration Si that obtains is that iron-based soft magnetic powder carries out oxidation processes, being produced on the surface oxidation high concentration Fe-Si that has oxide layer on the diffusion layer of high concentration Si is the iron-base soft magnetic material powder, at this surface oxidation high concentration Fe-Si is to add the Mg powder in the iron-base soft magnetic material powder to mix, with the mixed-powder that obtains 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1Heat in the inert gas environment of MPa or the vacuum environment, the surface that is formed on Fe-Si and is iron-based soft magnetic powder forms the deposited oxide film that is made of Mg, Si, Fe and O, and obtains as inferior result of study:
(22) should constitute by Mg, Si, Fe and O the Mg that contains of deposited oxide film have the concentration slope of the Mg that the most surperficial approaching more Mg amount increases more, O has the concentration slope of the O that the most surperficial approaching more O amount increases more, on the other hand, Fe has the concentration slope that the most surperficial approaching more Fe amount reduces more, Si has the concentration slope of the Si that the near surface the most surperficial approaching more Si amount at deposited oxide film increases more
(23) are in the blank of the described deposited oxide film that is made of Mg, Si, Fe and O, Mg and O contain MgO solid solution wustite (material of MgO solid solution in wustite (FeO)) the type phase of crystalline, the part of Fe and Si is as metal Fe or Fe-Si alloy and contain, the described deposited oxide film that is made of Mg, Si, Fe and O is owing to contain metal Fe, so have toughness, the distortion of powder when following the press-powder shaping easily
(24) described deposited oxide film that is made of Mg, Si, Fe and O is the following fine crystal tissue of 200nm owing to have the crystallization particle diameter, thus have toughness, the distortion of powder when following the press-powder shaping easily,
Also obtain following achievement in research:
Formed by Mg on its surface, Si, the Fe-Si that the deposited oxide film of the deposited oxide film that Fe and O constitute coats is an iron-based soft magnetic powder, with existing Fe-Si be the surface of iron-based soft magnetic powder form contain Mg ferrite oxide-film to contain the Fe-Si that Mg ferrite oxide-film coats be that iron-based soft magnetic powder is compared, because oxide-film is that the connecting airtight property of iron-based soft magnetic powder is obviously superior with respect to Fe-Si, so in stamping process, seldom occur as the oxide-film of insulating coating is destroyed and the situation that Fe-Si is an iron-based soft magnetic powder to contact with each other, in addition, described by Mg, Si, the deposited oxide film that Fe and O constitute with contain Mg ferrite oxide-film and compare, stable on the chemistry, even fire so after drawing, carry out the high temperature destressing, the insulating properties of oxide-film can not descend yet, can keep high resistance, therefore eddy current losses is low, and then carrying out under the situation that destressing fires, can further reduce coercive force, can suppress magnetic hysteresis loss lower, therefore the composite soft magnetic material that can obtain having low iron loss.
The present invention just is being based on such achievement in research and is proposing, and it has following feature:
(35) Fe-Si that coats of a kind of deposited oxide film is an iron-based soft magnetic powder, wherein, is that the surface of iron-based soft magnetic powder is formed with the deposited oxide film that is made of Mg, Si, Fe and O at Fe-Si.
(36) Fe-Si that coats of the deposited oxide film of described (35) record is an iron-based soft magnetic powder, and wherein, described Fe-Si is that iron-based soft magnetic powder has: contain Si:0.1～10 quality %, all the other are grouped into for one-tenth that Fe and unavoidable impurities constitute.
(37) Fe-Si of the deposited oxide film coating of described (35) or (36) record is an iron-based soft magnetic powder, wherein, the described deposited oxide film that constitutes by Mg, Si, Fe and O have towards surperficial Mg and O amount increase, towards surperficial Fe amount reduces, Si increases more at the near surface the most surperficial approaching more Si amount of deposited oxide film concentration slope.
(38) Fe-Si of the deposited oxide film coating of described (35), (36) or (37) record is an iron-based soft magnetic powder, wherein, in the deposited oxide film that described Mg, Si, Fe and O constitute, contain metal Fe or Fe-Si alloy mutually as the MgO solid solution wustite of crystalline.
(39) Fe-Si of the deposited oxide film coating of described (35), (36), (37) or (38) record is an iron-based soft magnetic powder, wherein, to have the average crystallite particle diameter be the following fine crystal tissue of 200nm to the deposited oxide film that constitutes of described Mg, Si, Fe and O.
Generally, so-called " deposited oxide film " this term ordinary representation for example is deposited on oxide scale film on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, but of the present invention is the deposited oxide film that is made of Mg, Si, Fe and O that the surface of iron-based soft magnetic powder forms at Fe-Si, and expression is along with Fe-Si is the Si on iron-based soft magnetic powder surface and Mg reaction and be the epithelium that the surface of iron-based soft magnetic powder forms at this Fe-Si.And, at this Fe-Si is the thickness of the deposited oxide film that is made of Mg, Si, Fe and O that forms of the surface of iron-based soft magnetic powder preferably in the scope at 5nm～500nm, to obtain press-powder the be shaped high magnetic flux density and the high resistivity of the composite soft magnetic material firing and obtain.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, the magnetic flux density of the composite soft magnetic material after then press-powder is shaped descends, and is not preferred.More preferably thickness is in the scope of 5nm～200nm.
The Fe-Si that coats at the deposited oxide film of described (35)～(39) records is the deposited oxide film that is made of Mg, Si, Fe and O that the surface of iron-based soft magnetic powder forms, its crystal grain is fine more good more, and preferably the crystallization particle diameter has the following fine crystal tissue of 200nm.By having such fine crystal tissue, the micro-crystallization deposited oxide film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, can prevent also that when firing Fe-Si from being iron-based soft magnetic powder contact combination each other, in addition, fire even carry out the high temperature destressing, oxide is also stable, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, the magnetic flux density of the composite soft magnetic material after then press-powder is shaped descends, and is therefore not preferred.
The Fe-Si that uses when the Fe-Si of the deposited oxide film coating of making described (35)～(39) is iron-based soft magnetic powder is that iron-based soft magnetic powder preferably uses the powder of average grain diameter in the scope of 5～500 μ m.Its reason is, if average grain diameter is more much smaller than 5 μ m, then the compressibility of powder descends, the volume ratio of powder reduces, so the decline of the value of magnetic flux density, and is therefore not preferred, on the other hand, if average grain diameter is more much bigger than 500 μ m, then the vortex flow of powder inside increases, and the permeability under the high frequency reduces.
The Fe-Si that coats at described deposited oxide film of the present invention is the composite material that mixes organic insulation or inorganic insulating material or organic insulation and inorganic insulating material in the iron-based soft magnetic powder, can make the composite soft magnetic material that resistivity and intensity have further improved.At this moment, in organic insulation, can use epoxy resin or fluororesin, phenolic resins, polyurethane resin, silicone resin, mylar, phenoxy resin, Lauxite, isocyanate resin, acrylic resin, polyimide resin, PPS resin etc.In addition, in inorganic insulating material, can use phosphate such as ferric phosphate, various glassy insulant, be the waterglass of principal component, insulating properties oxide etc. with sodium metasilicate.
In addition, be that iron-based soft magnetic powder carries out the press-powder shaping by the Fe-Si that deposited oxide film of the present invention is coated, the press-powder formed body that obtains is fired for 500～1000 ℃ in temperature, can make composite soft magnetic material.
The Fe-Si that adopts deposited oxide film of the present invention to coat is that the composite soft magnetic material that iron-based soft magnetic powder is made has high density, high strength, high resistivity and high magnetic flux density, this composite soft magnetic material is owing to the feature with high magnetic flux density, the low iron loss of high frequency, so can be as the material of the various electromagnetic circuit parts of bringing into play this characteristic action.Described electromagnetic circuit parts have: magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, reactor, transformer, choke core or magnetic sensor iron core etc.And, the Fe-Si that is assembled with employing oxide-film coating of the present invention is that the electric equipment of the electromagnetic circuit parts of the high-resistance composite soft magnetic material formation of having of iron-based soft magnetic powder has motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, transverter, transformer, relay, biosensor systems etc., can realize high efficiency, high-performance and the small-sized light weight of electric equipment.
In addition, the inventor has at first invented following powder in order to solve described problem points:
(a) be coated with at least on the surface of iron powder and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O contain the powder that Mg iron oxide film coats iron,
(b) a kind of iron powder that contains the coating of Mg iron oxide film, be coated with at least on the surface of iron powder and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, wherein, at described iron powder and the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer.
(c) as described (a) or (b) record contain the iron powder that Mg iron oxide film coats, wherein, in the Mg-Fe-O ternary system oxide deposited film of the iron powder that the described Mg of containing oxide-film coats, contain (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.
(d) as described (a) and (b) or (c) record contain the iron powder that Mg iron oxide film coats, wherein, describedly contain at least that (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200m to the Mg-Fe-O ternary system oxide deposited film of O.
(e) as described (a) and (b), (c) or (d) record contain the iron powder that Mg iron oxide film coats, wherein, describedly contain at least that (it is the most surperficial to be made of MgO in fact for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O.
Described (a) of foregoing invention, (b), (c), (d) or (e) record contains the iron powder that Mg iron oxide film coats, by in advance in the oxidizing gas environment heating iron powder etc. implement oxidation processes, the surface that is produced on iron powder has formed the iron powder (hereinafter referred to as the oxidation processes iron powder) of iron oxide film, in this oxidation processes iron powder, add the Mg powder, mix, the mixed-powder that obtains is heated in inert gas environment or vacuum environment, further in oxidative environment, heat afterwards, obtain by implementing such oxidation processes, the iron powder that contains the coating of Mg iron oxide film of described invention, make based on following opinion:
(25) are at general known MgO-FeO-Fe 2O 3Representational in the system (Mg, Fe) O, (Mg, Fe) 3O 4Among the various oxides of Mg-Fe-O ternary system, formed at least on the surface of iron powder and to have contained (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and coated this on the surface of iron powder and contained (Mg at least, Fe) iron powder that contains the coating of Mg oxide-film of the Mg-Fe-O ternary system oxide deposited film of O, having formed the iron powder that contains the coating of Mg oxide-film that contains the Mg ferrite membrane with existing surface in iron powder compares, oxide-film is obviously superior with respect to the connecting airtight property of iron powder, therefore in stamping process, the situation that iron powder contacts with each other as the oxide-film of insulating coating is destroyed seldom appears, even carrying out the high temperature destressing after drawing fires, the insulating properties of oxide-film can not descend yet, can keep high resistance, therefore eddy current losses is low, and then when carrying out destressing and fire, owing to can further reduce coercive force, so can suppress magnetic hysteresis loss lower, therefore, can obtain having the composite soft magnetic material of low iron loss.
(26) more preferably, in the Mg-Fe-O ternary system oxide deposited film of the iron powder that the described Mg of containing oxide-film coats, contain (Mg, Fe) O is the MgO solid solution wustite (material of MgO solid solution in wustite (FeO)) of crystalline.
(27) are in described iron powder and contain (Mg at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O is formed with dense sulphur layer, and sulphur concentration is than the concentration height as the sulphur of unavoidable impurities that contains at the central part of iron powder in this dense sulphur layer.
(28) are described to be contained at least, and (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide deposited film of O.
(29) form on the surface of described iron powder contains at least, and (amount of its most surperficial MgO that contains is The more the better for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and most preferably, it is the most surperficial to be made of MgO in fact.
The iron powder that Mg iron oxide film coats that contains for described (a)～(d) that make these foregoing invention, at first, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this oxidation processes iron powder, add the Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1After heating in the inert gas environment of MPa or the vacuum environment, further in the oxidizing gas environment, heat for 50～350 ℃, implement oxidation processes then, make thus with temperature.
In addition, at least contain (Mg in described (e) of foregoing invention record, Fe) the most surperficial following manufacturing of Mg-Fe-O ternary system oxide deposited film that constitutes by MgO in fact of the Mg-Fe-O ternary system oxide deposited film of O, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this powder, add more Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1After heating in the inert gas environment of MPa or the vacuum environment, further in the oxidizing gas environment, heat for more time, implement oxidation processes then, make thus.
Described described (a)～(e) in preceding invention contain the Mg wustite that contains in the Mg-Fe-O ternary system oxide deposited film that iron powder surface that Mg iron oxide film coats forms can not be (Mg, Fe): O=1: 1, but O has the solid solution width.
So-called " deposited film " this term ordinary representation for example is deposited on epithelium on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, but what form on the surface of described iron powder contains (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O, expression are accompanied by the iron oxide (Fe-O) on the iron powder surface with iron oxide film and Mg and react and be deposited on the lip-deep epithelium of this iron powder.And containing at least of forming on this iron powder surface, (Mg, Fe) thickness of the Mg-Fe-O ternary system oxide deposited film of O was preferably in the scope of 5nm～500nm, to obtain the high magnetic flux density and the high resistivity of the composite soft magnetic material after press-powder is shaped.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, the magnetic flux density of the composite soft magnetic material after then press-powder is shaped descends, and is not preferred.More preferably thickness is in the scope of 5nm～200nm.
In addition, what form on the surface that contains the iron powder that Mg iron oxide film coats of described (a)～(e) of invention before contains (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O, at the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer.Having this dense sulphur layer can measure sulphur concentration by the auger electrons optical spectroscopy, represents with curve map, confirms according to the sulphur concentration peak value.Owing to have so dense sulphur layer at borderline region, so contain (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O further improves with respect to the connecting airtight property on iron powder surface, deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, can keep high resistance, think that therefore eddy current losses reduces.The sulphur of dense sulphur layer contains the sulphur as unavoidable impurities in iron powder, most of sulphur that is contained by the surface portion in this iron powder is supplied with.
What form on the surface that contains the iron powder that Mg iron oxide film coats of described (a)～(e) contains (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O, its crystal grain is fine more good more, and preferably the crystallization particle diameter has the following fine crystal tissue of 200nm.By having such fine crystal tissue, micro-crystallization Mg-Fe-O ternary system oxide deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, in addition, fire even carry out the high temperature destressing, oxide is also stable, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, then the thickness of Mg-Fe-O ternary system oxide deposited film becomes thicker than 500nm, and the magnetic flux density of the composite soft magnetic material that press-powder is shaped descends, and is therefore not preferred.
In addition, containing at least of forming on the surface that contains the iron powder that Mg iron oxide film coats of described (e), (amount of the MgO that it is the most surperficial was The more the better, most preferably is made of MgO in fact for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O.If the most surperficial MgO that comes down to, then when the firing of the press-powder body of drawing, also prevent the diffusion of Fe, can prevent iron powder contact combination each other, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.
More than, have been described in detail for the iron powder that Mg iron oxide film coats that contains in (a)～(e) of preceding invention record, the object of the invention provides a kind of by further coating MgO/SiO on the described surface that contains the iron powder that Mg iron oxide film coats in (a)～(e) of preceding invention record 2The MgO-SiO of molar ratio in 1.0～3.0 scopes 2System complex oxide film, and composite soft magnetic powder and manufacture method thereof that compression molding and the property fired are further improved.
That is, usually, MgO-SiO 2The electrical insulating property height of system complex oxide film, and has softer hardness (Mohs' hardness 1～4), and owing to also have good antifriction function and lubrication, so when being shaped, can also play a role as lubriation material, therefore, on the surface of the iron powder that contains the coating of Mg iron oxide film that (a)～(e) of invention before puts down in writing, also coated MgO-SiO 2The composite soft magnetic powder of system complex oxide film, compression molding further improves, and because MgO-SiO 2The fusing point of system complex oxide film is lower than MgO, so with MgO-SiO 2The property fired that contains the composite soft magnetic powder of the present invention on the iron powder that Mg iron oxide film coats that the system complex oxide film is coated on described (a)～(e) record further improves.
Therefore, the present invention has following feature:
(48) a kind of composite soft magnetic powder, wherein, (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O is coated on the surface of the iron powder that the lip-deep Mg of the containing iron oxide film of iron powder coats, and also is coated with MgO/SiO containing at least 2The MgO-SiO of molar ratio in 1.0～3.0 scope 2The system complex oxide film.
(49) a kind of composite soft magnetic powder wherein, also is coated with MgO/SiO on the surface of the iron powder that contains the coating of Mg iron oxide film 2The MgO-SiO of molar ratio in 1.0～3.0 scope 2The system complex oxide film, the iron powder that the wherein said Mg of containing iron oxide film coats is coated with at least on the surface of iron powder and contains (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and at the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part of iron powder in this dense sulphur layer.
(50) the composite soft magnetic powder of described (48) or (49) record, wherein, contain in the Mg-Fe-O ternary system oxide film deposition film of the iron powder that the described Mg of containing oxide-film coats (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.
(51) the composite soft magnetic powder of described (48), (49) or (50) record wherein, describedly contains at least that (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide deposited film of O.
(52) the composite soft magnetic powder of described (48), (49), (50) or (51) record wherein, describedly contains at least that (it is the most surperficial to be made of MgO in fact for Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O.
The composite soft magnetic powder of described (48) of the present invention, (49), (50), (51) or (52) record can be by manufacturing as follows: make MgO and SiO 2The mixed oxide sol solution attached to described (a) and (b), (c), (d) or (e) on the surface that contains the iron powder that Mg iron oxide film coats of record, afterwards, carry out heat drying and make, wherein said MgO and SiO 2The mixed oxide sol solution be that calculating with respect to 1 part of alkoxy silane solution with Capacity Ratio is that 1～3 part of ratio in the scope is mixed and obtained with alkoxyl magnesium solution.
(53) a kind of composite soft magnetic material wherein, contains Mg-Fe-O ternary system oxide, and this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
The inventor has formerly invented the following iron powder that Mg iron oxide film coats that contains in order to solve described problem points.
(f) a kind of iron powder that contains the coating of Mg iron oxide film wherein, is coated with the Mg-Fe-O ternary system oxide deposited film of metal Fe microparticulate in blank on the surface of iron powder;
(g) a kind of iron powder that contains the coating of Mg oxide-film, wherein, the iron powder that the described Mg of containing oxide-film coats is coated with the Mg-Fe-O ternary system oxide deposited film that is dispersed with metal Fe particulate in the blank on the surface of iron powder, this Mg-Fe-O ternary system oxide deposited film has the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside;
(h) a kind of iron powder that contains the coating of Mg iron oxide film, be be coated with on the surface of iron powder described (f) and (g) record Mg-Fe-O ternary system oxide deposited film contain the iron powder that Mg iron oxide film coats, wherein, borderline region at described iron powder and described Mg-Fe-O ternary system oxide deposited film has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part of iron powder in this dense sulphur layer;
(i) described (f), (g), (h) or (i) record contain the iron powder that the Mg oxide-film coats, wherein, the Mg-Fe-O ternary system oxide deposited film that the atomic particle of described metal Fe is dispersed in the blank has the MgO solid solution wustite phase of crystalline in blank;
(j) described (f), (g), (h), (i) or (j) record contain the iron powder that the Mg oxide-film coats, wherein, it is the following fine crystal tissue of 200nm that described Mg-Fe-O ternary system oxide deposited film has the crystallization particle diameter;
(k) described (f), (g), (h), (i) or (j) record contain the iron powder that the Mg oxide-film coats, wherein, the atomic particle of described metal Fe is dispersed in the most surperficial the formation MgO in fact of the Mg-Fe-O ternary system oxide deposited film in the blank.
Described described (f) in preceding invention, (g), (h), (i), (j) or (k) record contains following the obtaining of iron powder that Mg iron oxide film coats, by in advance in the oxidizing gas environment heating iron powder etc. implement oxidation processes, the surface that is produced on iron powder has formed the iron powder (hereinafter referred to as the oxidation processes iron powder) of iron oxide film, in this oxidation processes iron powder, add the Mg powder, mix, the mixed-powder that obtains is heated while rotating in inert gas environment or vacuum environment, further in oxidative environment, heat afterwards, obtain by implementing such oxidation processes.
The Mg-Fe-O ternary system oxide deposited film in the iron powder that contains the coating of Mg iron oxide film of preceding invention that obtains like this obtains based on following these opinions:
(30) with existing on the surface of iron powder chemistry formed the Mg iron oxide film that contains that contains the Mg ferrite membrane and compared, connecting airtight property with respect to iron powder is obviously superior, therefore in stamping process, the situation that iron powder contacts with each other as the oxide-film of insulating coating is destroyed seldom appears, even after drawing, fire, the insulating properties that contains Mg iron oxide film can not descend yet, can keep high resistance, therefore eddy current losses is low, and then when firing, owing to can further reduce coercive force, so can suppress magnetic hysteresis loss lower, therefore, can obtain having the composite soft magnetic material of low iron loss
(31) described Mg-Fe-O ternary system oxide deposited film, metal Fe microparticulate have the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside in blank,
(32) described iron powder that contains the coating of Mg iron oxide film, borderline region at iron powder and the metal Fe microparticulate Mg-Fe-O ternary system oxide deposited film in the blank is formed with dense sulphur layer, sulphur concentration is than the concentration height as the sulphur of unavoidable impurities that contains at the central part of iron powder in this dense sulphur layer
The Mg-Fe-O ternary system oxide deposited film that the atomic particle of (33) described metal Fe is distributed in the blank contains MgO solid solution wustite phase (material of MgO solid solution in wustite (FeO)),
It is the following fine crystal tissue of 200nm that (34) described Mg-Fe-O ternary system oxide deposited film has the crystallization particle diameter,
(35) described Mg-Fe-O ternary system oxide deposited film, the amount of its most surperficial MgO that contains is The more the better, and most preferably it the most surperficially is made of MgO in fact.
Further specify these manufacture methods in the iron powder that contains the coating of Mg iron oxide film of described (f)～(j) of preceding invention record, at first, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this powder, add the Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1Heat while rotating in the inert gas environment of MPa or the vacuum environment, further in oxidative environment, heat for 50～350 ℃ as required afterwards, implement oxidation processes, make thus with temperature.
In addition, the most surperficial following manufacturing of Mg-Fe-O ternary system oxide deposited film that constitutes by MgO in fact at the metal Fe microparticulate of described (k) of the preceding invention record Mg-Fe-O ternary system oxide deposited film in the blank, by in the oxidizing gas environment, iron powder being heated to 50～500 ℃ of temperature in advance, carry out oxidation processes, thereby the surface that is produced on iron powder has formed the oxidation processes iron powder of iron oxide film, in this powder, add more Mg powder and mix, with the mixed-powder that obtains at 150～1100 ℃ of temperature, pressure 1 * 10 -12～1 * 10 -1In the inert gas environment of MPa or the vacuum environment while rotate heat after, further in the oxidizing gas environment, heat for more time for 50～350 ℃ with temperature, implement oxidation processes then, make thus.
Usually, so-called " deposited film " this term ordinary representation for example is deposited on epithelium on the substrate by the epithelium constituting atom of vacuum evaporation or sputter, but among the present invention, the atomic particle of metal Fe that surface in iron powder of the present invention forms is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, and expression is accompanied by the iron oxide (Fe-O) on oxidation processes iron powder surface and Mg and reacts and be deposited on the lip-deep epithelium of this iron powder.And the atomic particle of metal Fe of the present invention is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, because the atomic particle of metal Fe is distributed to containing in the Mg oxide-film blank of Mg-Fe-O ternary system oxide deposited film, so have very strong toughness.Therefore, the distortion of the iron powder in the time of can fully following drawing, and oxide-film is obviously good with respect to the connecting airtight property of iron powder.And then the atomic particle of metal Fe of the present invention is distributed to the Mg-Fe-O ternary system oxide deposited film in the blank, preferably contains MgO solid solution wustite, and this MgO solid solution wustite is more preferably crystalline.
The atomic particle of metal Fe that the surface of iron powder of the present invention forms is distributed to the thickness of the Mg-Fe-O ternary system oxide deposited film in the blank, preferably in the scope of 5～500nm, to obtain the high magnetic flux density and the high resistivity of the composite soft magnetic material after press-powder is shaped.If Film Thickness Ratio 5nm is thin, the resistivity of the composite soft magnetic material after then press-powder is shaped is not enough, and eddy current losses increases, therefore not preferred, on the other hand, if Film Thickness Ratio 500nm is thick, then the be shaped magnetic flux density of thick composite soft magnetic material of press-powder descends, and is not preferred.More preferably thickness is in the scope of 5～200nm.
The Mg-Fe-O ternary system oxide deposited film that forms on the surface that contains the iron powder that Mg iron oxide film coats in preceding invention of described (f)～(k) record, described metal Fe microparticulate in the blank Mg-Fe-O ternary system oxide deposited film and the borderline region of iron powder have dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer.Having this dense sulphur layer can measure sulphur concentration by the auger electrons optical spectroscopy, and it is represented with curve map, confirms according to the sulphur concentration peak value.Owing to have so dense sulphur layer at borderline region, so the Mg-Fe-O ternary system oxide deposited film of metal Fe microparticulate in the blank further improves with respect to the connecting airtight property on iron powder surface, deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, can keep high resistance, so eddy current losses reduces.The sulphur of dense sulphur layer contains the sulphur as unavoidable impurities in iron powder, think that most of sulphur that is contained by the surface portion in this iron powder supplies with.
At the Mg-Fe-O ternary system oxide deposited film that the surface that contains the iron powder that Mg iron oxide film coats in preceding invention of described (f)～(k) record forms, its crystal grain is fine more good more, preferably has the following fine crystal tissue of crystallization particle diameter 200nm.By having such fine crystal tissue, micro-crystallization Mg-Fe-O ternary system oxide deposited film can follow the distortion of powder and prevent to destroy coating when press-powder was shaped, when firing, also can prevent the iron powder combination that contacts with each other, in addition, fire even carry out the high temperature destressing, oxide is also stable, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.If the crystallization particle diameter is greater than 200nm, then the thickness of Mg-Fe-O ternary system oxide deposited film becomes thicker than 500nm, and the magnetic flux density of the composite soft magnetic material that press-powder is shaped descends, and is therefore not preferred.
In addition, at the Mg-Fe-O ternary system oxide deposited film that the surface that contains the iron powder that Mg iron oxide film coats of described (k) forms, the amount of the MgO that it is the most surperficial is The more the better, most preferably is made of MgO in fact.If the most surperficial MgO that comes down to, then when the firing of the press-powder body of drawing, also prevent the diffusion of Fe, can prevent iron powder contact combination each other, can prevent that insulating properties from descending, the resistance height, eddy current losses reduces.
The object of the invention provides a kind of by on the surface that contains the iron powder that Mg iron oxide film coats of (f)～(k) of invention before record, further coats MgO/SiO 2The MgO-SiO of molar ratio in 1.0～3.0 scopes 2The composite soft magnetic powder that the system complex oxide film forms.
That is, the present invention has following feature:
(54) a kind of composite soft magnetic powder wherein, is coated at the Mg-Fe-O ternary system oxide deposited film of metal Fe microparticulate in blank on the surface of the iron powder that the lip-deep Mg of the containing iron oxide film of iron powder coats, and also is coated with MgO/SiO 2The MgO-SiO of molar ratio in 1.0～3.0 scope 2The system complex oxide film,
(55) a kind of composite soft magnetic powder wherein, also is coated with MgO/SiO on the surface of the iron powder that contains the coating of Mg oxide-film 2The MgO-SiO of molar ratio in 1.0～3.0 scope 2The system complex oxide film, the iron powder that the wherein said Mg of containing iron oxide film coats is coated with on the surface of iron powder and is dispersed with metal Fe particulate Mg-Fe-O ternary system oxide deposited film in blank, this Mg-Fe-O ternary system oxide deposited film has the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside
(56) the composite soft magnetic powder of described (1) or (2) record, wherein, the iron powder that the described Mg of containing oxide-film coats is to contain the iron powder that Mg iron oxide film coats, its borderline region in Mg-Fe-O ternary system oxide deposited film and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part of iron powder in this dense sulphur layer
(57) the composite soft magnetic powder of described (54), (55) or (56) record, wherein, the Mg-Fe-O ternary system oxide deposited film that the atomic particle of described metal Fe is dispersed in the blank has the MgO solid solution wustite phase of crystalline in blank,
(58) the composite soft magnetic powder of described (54), (55), (56) or (57) record, wherein, it is the following fine crystal tissue of 200nm that described Mg-Fe-O ternary system oxide deposited film has the crystallization particle diameter,
(59) the composite soft magnetic powder of described (54), (55), (56), (57) or (58) record, wherein, described Mg-Fe-O ternary system oxide deposited film, it is the most surperficial to be made of MgO in fact.
Described (54), (55), (56), (57), (58) or the composite soft magnetic powder of the present invention of (59) record can followingly make: calculate with respect to alkoxy silane solution with Capacity Ratio: alkoxyl magnesium solution be before the ratio in 1: 1～3 scopes is blended in invention contain the iron powder that Mg iron oxide film coats, obtain the mixed oxide sol solution of MgO and SiO2, the mixed oxide sol solution that makes described MgO and SiO2 is attached to described (f), (f), (h), (i), (j) or (k) on the surface that contains the iron powder that Mg iron oxide film coats of record, afterwards, carrying out heat drying makes.
(60) a kind of composite soft magnetic material wherein, contains Mg-Fe-O ternary system oxide, and this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
Description of drawings
Fig. 1 is that expression utilizes auger electrons light-dividing device mensuration to contain (Mg, Fe) result's of the sulphur concentration of the depth direction of the Mg-Fe-O ternary system oxide deposited film of O distribution curve map at least;
Fig. 2 is that expression utilizes the auger electrons light-dividing device to measure result's the curve map that the atomic particle of metal Fe is dispersed in the CONCENTRATION DISTRIBUTION of Mg, the O of depth direction of the Mg-Fe-O ternary system oxide deposited film in the blank and Fe;
Fig. 3 is that expression utilizes the auger electrons light-dividing device to measure the result's that sulphur concentration that the atomic particle of metal Fe is dispersed in the depth direction of the Mg-Fe-O ternary system oxide deposited film in the blank distributes curve map;
Fig. 4 is that the electron microscope that expression metal Fe atomic particle is dispersed in the section structure of the Mg-Fe-O ternary system oxide deposited film in the blank is organized photo;
Fig. 5 is the transmission electron microscope photo of the section structure of the deposited film that formed by the iron powder that deposited film of the present invention coats;
Fig. 6 is the curve map of CONCENTRATION DISTRIBUTION of Mg, O, P and Fe of the depth direction of the deposited film that forms of the iron powder of utilizing auger electrons light-dividing device investigation to be coated by deposited film of the present invention;
Fig. 7 is the curve map of CONCENTRATION DISTRIBUTION of Mg, Si, O and the Fe of the expression depth direction that utilizes auger electrons light-dividing device investigation deposited oxide film;
Fig. 8 is that expression utilizes the auger electrons light-dividing device to measure result's the curve map of CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of the depth direction of deposited oxide film.
The specific embodiment
＜embodiment 1 〉
As material powder, prepare average grain diameter and be the pure iron powder that 70 μ m contain denier, and then preparing average grain diameter is the Mg powder of 50 μ m as the sulphur of unavoidable impurities.By in atmosphere, 220 ℃ of temperature, keep under 2 hours the condition described pure iron powder being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder in the oxidation processes iron powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % is added and is mixed, and makes mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 2.7 * 10 -4MPa kept 1 hour down, afterwards further in atmosphere by 200 ℃ of temperature, kept 1 hour, thereby the surface that is produced on iron powder coats the iron powder 1 that the Mg of the containing oxide-film of the present invention of deposited film coats.Observe the tissue that contains the deposited film that forms on the iron powder 1 of Mg oxide-film coating in the present invention under electron microscope, obtain the thickness and the maximum crystallization particle diameter of this deposited film, its result is as shown in table 1.In addition, according to the electron ray diffraction pattern that the deposited film that contains the iron powder 1 that the Mg oxide-film coats from the present invention obtains, recognize the MgO solid solution wustite phase that contains crystalline.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 1 that contains the Mg oxide-film in the present invention and coat, resolve, recognize at least and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O in conjunction with energy.And then the result of the method investigation iron powder by utilizing the auger electrons light-dividing device and the borderline region of Mg-Fe-O ternary system oxide deposited film is shown in the curve map of Fig. 1.The longitudinal axis is represented the peak strength of auger electrons in the curve map of Fig. 1, and on the other hand, transverse axis represents to coat the etching period of deposited film, and it is dark more that the long more expression of etching period coats the position of deposited film.Expression sulphur concentration peak value in the curve map of the sulphur concentration that detects by the auger electrons optical spectroscopy of Fig. 1, observing this curve map can recognize, etching period about 10～15 minutes deposited film and the borderline region of iron powder have dense sulphur layer, its sulfur impurity that contains than the central part in iron powder (background) detects the peak value of sulphur more significantly by the auger electrons optical spectroscopy, so contain the higher sulphur of concentration of the sulphur that concentration ratio iron powder central part contains.
＜embodiment 2 〉
By in atmosphere, 210 ℃ of temperature, keep under three hours the condition pure iron powder of preparing at embodiment 1 being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder with than the mode of embodiment more than 1 in the oxidation processes iron powder: Mg powder=99.5 quality %: the ratio of 0.5 quality % is added and is mixed, make mixed-powder, with the mixed-powder that obtains at 670 ℃ of temperature, pressure 1 * 10 -5MPa kept 1 hour down, further pass through 200 ℃ of temperature afterwards in atmosphere, kept 1 hour, thereby the present invention who is produced on the surface coating deposited film of iron powder contains the iron powder 2 that the Mg oxide-film coats.Observe the tissue that the present invention contains the deposited film of the iron powder 2 that the Mg oxide-film coats under electron microscope, obtain the thickness and the maximum crystallization particle diameter of this deposited film, its result is as shown in table 1.In addition, according to the electron ray diffraction pattern that obtains from this deposited film, recognize the MgO solid solution wustite phase that contains crystalline.
And then, analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 2 that contains the Mg oxide-film in the present invention and coat, parsing is in conjunction with energy, recognize that this deposited film is to contain (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and the most surperficial formation of Mg-Fe-O ternary system oxide deposited film by MgO.And then, investigate the CONCENTRATION DISTRIBUTION of Mg, O and Fe similarly to Example 1 by the method for utilizing the auger electrons light-dividing device, borderline region at iron powder and Mg-Fe-O ternary system oxide deposited film has dense sulphur layer as can be known, the concentration height of the sulphur that the concentration ratio iron powder central part of the sulphur in this dense sulphur layer contains.
＜embodiment 3 〉
By in atmosphere, 220 ℃ of temperature, keep under 1.5 hours the condition pure iron powder of preparing at embodiment 1 being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder with than the mode of embodiment more than 1 in the oxidation processes iron powder: Mg powder=99.7 quality %: the ratio of 0.3 quality % is added and is mixed, make mixed-powder, with the mixed-powder that obtains at 640 ℃ of temperature, pressure 1 * 10 -4MPa kept 1 hour down, further pass through 200 ℃ of temperature afterwards in atmosphere, kept 1.5 hours, thereby the present invention who is produced on the surface coating deposited film of iron powder contains the iron powder 3 that the Mg oxide-film coats.Observe the tissue of this deposited film under electron microscope, its thickness and maximum crystallization particle diameter are as shown in table 1.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 3 that contains the Mg oxide-film in the present invention and coat, parsing is in conjunction with energy, recognize at least and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and the most surperficial formation of this Mg-Fe-O ternary system oxide deposited film by MgO.And then, utilize method similarly to Example 1 to investigate Mg, the O of this Mg-Fe-O ternary system oxide deposited film and the CONCENTRATION DISTRIBUTION of Fe by utilizing the auger electrons light-dividing device, borderline region at iron particle and Mg-Fe-O ternary system oxide deposited film has dense sulphur layer as can be known, the concentration height of the sulphur that the sulphur concentration in this dense sulphur layer contains than iron powder central part.
To contain iron powder 1～3 that the Mg oxide-film the coats mould of packing in the present invention that embodiment 1～3 obtains, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 1, further apply winding at the composite soft magnetic material that constitutes by the ring-type fired body, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 1.In addition, adopted the present invention who obtains at embodiment 2 to contain the composite soft magnetic material of the iron powder 2 of Mg oxide-film coating with transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually, from the electron ray diffraction pattern that obtains mutually according to described crystal boundary, recognize the Mg-Fe-O ternary system oxide that comprises the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually.
＜conventional example 1 〉
Be produced among the embodiment 1 chemistry on the surface of the pure iron powder of preparing and formed the iron powder 1 that the existing oxide that contains the Mg ferrite layer coats, the iron powder 1 that this existing oxide the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 1, further on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 1.
Figure 200580049193900441
From the result shown in the table 1 as can be known, the composite soft magnetic material that the iron powder 1～3 of using the present invention to contain the coating of Mg oxide-film is made, compare with the existing composite soft magnetic material that the iron powder 1 of using existing oxide to coat is made, aspect density, there is not big difference, but the composite soft magnetic material of iron powder 1 making that composite soft magnetic material that the iron powder 1～3 of using the present invention to contain the coating of Mg oxide-film is made and the existing oxide of use coat is compared, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has the characteristic that frequency must the more little grade of big more iron loss.As can be known, the present invention contains the iron powder 1～3 of Mg oxide-film coating and compares with the iron powder 1 that existing oxide coats, and is can provide to have the more soft magnetism material powder of the composite soft magnetic material of advantageous characteristic.
＜embodiment 4 〉
As material powder, prepare average grain diameter: 70 μ m's contains pure iron powder as the sulphur of unavoidable impurities, and then preparing average grain diameter is the Mg powder of 50 μ m.By in atmosphere, 220 ℃ of temperature, keep under 2 hours the condition described pure iron powder being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder in the oxidation processes iron powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % is added and is mixed, and makes mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 1 * 10 -4Under 1 hour the condition of maintenance, heat while rotate under the MPa, the present invention who is produced on the surface coating deposited film of iron powder thus contains the iron powder 4 that the Mg oxide-film coats.Observe the section structure that contains the deposited film that forms on the iron powder 4 of Mg oxide-film coating in the present invention under electron microscope, obtain the thickness and the maximum crystallization particle diameter of this deposited film, its result is as shown in table 2.That takes with the section structure of the described deposited film of transmission electron microscope observation the time organizes photo as shown in Figure 4.As can be seen from Figure 4, coat deposited film of the present invention on the surface of iron powder (upper right quarter), its thickness is that 40nm, maximum crystallization particle diameter are 20nm.In addition, obtain the electron ray diffraction pattern, recognize the MgO solid solution wustite phase that contains crystalline according to deposited film of the present invention from Fig. 4.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 4 that contains the Mg oxide-film in the present invention and coat, resolve, recognize that metal Fe microparticulate is in blank in conjunction with energy.In addition, recognize that metal Fe microparticulate is made of MgO to the most surperficial of deposited film in the blank.And then, Mg, the O of the depth direction by utilizing auger electrons light-dividing device investigation deposited film and the CONCENTRATION DISTRIBUTION of Fe.Its result as shown in Figure 2.The analysis result of the depth direction of the graphical representation deposited film of Fig. 2, in the curve map of Fig. 2, the longitudinal axis is represented the peak strength of auger electrons, and on the other hand, transverse axis is represented the etching period of deposited film, and the position of the long more deposited film of expression etching period is dark more.As can be seen from Figure 2, Mg and O have from the surface to inside minimizing and Fe and have the concentration slope that increases to inside.Therefore, the iron powder 4 that coats according to the Mg of containing oxide-film of the present invention as can be known: the Mg-Fe-O ternary system oxide deposited film that this deposited film is a metal Fe microparticulate in the blank; This Mg-Fe-O ternary system oxide deposited film have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside; The MgO solid solution wustite phase that contains crystalline; And the most surperficial of deposited film is to be made of MgO.
And then, utilize of the distribution of auger electrons light-dividing device to the borderline region investigation sulphur of iron powder and Mg-Fe-O ternary system oxide deposited film.Its result is shown in the curve map of Fig. 3.In the curve map of Fig. 3, the longitudinal axis is represented the peak strength of auger electrons, and on the other hand, transverse axis represents to coat the etching period of deposited film, and the expression etching period is long more, and the position that coats deposited film is dark more.Fig. 3 by expression sulphur concentration peak value in the curve map of the detected sulphur concentration of auger electrons optical spectroscopy, observe this curve map as can be known, etching period about 10～15 minutes deposited film and the borderline region of iron powder have dense sulphur layer, because its sulfur impurity that contains than the central part in iron powder (background) detects the peak value of sulphur more significantly by the auger electrons optical spectroscopy, so the concentration height of the sulphur that the concentration ratio iron powder central part of its sulphur contains.
＜embodiment 5 〉
By in atmosphere, 215 ℃ of temperature, keep under 3 hours the condition pure iron powder of preparing at embodiment 4 being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder with than the mode of embodiment more than 4 in the oxidation processes iron powder: Mg powder=99.5 quality %: the ratio of 0.5 quality % is added and is mixed, make mixed-powder, with the mixed-powder that obtains at 660 ℃ of temperature, pressure 1 * 10 -4MPa keeps down heating while rotate under 1 hour the condition, and the present invention that the surface that is produced on iron powder thus is coated with deposited film contains the iron powder 5 of Mg oxide-film coating.
Observe the section structure that contains the deposited film that forms on the surface of the iron powder 5 that the Mg oxide-film coats in the present invention under electron microscope, obtain the thickness and the maximum crystallization particle diameter of this deposited film, its result is as shown in table 2.In addition, according to the electron ray diffraction pattern that obtains from this deposited film, recognize the MgO solid solution wustite phase that contains crystalline.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 5 that contains the Mg oxide-film in the present invention and coat, resolve in conjunction with energy by X ray electronics optical spectroscopy, recognize metal Fe microparticulate in the deposited film blank, contain MgO solid solution wustite phase and the most surperficial of deposited film is made of MgO.Therefore, the iron powder 5 that coats according to the Mg of containing oxide-film of the present invention is as can be known: the Mg-Fe-O ternary system oxide deposited film that this deposited film is a metal Fe microparticulate in the blank, contain crystalline MgO solid solution wustite phase, with and the most surperficially constitute by MgO.
And then, method investigation by utilizing the auger electrons light-dividing device contains Mg, the O of the deposited film that the surface of the iron powder 5 that the Mg oxide-film coats forms and the CONCENTRATION DISTRIBUTION of Fe in the present invention similarly to Example 4, and as can be known: it is to have Mg and O to reduce and the Mg-Fe-O ternary system oxide deposited film of the concentration slope that Fe increases to inside from the surface to inside; Borderline region at iron powder and Mg-Fe-O ternary system oxide deposited film has dense sulphur layer, the concentration height of the sulphur that the concentration ratio iron powder central part of the sulphur in this dense sulphur layer contains.
＜embodiment 6 〉
By in atmosphere, 220 ℃ of temperature, keep under 2 hours the condition pure iron powder of preparing at embodiment 4 being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder with than the mode of embodiment more than 4 in the oxidation processes iron powder: Mg powder=99.7 quality %: the ratio of 0.3 quality % is added and is mixed, make mixed-powder, with the mixed-powder that obtains at 640 ℃ of temperature, pressure 1 * 10 -5MPa keeps down heating while rotate under 1 hour the condition, and the present invention that the surface that is produced on iron powder thus is coated with deposited film contains the iron powder 6 of Mg oxide-film coating.Under electron microscope, observe the section structure of this deposited film, table 2 its thickness of expression and maximum crystallization particle diameter.In addition, recognize the MgO solid solution wustite phase that contains crystalline according to the electron ray diffraction pattern that obtains from this deposited film.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder 6 that contains the Mg oxide-film in the present invention and coat, from conjunction with the energy spectra to: the atomic particle of metal Fe is distributed to the deposited film blank at least; Contain MgO solid solution wustite phase; And the most surperficial formation of this Mg-Fe-O ternary system oxide deposited film by MgO.Therefore, the iron powder 6 that coats according to the Mg of containing oxide-film of the present invention as can be known: the Mg-Fe-O ternary system oxide deposited film that this deposited film is a metal Fe microparticulate in the blank; The MgO solid solution wustite phase that contains crystalline; With and the most surperficially constitute by MgO.
And then, by method similarly to Example 4, utilize the auger electrons light-dividing device to investigate this deposited film, as can be known: be that the CONCENTRATION DISTRIBUTION of Mg, O and Fe has Mg and O and reduces and the Mg-Fe-O ternary system oxide deposited film of the concentration slope that Fe increases to inside from the surface to inside; And then has dense sulphur layer, the concentration height of the sulphur that the concentration ratio iron powder central part of sulphur contains in this dense sulphur layer at the borderline region of iron particle and Mg-Fe-O ternary system oxide deposited film.
To contain iron powder 4～6 that the Mg oxide-film the coats mould of packing in the present invention that embodiment 4～6 obtains, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 2, further on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 2.In addition, adopted the present invention who obtains at embodiment 4～6 to contain the composite soft magnetic material of the iron powder 4～6 of Mg oxide-film coating with transmission electron microscope observation, all observe the iron particle phase and this iron particle of encirclement crystal boundary phase mutually that generate by iron powder, from the electron ray diffraction pattern that obtains mutually according to described crystal boundary, recognize the Mg-Fe-O ternary system oxide that comprises the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually.
＜conventional example 2 〉
Be produced among the embodiment 4 chemistry on the surface of the pure iron powder of preparing and formed the iron powder 2 that the existing oxide that contains the Mg ferrite layer coats, the iron powder 2 that this existing oxide the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of tabular fired body is measured, its result is as shown in table 2, further on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 2.
Figure 200580049193900491
From the result shown in the table 2 as can be known, the composite soft magnetic material that the iron powder 4～6 of using the present invention to contain the coating of Mg oxide-film is made, compare with the existing composite soft magnetic material that the iron powder 2 of using existing oxide to coat is made, aspect density, there is not big difference, but the composite soft magnetic material of iron powder 2 making that composite soft magnetic material that the iron powder 4～6 of using the present invention to contain the coating of Mg oxide-film is made and the existing oxide of use coat is compared, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially have frequency and become big more, the iron loss characteristic such as more little that becomes, therefore, the present invention contains the iron powder 4～6 of Mg oxide-film coating and compares with the iron powder 2 that existing oxide coats, and is can provide to have the more soft magnetism material powder of the composite soft magnetic material of advantageous characteristic.
＜embodiment 7 〉
As material powder, prepare to have average grain diameter: the iron powder that the phosphate of selling on the market of 70 μ m coats, and then, prepare average grain diameter: the Mg powder of 50 μ m.By the iron powder that described phosphate is coated, the iron powder that the Mg powder is coated by phosphate: Mg powder=99.8 quality %: the ratio of 0.2 quality % is added and is mixed, the making mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 1 * 10 -4MPa heats while rotating under 1 hour the condition of maintenance down, and the surface that is produced on iron powder thus coats the iron powder of the deposited film coating of the present invention of deposited film.Observe the section structure of the deposited film that forms on the iron powder that deposited film of the present invention coats under transmission electron microscope, this transmission electron microscope organizes photo as shown in Figure 5.Obtain the thickness and the maximum crystallization particle diameter of the deposited film that the iron powder that coats at deposited film of the present invention forms from the photo of Fig. 5, its result is as shown in table 3.
And then the graphical representation of Fig. 6 is utilized the result of the CONCENTRATION DISTRIBUTION of Mg, O, P and Fe on the auger electrons light-dividing device investigation deposited film depth direction.The element that constitutes deposited film from the result shown in the curve map of Fig. 6 as can be known is Mg, Fe, P and O.
Further, analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder that coats at deposited film of the present invention, parsing is in conjunction with energy, recognize, the iron phosphide microparticulate and exists Mg-Fe-P-O quaternary system phosphate compounds that is made of Mg, Fe, P and O and the Mg-Fe-O ternary system oxide that is made of Mg, Fe and O in blank.And then, the electron ray diffraction pattern of the deposited film that forms from the surface of the iron powder that coats at deposited film of the present invention is recognized Mg-Fe-P-O quaternary system phosphate compounds that is made of Mg, Fe, P and O and the MgO solid solution wustite phase that is contained crystalline by the Mg-Fe-O ternary system oxide that Mg, Fe and O constitute.
The iron powder that the deposited film of the present invention that obtains the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, density and resistivity to the composite soft magnetic material that is made of this tabular fired body are measured, its result is as shown in table 3, further on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 3.
In addition, adopted the composite soft magnetic material of the iron powder of deposited film coating of the present invention with transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually, from the electron ray diffraction pattern that obtains mutually according to described crystal boundary, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually.
＜conventional example 3 〉
Be produced on chemistry on the surface of pure iron powder and formed the iron powder that the existing oxide that contains the Mg ferrite layer coats, the iron powder that this existing oxide the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep carrying out sintering under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type sintered body constitutes, density and resistivity to the composite soft magnetic material that is made of tabular sintered body are measured, its result is as shown in table 3, further on the composite soft magnetic material that constitutes by the ring-type sintered body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 3.
Figure 200580049193900521
From the result shown in the table 3 as can be known, the composite soft magnetic material that the iron powder of using deposited film of the present invention to coat is made, compare with the existing composite soft magnetic material that the iron powder of using existing oxide to coat is made, aspect density, there is not big difference, but the composite soft magnetic material that the iron powder of using deposited film of the present invention to coat is made is compared with the composite soft magnetic material that the iron powder of using existing oxide to coat is made, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially have frequency and become big more, the iron loss characteristic such as more little that becomes, therefore, the iron powder that deposited film of the present invention coats is compared with the iron powder that existing oxide coats, and is can provide to have the more soft magnetism material powder of the composite soft magnetic material of advantageous characteristic.
＜embodiment 8 〉
As material powder, prepare to have contain Si:3 quality %, all the other are grouped into by the one-tenth that Fe and unavoidable impurities constitute, and have average grain diameter: the iron Si powder of the air water atomizing of 70 μ m, further prepare average grain diameter: the Mg powder of 50 μ m.
The iron Si powder of described air water atomizing is formed with autoxidation on the surface and the oxide-film that forms.In this iron Si powder, with the Mg powder in the iron Si powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % is added and is mixed, and makes mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 2.7 * 10 -4After MPa kept 1 hour down, further by in atmosphere 200 ℃ of temperature, kept 1 hour, thereby coat deposited oxide film on the surface of iron Si powder, makes the iron Si powder of deposited oxide film coating of the present invention.
By utilizing the auger electrons light-dividing device to investigate the CONCENTRATION DISTRIBUTION of Mg, Si, O and Fe of depth direction of the deposited oxide film of this deposited oxide film iron Si powder, its result is shown in the curve map of Fig. 7.The analysis result of the depth direction of the graphical representation deposited film of Fig. 7, in the curve map of Fig. 7, the longitudinal axis is represented the peak strength of auger electrons, and on the other hand, transverse axis is represented the etching period of deposited film, and the long more deposited film of expression etching period inside is dark more.As can be seen from Figure 7, have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside, and Si has near surface and approaches the Si concentration slope that the most surperficial its Si amount increases more more.
In addition, analyze,, recognize and contain metal Fe or Fe-Si alloy by resolving in conjunction with energy by the deposited oxide film that forms on the surface of x-ray photoelectron light-dividing device to the iron Si powder that coats at this deposited oxide film.
And then the electron ray diffraction pattern of the deposited film that forms from the iron Si powder surface that coats at deposited film of the present invention is recognized the MgO solid solution wustite phase that contains crystalline in Mg-Si-Fe-O quaternary system deposited oxide film.
Therefore, recognize: the deposited oxide film that forms on the surface of the iron Si powder that deposited oxide film of the present invention coats is the Mg-Si-Fe-O quaternary system deposited oxide film that is made of Mg, Si, Fe and O, this Mg-Si-Fe-O quaternary system deposited oxide film have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside, and have the concentration slope that approaches the Si that the most surperficial Si amount increases more more; Contain metal Fe or Fe-Si alloy; Mg-Si-Fe-O quaternary system deposited oxide film contains MgO solid solution wustite phase of crystalline or the like.And then the tissue of the deposited oxide film of the iron Si powder that coats with the electron microscope observation deposited oxide film is measured the thickness and the maximum crystallization particle diameter of this deposited oxide film, and the result is that the average thickness of deposited oxide film is 40nm, and maximum crystallization particle diameter is 10nm.
The iron Si powder that the deposited oxide film of the present invention that so obtains the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 600 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular press-powder fired body is measured, its result is as shown in table 4, further apply winding at the composite soft magnetic material that constitutes by ring-type press-powder fired body, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.Adopted the composite soft magnetic material of the iron Si powder of deposited film coating of the present invention with transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually, from the electron ray diffraction pattern that obtains mutually according to described crystal boundary, recognize that crystal boundary contains the MgO solid solution wustite phase of crystalline mutually.
＜conventional example 4 〉
Being produced among the embodiment 8 on the surface of the iron Si powder of preparing chemistry has formed and contains Mg and change into existing the changing into of handling film and handle the iron Si powder that film coats, this existing changing into is handled iron Si powder that film coats mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 600 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of tabular press-powder fired body is measured, its result is as shown in table 4, further on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
＜embodiment 9 〉
In the iron Si powder that the deposited oxide film of the present invention that embodiment 8 makes coats, add silicone resin with 1 quality %, obtain mixed-powder after the mixing, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in vacuum environment, 800 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular press-powder fired body is measured, its result is as shown in table 4, further on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.In addition, with this composite soft magnetic material of transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually,, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually from the electron ray diffraction pattern that obtains mutually according to described crystal boundary.
＜conventional example 5 〉
Chemistry has formed and has contained Mg and change into handle film existing and change into and handle in the iron Si powder that film coats on the surface of the iron Si powder that conventional example 4 is made, add the silicone resin of 1 quality %, mix and obtain mixed-powder, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in vacuum environment, 800 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular press-powder fired body is measured, its result is as shown in table 4, further on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
＜embodiment 10 〉
In the iron Si powder that the deposited oxide film of the present invention that embodiment 8 makes coats, add the pi resin with 1 quality %, obtain mixed-powder after the mixing, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 550 ℃ of temperature, keep making its heat cure under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of tabular press-powder fired body is measured, and its result is as shown in table 4.In addition, with this composite soft magnetic material of transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually,, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually from the electron ray diffraction pattern that obtains mutually according to described crystal boundary.
Further on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, magnetic characteristics such as iron loss when the iron loss when measuring magnetic flux density, coercive force and magnetic flux density 1.5T and frequency 50Hz and magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
＜conventional example 6 〉
Chemistry has formed and has contained Mg and change into handle film existing and change into and handle in the iron Si powder that film coats on the surface of the iron Si powder that conventional example 4 is made, add the pi resin of 1 quality %, mix and obtain mixed-powder, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 550 ℃ of temperature, keep making its heat cure under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of tabular press-powder fired body is measured, its result is as shown in table 4, in addition, on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
＜embodiment 11 〉
In the iron Si powder that the deposited oxide film of the present invention that embodiment 8 makes coats, add the PPS resin with 1 quality %, obtain mixed-powder after the mixing, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that ring-type press-powder fired body constitutes, resistivity to the composite soft magnetic material that is made of tabular press-powder fired body is measured, and its result is as shown in table 4.In addition, with this composite soft magnetic material of transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually,, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually from the electron ray diffraction pattern that obtains mutually according to described crystal boundary.
Further on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, magnetic characteristics such as iron loss when the iron loss when measuring magnetic flux density, coercive force and magnetic flux density 0.1T and frequency 10kHz and magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
＜conventional example 7 〉
Chemistry has formed and has contained Mg and change into handle film existing and change into and handle in the iron Si powder that film coats on the surface of the iron Si powder that conventional example 4 is made, add the PPS resin of 1 quality %, mix and obtain mixed-powder, with this mixed-powder mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, the composite soft magnetic material that making is made of the press-powder fired body of tabular and ring-type, resistivity to the composite soft magnetic material that is made of this tabular press-powder fired body is measured, its result is as shown in table 4, in addition, on the composite soft magnetic material that constitutes by ring-type press-powder fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 10kHz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 4.
Figure 200580049193900581
From the result shown in the table 4 as can be known, the composite soft magnetic material of the press-powder fired body of the iron Si powder that the deposited oxide film of making at embodiment 8 of the present invention coats, compare with the existing composite soft magnetic material of making in conventional example 4 that changes into the press-powder fired body of the iron Si powder of handling the film coating, aspect density, there is not big difference, but the composite soft magnetic material that the iron Si powder of using the deposited oxide film of the present invention made at embodiment 8 to coat is made is compared with the existing composite soft magnetic material of making in conventional example 4 that changes into the press-powder fired body of handling the iron Si powder that film coats, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency and becomes big more, the iron loss characteristic such as more little that becomes.
And then as can be known, the press-powder fired body that accompanies the insulating materials of silicone resin between the particle of the iron Si powder that the deposited oxide film of the present invention that embodiment 9 makes coats is a composite soft magnetic material, compare with the existing composite soft magnetic material of making in conventional example 5 that changes into the press-powder fired body of the insulating materials that accompanies silicone resin between the particle of handling the iron Si powder that film coats, aspect density, there is not big difference, but between the particle of the iron Si powder that the deposited oxide film of the present invention that embodiment 9 makes coats, accompany the composite soft magnetic material of press-powder fired body of the insulating materials of silicone resin, compare with the existing composite soft magnetic material of making in conventional example 5 that changes into the press-powder fired body of the insulating materials that accompanies silicone resin between the particle of handling the iron Si powder that film coats, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency and becomes big more, the iron loss characteristic such as more little that becomes.
In addition we know, between the particle of the iron Si powder that the deposited oxide film of the present invention that embodiment 10 makes coats, accompany the composite soft magnetic material of press-powder fired body of the insulating materials of polyimide resin, compare with the existing composite soft magnetic material of making in conventional example 6 that changes into the press-powder fired body of the insulating materials that accompanies polyimide resin between the particle of handling the iron Si powder that film coats, and between the particle of the iron Si powder that the deposited oxide film of the present invention that embodiment 6 makes coats, accompany the composite soft magnetic material of press-powder fired body of the insulating materials of PPS resin, compare with the existing composite soft magnetic material of making in conventional example 7 that changes into the press-powder fired body of the insulating materials that accompanies the PPS resin between the particle of handling the iron Si powder that film coats, also show same result.
＜embodiment 12 〉
The iron Si powder that the deposited oxide film of making at embodiment 8 of the present invention is coated has been implemented after silane is the pre-treatment of coupling agent, the silicone resin of 1.0 quality % is added being diluted in the organic solvent, afterwards 20 ℃ dry down, make mixed-powder.In this mixed-powder, add the zinc stearate of 0.1 quality %, the shaping mixed-powder, making has external diameter: 35mm, internal diameter: 25mm, height: the ring-type press-powder body of 5mm size and have external diameter: 50mm, internal diameter: 25mm, height: the ring-type press-powder body of 25mm size, with these press-powder bodies in vacuum environment, 850 ℃ of following destressings fire, and make the composite soft magnetic material that little external diameter ring-type press-powder fired body and big external diameter ring-type press-powder fired body constitute.With these composite soft magnetic materials of transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually, from the electron ray diffraction pattern that obtains mutually according to described crystal boundary, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually.
Apply winding on little external diameter ring-type press-powder fired body, measure the iron loss of direct current magnetic characteristic and 0.1T, 10kHz, its result as shown in Figure 4.By measuring the inductance under the 20kHz of this little external diameter ring-type press-powder fired body when superposeing the 20A direct current, obtain the permeability of interchange, its result is as shown in table 5.
Then, adopt big external diameter ring-type press-powder fired body to apply winding, make the roughly certain reactor of inductance.This reactor is connected on the general Switching Power Supply that has source filter, measures the efficient (%) of power output with respect to input power 1000W and 1500W, its result is as shown in table 5.
＜embodiment 13 〉
As material powder, preparation have contain Si:6.5 quality %, one-tenth that all the other are made of Fe and unavoidable impurities is grouped into and average grain diameter is the iron Si powder of air water atomizing of the powder shape subglobular of 55 μ m, further preparing average grain diameter is the Mg powder of 40 μ m.The iron Si powder of this air water atomizing is kept under 1 hour the condition with 220 ℃ in atmosphere, powder surface is carried out oxidation processes, in the iron Si powder of air water after this oxidation processes atomizing by the iron Si powder of air water atomizing: the ratio interpolation Mg powder of Mg powder=99.6: 0.4, the mixing manufacture mixed-powder, by with this mixed-powder under 600 ℃ of temperature, pressure 1 * 10 -5MPa kept 1.5 hours down, and the surface that is produced on the iron Si powder of air water atomizing coats the deposited oxide film iron Si powder of the present invention of deposited oxide film.
Utilize the auger electrons light-dividing device to investigate the CONCENTRATION DISTRIBUTION of Mg, Si, O and Fe of depth direction of the deposited oxide film of the iron Si powder that this deposited oxide film coats, its result, have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside, and Si has the concentration slope of the Si that increases more near surface the most surperficial approaching more Si amount.
In addition, analyze,, recognize and contain metal Fe or Fe-Si alloy by resolving in conjunction with energy by the deposited oxide film that forms on the surface of x-ray photoelectron light-dividing device to the iron Si powder that coats at this deposited oxide film.
Therefore as can be known: the deposited oxide film that forms on the surface of the iron Si powder that deposited oxide film of the present invention coats is the Mg-Si-Fe-O quaternary system deposited oxide film that is made of Mg, Si, Fe and O, this Mg-Si-Fe-O quaternary system deposited oxide film have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside, and have the concentration slope that approaches the Si that the most surperficial Si amount increases more more; Contain metal Fe or Fe-Si alloy.And then the tissue of the deposited oxide film of the iron Si powder that coats with the electron microscope observation deposited oxide film is measured the thickness and the maximum crystallization particle diameter of this deposited oxide film, its result, and the average thickness of deposited oxide film is 60nm, maximum crystallization particle diameter is 20nm.
Deposited oxide film iron Si powder of the present invention is being implemented after silane is the pre-treatment of coupling agent, the silicone resin dilution of 1.0 quality % is being added in the organic solvent, afterwards 250 ℃ dry down, make mixed-powder.In this mixed-powder, add the zinc stearate of 0.1 quality %, the shaping mixed-powder, making has external diameter: 35mm, internal diameter: 25mm, height: the ring-type press-powder body of 5mm size and have external diameter: 50mm, internal diameter: 25mm, height: the ring-type press-powder body of 25mm size, these press-powder bodies are fired with 850 ℃ of destressings in vacuum environment, made the composite soft magnetic material that constitutes by little external diameter ring-type press-powder fired body and big external diameter ring-type press-powder fired body.With these composite soft magnetic materials of transmission electron microscope observation, observe the iron particle phase and surround this iron particle crystal boundary phase mutually, recognize the MgO solid solution wustite phase that contains crystalline at crystal boundary mutually from the electron ray diffraction pattern that obtains mutually according to described crystal boundary.
Apply winding on little external diameter ring-type press-powder fired body, measure the iron loss of direct current magnetic characteristic and 0.1T, 10kHz, its result is as shown in table 5.By measuring the inductance under the 20kHz of this little external diameter ring-type press-powder fired body when superposeing the 20A direct current, obtain the permeability of interchange, its result is as shown in table 5.
Then, on big external diameter ring-type press-powder fired body, apply winding, make the roughly certain reactor of inductance.This reactor is connected on the general Switching Power Supply that has source filter, measures the efficient (%) of power output with respect to input power 1000W and 1500W, its result is as shown in table 5.
＜conventional example 8 〉
To have embodiment prepare contain Si:3 quality %, all the other are grouped into by the one-tenth that Fe and unavoidable impurities constitute, and average grain diameter be the iron Si powder of the air water atomizing of 70 μ m to have implemented silane be after the pre-treatment of coupling agent, make the mixed-powder that has mixed 1.0 quality % silicone resins, 0.2 quality %MgO powder.The mixed-powder that obtains is carried out press-powder be shaped, the press-powder body that obtains is fired with 850 ℃ of destressings in vacuum environment, make press-powder fired body with and size identical shaped with embodiment 12.
Apply winding on little external diameter ring-type press-powder fired body, measure the iron loss of direct current magnetic characteristic and 0.1T, 10kHz, its result is as shown in table 5.By measuring the inductance under the 20kHz of this little external diameter ring-type press-powder fired body when superposeing the 20A direct current, obtain the permeability of interchange, its result is as shown in table 5.
Then, on big external diameter ring-type press-powder fired body, apply winding, make the roughly certain reactor of inductance.This reactor is connected on the general Switching Power Supply that has source filter, measures the efficient (%) of power output with respect to input power 1000W and 1500W, its result is as shown in table 5.
Figure 200580049193900631
[0333]From the result shown in the table 5 as can be known, the composite soft magnetic material of the embodiment 12～13 that the press-powder fired body of the iron Si powder that is coated by deposited oxide film of the present invention constitutes, compare with the composite soft magnetic material of the conventional example 8 of using the iron Si powder to make, coercive force is little, iron loss is little, dc superposition characteristic is good, and, the Switching Power Supply that is connected with the reactor of the composite soft magnetic material making of using embodiment 12～13, than the power supply that the reactor of making is connected with using the composite soft magnetic material of making in conventional example 8, efficient is improved, therefore as can be known, have the reactor of the iron core that the composite soft magnetic material of the press-powder fired body that accompanies silicone resin between the iron Si powder particle that deposited oxide film of the present invention coats constitutes, its characteristic further improves.
＜embodiment 14 〉
As material powder, prepare average grain diameter 75 μ m, be iron-based soft magnetic powder by Si:1 quality %, Fe-Si that all the other are made of Fe and unavoidable impurities, further prepare the following pure Si powder of average grain diameter 1 μ m.And then the Mg powder of preparation average grain diameter 50 μ m.
At first, at Fe-Si is in the iron-based soft magnetic powder, by Fe-Si is iron-based soft magnetic powder: pure Si powder=99.5 quality %: 0.5 quality % cooperates pure Si powder, the mixing manufacture mixed-powder, the mixed-powder that obtains is kept heat-treating under 1 hour the condition with 950 ℃ of temperature in hydrogen environment, be the diffusion layer of the surface formation high concentration Si of iron-based soft magnetic powder thus at Fe-Si, afterwards, by keeping under the condition with 250 ℃ of temperature in atmosphere, being produced on the surface oxidation Fe-Si that has oxide layer on the diffusion layer of high concentration Si is the iron-base soft magnetic material powder.
At this surface oxidation Fe-Si is in the iron-base soft magnetic material powder, in surface oxidation Fe-Si is the iron-base soft magnetic material powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % cooperates preprepared Mg powder, the mixing manufacture mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 2.7 * 10 -4 Keep 1 hour while rotating under the condition of MPa, it is iron-based soft magnetic powder (below, be called the powder that deposited oxide film of the present invention coats) 1 that the surface that is produced on Fe-Si thus and is iron-based soft magnetic powder is formed with Fe-Si that the deposited oxide film of the present invention of the deposited oxide film that is made of Mg, Si, Fe and O coats.
Analyze by the x-ray photoelectron light-dividing device, confirm in conjunction with energy by resolving: the deposited oxide film that forms on the powder 1 that deposited oxide film of the present invention coats is the deposited oxide film that is made of Mg, Si, Fe and O; And in the blank of this deposited oxide film, contain metal Fe and Fe-Si alloy.And then, with the tissue of the deposited oxide film in the powder 1 of electron microscope observation deposited oxide film coating of the present invention, measuring the thickness and the maximum crystallization particle diameter of this deposited oxide film, the result is as shown in table 6.Further confirm by the electron ray diffraction pattern: Mg that contains in the deposited oxide film that is made of described Mg, Si, Fe and O and O contain with the form of the MgO solid solution wustite phase of crystalline.
Further, utilize the auger electrons light-dividing device to measure the CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of the depth direction of the deposited oxide film that is made of Mg, Si, Fe and O, its result is as shown in table 6.Mensuration figure when utilizing the auger electrons light-dividing device to measure the CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of depth direction of the deposited oxide film that is made of Mg, Si, Fe and O of powder 1 that deposited oxide film of the present invention coats as shown in Figure 8.In Fig. 8, because the etching period of transverse axis is 0 place is the most surperficial, so in Fig. 8, Mg that contains in the deposited oxide film that is made of Mg, Si, Fe and O and O have the concentration slope towards surperficial Mg and the increase of O amount, Fe has the concentration slope that reduces towards the surface, and the near surface that Si has at deposited oxide film approaches the concentration slope that the most surperficial Si amount increases more more.
The powder 1 that the deposited oxide film of the present invention that so obtains the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 6, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, magnetic characteristics such as iron loss during with magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 6.
＜conventional example 9 〉
Be produced on Fe-Si that embodiment 14 prepares and be chemistry on the surface of iron-based soft magnetic powder formed Fe-Si that the existing Mg of the containing ferrite magnetic oxide that contains Mg ferrite magnetic oxide layer coats be iron-based soft magnetic powder (below, be called the powder that existing deposited oxide film coats), the powder that this existing deposited oxide film the is coated mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 6, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 1.5T and frequency 50Hz, and the magnetic characteristics such as iron loss when magnetic flux density 1.0T and frequency 400Hz, these results are as shown in table 6.
From the result shown in the table 6 as can be known, the powder 1 that the deposited oxide film of making at embodiment 14 of the present invention coats, with using the Fe-Si that contains the coating of Mg ferrite magnetic oxide that makes in conventional example 9 is that the composite soft magnetic material that iron-based soft magnetic powder is made is compared, aspect density, there is not big difference, but the composite soft magnetic material that the powder 1 that uses the deposited oxide film coating of making at embodiment 14 of the present invention is made, with the Fe-Si that the Mg ferrite magnetic oxide coats of containing of the powder that uses the existing deposited oxide film made in conventional example 9 to coat is iron-based soft magnetic powder and the composite soft magnetic material made is compared, the magnetic flux density height, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency and becomes big more, the iron loss characteristic such as more little that becomes.
＜embodiment 15 〉
As material powder, preparing to have the granularity shown in the table 7 and containing Si:1 quality %, Fe-Si that all the other are made of Fe and unavoidable impurities is iron-based soft magnetic powder.Further prepare average grain diameter: pure Si powder and average grain diameter that 1 μ m is following: the Mg powder of 50 μ m.
Different Fe-Si is in the iron-based soft magnetic powder in these granularities, by Fe-Si is iron-based soft magnetic powder: pure Si powder=97 quality %: 2 quality % cooperate pure Si powder, the mixing manufacture mixed-powder, with the mixed-powder that obtains in hydrogen environment, 950 ℃ of temperature, keep heat-treating under 1 hour the condition, be the diffusion layer of the surface formation high concentration Si of iron-based soft magnetic powder thus at Fe-Si, afterwards, by in atmosphere, keep under the condition of 220 ℃ of temperature, being produced on the surface oxidation Fe-Si that has oxide layer on the diffusion layer of high concentration Si is the iron-base soft magnetic material powder.
For this surface oxidation Fe-Si is the iron-base soft magnetic material powder, in surface oxidation Fe-Si is the iron-base soft magnetic material powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % cooperates preprepared Mg powder, the mixing manufacture mixed-powder, by the mixed-powder implementing to obtain at 650 ℃ of temperature, pressure 2.7 * 10 -4Under the condition of MPa while rotate the processing that keeps 1 hour (below, to be the iron-base soft magnetic material powder according to this surface oxidation Fe-Si: Mg powder=99.8 quality %: the ratio of 0.2 quality % cooperates back mixing manufacture mixed-powder, at 650 ℃ of temperature, pressure 2.7 * 10 -4Be called " Mg coats processing " while making the mixed-powder that obtains rotate the processing that kept 1 hour under the condition of MPa), thus the Fe-Si that implements to be produced on the deposited oxide film coating that forms the deposited oxide film that is made of Mg, Si, Fe and O on the surface that Fe-Si is an iron-based soft magnetic powder is the method for the present invention 1～3 of iron-based soft magnetic powder.
Analyze by the x-ray photoelectron light-dividing device, confirm in conjunction with energy by resolving: the Fe-Si that coats at the deposited oxide film that obtains by method 1～3 of the present invention is that the deposited oxide film that forms on the iron-based soft magnetic powder is the deposited oxide film that is made of Mg, Si, Fe and O; And in the blank of this deposited oxide film, contain metal Fe and Fe-Si alloy.And then, the Fe-Si that coats with the electron microscope observation oxide-film is the tissue of the deposited oxide film on the iron-based soft magnetic powder, and further confirm by the electron ray diffraction pattern: Mg that contains in the deposited oxide film that is made of described Mg, Si, Fe and O and O contain with the form of the MgO solid solution wustite phase of crystalline.Further, utilize the auger electrons light-dividing device to measure the CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of the depth direction of the deposited oxide film that is made of Mg, Si, Fe and O, as can be known: Mg that contains in the deposited oxide film and O have the concentration slope, the Fe that increase towards surperficial Mg and O amount and have the near surface that the concentration slope, the Si that reduce towards the surface have at deposited oxide film and approach the concentration slope that the most surperficial Si amount increases more more.
The Fe-Si that coats for the deposited oxide film that is obtained by method 1～3 of the present invention is an iron-based soft magnetic powder, add the mixing silicone resin with match ratio 2 quality %, making is the resin-coating composite powder on the surface of iron-based soft magnetic powder by the Fe-Si that silicone resin has coated the deposited oxide film coating, this resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 7, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 7.
＜conventional example 10 〉
As material powder, preparation has the granularity shown in the table 7 and contains Si:1 quality %, Fe-Si that all the other are made of Fe and unavoidable impurities is iron-based soft magnetic powder, be not that iron-based soft magnetic powder carries out Mg coating processing to this Fe-Si, add silicone resin with match ratio 2 quality %, mix, making and having coated Fe-Si by silicone resin is the resin-coating composite powder on iron-based soft magnetic powder surface.This resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 7, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 7.
Figure 200580049193900711
Hence one can see that, compares the magnetic flux density height by the composite soft magnetic material that method 1～3 of the present invention is made with the composite soft magnetic material of making by existing method 1, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency big more, the iron loss characteristic such as more little that becomes that becomes.
＜embodiment 16 〉
As material powder, preparing to have the granularity shown in the table 8 and containing Si:3 quality %, Fe-Si that all the other are made of Fe and unavoidable impurities is iron-based soft magnetic powder.Further prepare average grain diameter: pure Si powder and average grain diameter that 1 μ m is following: the Mg powder of 50 μ m.
At the different Fe-Si of these granularities is to be iron-based soft magnetic powder by Fe-Si in the iron-based soft magnetic powder: pure Si powder=99.5 quality %: 0.5 quality % cooperates pure Si powder, the mixing manufacture mixed-powder, with the mixed-powder that obtains in hydrogen environment, 950 ℃ of temperature, keep heat-treating under 1 hour the condition, be the diffusion layer of the surface formation high concentration Si of iron-based soft magnetic powder thus at Fe-Si, afterwards, by in atmosphere, keep under the condition of 220 ℃ of temperature, being produced on the surface oxidation Fe-Si that has oxide layer on the diffusion layer of high concentration Si is the iron-base soft magnetic material powder.
Implement method 4～6 of the present invention, by being that the iron-base soft magnetic material powder is implemented Mg and coated and handle to this surface oxidation Fe-Si, being produced on Fe-Si and being the Fe-Si that the deposited oxide film that forms the deposited oxide film that is made of Mg, Si, Fe and O on the surface of iron-based soft magnetic powder coats is iron-based soft magnetic powder.
Analyze by the x-ray photoelectron light-dividing device, confirm in conjunction with energy by resolving: the Fe-Si that coats at the deposited oxide film that obtains by method 4～6 of the present invention is that the deposited oxide film that forms on the iron-based soft magnetic powder is the deposited oxide film that is made of Mg, Si, Fe and O; And in the blank of this deposited oxide film, contain metal Fe and Fe-Si alloy.And then, the Fe-Si that coats with the electron microscope observation oxide-film is the tissue of the deposited oxide film on the iron-based soft magnetic powder, further confirms by the electron ray diffraction pattern: Mg that contains in the deposited oxide film that is made of described Mg, Si, Fe and O and O are that the mode with the MgO solid solution wustite phase of crystalline contains.Further, utilize the auger electrons light-dividing device to measure the CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of the depth direction of the deposited oxide film that is made of Mg, Si, Fe and O, as can be known: Mg that contains in the deposited oxide film and O have the concentration slope, the Fe that increase towards surperficial Mg and O amount and have the near surface that the concentration slope, the Si that reduce towards the surface have at deposited oxide film and approach the concentration slope that the most surperficial Si amount increases more more.
The Fe-Si that coats for the deposited oxide film that is obtained by method 4～6 of the present invention is an iron-based soft magnetic powder, add silicone resin and mixing with match ratio 2 quality %, making is the resin-coating composite powder on the surface of iron-based soft magnetic powder by the Fe-Si that silicone resin has coated the deposited oxide film coating, this resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 8, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 8.
＜conventional example 11 〉
As material powder, preparation has the granularity shown in the table 8 and contains Si:1 quality %, Fe-Si that all the other are made of Fe and unavoidable impurities is iron-based soft magnetic powder, be not that iron-based soft magnetic powder carries out Mg coating processing to this Fe-Si, add silicone resin with match ratio 2 quality %, mix, making and having coated Fe-Si by silicone resin is the resin-coating composite powder on the surface of iron-based soft magnetic powder.This resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 8, in addition, on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 8.
Figure 200580049193900741
Hence one can see that, compares the magnetic flux density height by the composite soft magnetic material that method 4～6 of the present invention is made with the composite soft magnetic material of making by existing method 2, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency big more, the iron loss characteristic such as more little that becomes that becomes.
＜embodiment 17 〉
As material powder, prepare Fe powder with the granularity shown in the table 9.Further prepare following pure Si powder of average grain diameter 1 μ m and the Mg powder of average grain diameter 50 μ m.
In the different Fe powder of these granularities, in the Fe powder: pure Si powder=97 quality %: the ratio of 3 quality % cooperates pure Si powder, the mixing manufacture mixed-powder, with the mixed-powder that obtains in hydrogen environment, under 1 hour condition of 950 ℃ of maintenances of temperature, heat-treat, be the diffusion layer of the surface formation high concentration Si of iron-based soft magnetic powder thus at Fe-Si, afterwards, by in atmosphere, keep under the condition of 220 ℃ of temperature, being produced on the surface oxidation Fe-Si that has oxide layer on the diffusion layer of high concentration Si thus is the iron-base soft magnetic material powder.
Implement method 7～9 of the present invention, by being that the iron-base soft magnetic material powder is implemented Mg and coated and handle to this surface oxidation Fe-Si, being produced on Fe-Si and being the Fe-Si that the deposited oxide film that forms the deposited oxide film that is made of Mg, Si, Fe and O on the surface of iron-based soft magnetic powder coats is iron-based soft magnetic powder.
Analyze by the x-ray photoelectron light-dividing device, confirm in conjunction with energy by resolving: the Fe-Si that coats at the deposited oxide film that obtains by method 7～9 of the present invention is that the deposited oxide film that forms on the iron-based soft magnetic powder is the deposited oxide film that is made of Mg, Si, Fe and O; And in the blank of this deposited oxide film, contain metal Fe and Fe-Si alloy.And then, the Fe-Si that coats with the electron microscope observation oxide-film is the tissue of the deposited oxide film on the iron-based soft magnetic powder, and further confirm by the electron ray diffraction pattern: Mg that contains in the deposited oxide film that is made of described Mg, Si, Fe and O and O are contained in the mode of the MgO solid solution wustite phase of crystalline.Further, utilize the auger electrons light-dividing device to measure the CONCENTRATION DISTRIBUTION of Mg, O, Si and Fe of the depth direction of the deposited oxide film that is made of Mg, Si, Fe and O, as can be known: Mg that contains in the deposited oxide film and O have the concentration slope, the Fe that increase towards surperficial Mg and O amount and have the concentration slope that reduces towards the surface, Si and have at the near surface of deposited oxide film and approach the concentration slope that the most surperficial Si amount increases more more.
The Fe-Si that coats for the deposited oxide film that is obtained by method 7～9 of the present invention is an iron-based soft magnetic powder, add silicone resin and mixing with match ratio 2 quality %, making is the resin-coating composite powder on iron-based soft magnetic powder surface by the Fe-Si that silicone resin has coated the deposited oxide film coating, this resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body and the external diameter of 5mm size: 50mm, internal diameter: 25mm, high: the ring-type press-powder body of 25mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 9, in addition, on the composite soft magnetic material that constitutes by path ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 9.
Measure the inductance under the 20kHz of this path ring-type press-powder fired body when stack 20A direct current, obtain the permeability of interchange, its result is as shown in table 7.Then, on big external diameter ring-type press-powder fired body, apply winding, make the roughly certain reactor of inductance.This reactor is connected on the general Switching Power Supply that has source filter, measures the efficient (%) of relative input power 1000W of power output and 1500W, its result is as shown in table 10.
＜conventional example 12 〉
As material powder, the Fe powder that preparation has the granularity shown in the table 9 does not carry out Mg to this Fe powder and coats processing, adds silicone resin with match ratio 2 quality %, mixes, and makes the resin-coating composite powder that has been coated the Fe powder surface by silicone resin.This resin-coating composite powder is packed in the mould that is heated to 120 ℃, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size, has external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size and have external diameter: 50mm, internal diameter: 25mm, high: the ring-type press-powder body of 25mm size, with the press-powder body that obtains in a vacuum, 700 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, resistivity to the composite soft magnetic material that is made of this tabular fired body is measured, its result is as shown in table 9, further on the composite soft magnetic material that constitutes by path ring-type fired body, apply winding, measure magnetic flux density, coercive force, and the iron loss when magnetic flux density 0.1T and frequency 20Hz, these results are as shown in table 9.
Measure the inductance under the 20kHz of this path ring-type press-powder fired body when stack 20A direct current, obtain the permeability of interchange, its result is as shown in table 7.Then, on big external diameter ring-type press-powder fired body, apply winding, make the roughly certain reactor of inductance.This reactor is connected on the general Switching Power Supply that has source filter, measures the efficient (%) of relative input power 1000W of power output and 1500W, its result is as shown in table 10.
Figure 200580049193900781
Figure 200580049193900791
[0387]Hence one can see that, compares the magnetic flux density height by the composite soft magnetic material that method 7～9 of the present invention is made with the composite soft magnetic material of making by existing method 3, coercive force is little, and resistivity obviously improves, therefore, iron loss is obviously little, especially has frequency big more, the iron loss characteristic such as more little that becomes that becomes.
＜embodiment 18 〉
As material powder, prepare to have average grain diameter 70 μ m and contain the pure iron powder as the sulphur of unavoidable impurities of denier, and then preparing average grain diameter is the Mg powder of 50 μ m.
At first, by in atmosphere, 220 ℃ of temperature, keep under 2 hours the condition described pure iron powder being carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film.For this oxidation processes iron powder, with pre-prepd Mg powder in the oxidation processes iron powder: Mg powder=99.8 quality %: the ratio of 0.3 quality % is added and is mixed, and makes mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 2.7 * 10 -4MPa kept 1 hour down, further kept 1 hour for 200 ℃ with temperature in atmosphere afterwards, thereby the surface that is produced on iron powder coated the iron powder that Mg iron oxide film coats that contains of deposited film.By the x-ray photoelectron light-dividing device deposited film that forms on the iron powder that contains the coating of Mg iron oxide film at this is analyzed, resolved, recognize at least and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O in conjunction with energy.
Investigate the iron powder of this iron powder that contains the coating of Mg iron oxide film and the borderline region of Mg-Fe-O ternary system oxide deposited film by the method for utilizing the auger electrons light-dividing device, the result recognizes: at the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O and iron powder has dense sulphur layer, in this dense sulphur layer because the sulfur impurity (background) that contains than the central part in iron powder detects the peak value of sulphur more significantly by the auger electrons optical spectroscopy, so contain the high sulphur of concentration of the sulphur that concentration ratio iron powder central part contains.And then, contain with electron microscope observation and to contain at least that (result's average thickness of this deposited film as can be known is 60nm for Mg, the Fe) tissue of the Mg-Fe-O ternary system oxide deposited film of O, and maximum crystallization particle diameter is 40nm in the iron powder that Mg iron oxide film coats.
Further, what water and hydrochloric acid had been added in preparation adds water decomposition alkoxy silane solution (prehydrosys alkoxysilane solution) and alkoxyl magnesium solution (magnesium-alkoxide solution) in advance, to add water decomposition alkoxy silane solution in advance: alkoxyl magnesium solution is that 1: 2 Capacity Ratio is mixed, and makes MgO and SiO 2The mixed oxide sol solution, with respect to the iron powder that Mg iron oxide film coats that contains of formerly making, with MgO and SiO 2Mixed oxide convert, add this MgO and the SiO of 0.2 quality % 2The mixed oxide sol solution, mix, coat by 2MgOSiO by the surface of under 150 ℃ of temperature, the mixed-powder that obtains being carried out heat drying, being produced on containing the iron powder that Mg iron oxide film coats 2The MgO-SiO that constitutes 2The composite soft magnetic powder of the present invention of system complex oxide film.
With this composite soft magnetic powder of the present invention mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the tabular press-powder body that obtains and ring-type press-powder body in nitrogen environment, 500 ℃ of temperature, keep firing under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type fired body constitutes, to by the relative density that obtains the composite soft magnetic material that tabular fired body constitutes, resistivity and bending strength are measured, its result is as shown in table 11, further on the composite soft magnetic material that constitutes by the ring-type fired body, apply winding, measure magnetic flux density by the BH plotter, these results are as shown in table 11.
＜conventional example 13 〉
Preparation has formed the iron powder that the Mg ferrite coats that contains that contains the Mg ferrite layer on the surface of pure iron powder with chemical method, containing in the iron powder that the Mg ferrite coats with silicone resin at this is 0.14, MgO is 0.06, all the other are that the ratio that contains the iron powder of Mg ferrite coating is mixed silicone resin and MgO powder, make existing mixed-powder, with the existing mixed-powder that the obtains mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep carrying out sintering under 30 minutes the condition, make thus by composite soft magnetic material tabular and that the ring-type sintered body constitutes.To measuring by the relative density, resistivity and the bending strength that obtain the composite soft magnetic material that tabular sintered body constitutes, its result is as shown in table 11, further on the composite soft magnetic material that constitutes by the ring-type sintered body, apply winding, measure magnetic flux density by the BH plotter, these results are as shown in table 11.
[table 11]
Figure 200580049193900821
[0398]From the result shown in the table 11 as can be known, compare with the composite soft magnetic material of making by existing composite soft magnetic powder by the composite soft magnetic material that composite soft magnetic powder of the present invention is made, all superior at aspects such as bending strength, magnetic flux density and resistivity.
As material powder, preparation has average grain diameter 70 μ m, contains the pure iron powder as the sulphur of unavoidable impurities, by in atmosphere, 220 ℃ of temperature, keep under 2 hours the condition, described pure iron powder is carried out oxidation processes, be produced on the oxidation processes iron powder that the surface has the iron oxide film thus.And then, the Mg powder of preparation average grain diameter 50 μ m.For this oxidation processes iron powder, with pre-prepd Mg powder in the oxidation processes iron powder: Mg powder=99.8 quality %: the ratio of 0.2 quality % is added and is mixed, and makes mixed-powder, with the mixed-powder that obtains at 650 ℃ of temperature, pressure 1 * 10 -4MPa heats while rotating under 1 hour the condition of maintenance down, and the surface that is produced on iron powder thus coats the iron powder that Mg iron oxide film coats that contains of deposited film.With the section structure of electron microscope observation at the deposited film of the surface of this iron powder formation, obtain the thickness and the maximum crystallization particle diameter of this deposited film, its thickness is 40nm as can be known, maximum crystallization particle diameter is 20nm.
Analyze by the deposited film that forms on the surface of x-ray photoelectron light-dividing device to the iron powder that contains Mg iron oxide film at this and coat, resolve, recognize that metal Fe microparticulate is in blank in conjunction with energy.In addition, recognize that metal Fe microparticulate is made of MgO to the most surperficial of deposited film in the blank.And then, utilizing Mg, the O of depth direction of auger electrons light-dividing device investigation deposited film and the CONCENTRATION DISTRIBUTION of Fe, the result recognizes that Mg and O have the concentration slope that the concentration slope, the Fe that reduce to inside from the surface have to be increased to inside.Therefore, recognize: the Mg-Fe-O ternary system oxide deposited film that the deposited film that forms on the surface that contains the iron powder that Mg iron oxide film coats is a metal Fe microparticulate in the blank; This Mg-Fe-O ternary system oxide deposited film have Mg and O from the surface to the concentration slope that reduce inside and Fe increases to inside; And the most surperficial of deposited film is made of MgO.And then, utilize of the distribution of auger electrons light-dividing device to the borderline region investigation sulphur of iron powder and Mg-Fe-O ternary system oxide deposited film, its result recognizes: the borderline region of deposited film and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration contains than the central part in iron powder in this dense sulphur layer.
Further, for preparing to have added water and hydrochloric acid adds water decomposition alkoxy silane solution and alkoxyl magnesium solution in advance, and to add water decomposition alkoxy silane solution in advance: alkoxyl magnesium solution is that 1: 2 Capacity Ratio is mixed, and makes MgO and SiO 2The mixed oxide sol solution, with respect to the iron powder that Mg iron oxide film coats that contains of formerly making, with MgO and SiO 2Mixed oxide convert, add this MgO and the SiO of 0.2 quality % 2The mixed oxide sol solution, mix, by having coated by 2MgOSiO on the surface of under 150 ℃ of temperature, the mixed-powder that obtains being carried out heat drying, being produced on containing the iron powder that Mg iron oxide film coats 2The MgO-SiO that constitutes 2The composite soft magnetic powder of the present invention of system complex oxide film.
With this composite soft magnetic powder of the present invention mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the tabular press-powder body that obtains and ring-type press-powder body in nitrogen environment, 500 ℃ of temperature, keep carrying out sintering under 30 minutes the condition, making is by composite soft magnetic material tabular and that the ring-type sintered body constitutes, to by the relative density that obtains the composite soft magnetic material that tabular sintered body constitutes, resistivity and bending strength are measured, its result is as shown in table 12, further on the composite soft magnetic material that constitutes by the ring-type sintered body, apply winding, measure magnetic flux density by the BH plotter, these results are as shown in table 12.
＜conventional example 14 〉
Preparation has formed the iron powder that the Mg ferrite coats that contains that contains the Mg ferrite layer on the surface of pure iron powder with chemical method, contain in the iron powder of Mg ferrite coating at this, with silicone resin is 0.14, MgO is 0.06, all the other are the ratio that contains the iron powder of Mg ferrite coating, mix silicone resin and MgO powder, make existing mixed-powder, with the existing mixed-powder that the obtains mould of packing into, by drawing, shaping has length: 55mm, wide: 10mm, high: the tabular press-powder body of 5mm size and have external diameter: 35mm, internal diameter: 25mm, high: the ring-type press-powder body of 5mm size, with the press-powder body that obtains in nitrogen environment, 500 ℃ of temperature, keep carrying out sintering under 30 minutes the condition, make thus by composite soft magnetic material tabular and that the ring-type sintered body constitutes.To measuring by the relative density, resistivity and the bending strength that obtain the composite soft magnetic material that tabular sintered body constitutes, its result is as shown in table 12, further on the composite soft magnetic material that constitutes by the ring-type sintered body, apply winding, measure magnetic flux density by the BH plotter, these results are as shown in table 12.
[table 12]
[0407]From the result shown in the table 12 as can be known, compare with the composite soft magnetic material of making by existing composite soft magnetic powder by the composite soft magnetic material that composite soft magnetic powder of the present invention is made, all superior at aspects such as bending strength, magnetic flux density and resistivity.
Industrial applicability
If the iron powder of using the Mg of containing oxide-film of the present invention to coat is made composite soft magnetic material, then owing to have high resistivity, so have low eddy current losses, and, because coercive force is low, so can stably make the composite soft magnetic material with low magnetic hysteresis loss with low cost, can bring superior effect in the electrical/electronic industry.
If the iron powder that the Mg oxide-film coats that contains with the atomic particles dispersed therein of metal Fe Mg-Fe-O ternary system oxide deposited film in the blank of the present invention is carried out the stamping composite soft magnetic material of making, then Mg-Fe-O ternary system oxide deposited film since the atomic particles dispersed therein of metal Fe in blank, so have very strong toughness, even carry out stamping to this iron powder that contains the coating of Mg oxide-film, the situation that the film breakage is also seldom arranged in forming process, therefore, the composite soft magnetic material that obtains is owing to have high resistivity, so have low eddy current losses, and, because coercive force is low, so can stably make the composite soft magnetic material with low magnetic hysteresis loss with low cost, can bring superior effect in the electrical/electronic industry.
If the iron powder that deposited film of the present invention coats is carried out stamping manufacturing composite soft magnetic material, then deposited film since the iron phosphide microparticulate in blank, so have very strong toughness, even carry out stamping to the iron powder that this deposited film coats, the situation that the film breakage is also seldom arranged in forming process, therefore, the composite soft magnetic material that obtains is owing to have high resistivity, so have low eddy current losses, and, because coercive force is low, so can stably make the composite soft magnetic material with low magnetic hysteresis loss with low cost, can bring superior effect in the electrical/electronic industry.
If the iron Si powder of using deposited oxide film of the present invention to coat is made composite soft magnetic material, then owing to have high resistivity, so have low eddy current losses, and, because coercive force is low, so can stably make the composite soft magnetic material with low magnetic hysteresis loss with low cost, can bring superior effect in the electrical/electronic industry.
If being iron-based soft magnetic powder, the Fe-Si that uses deposited oxide film of the present invention to coat makes composite soft magnetic material, then owing to have high resistivity, so have low eddy current losses, and, because coercive force is low, so can stably make the composite soft magnetic material with low magnetic hysteresis loss with low cost, can bring superior effect in the electrical/electronic industry.
According to the present invention, the composite soft magnetic material with high strength and high resistance and high magnetic flux density can be provided, in electric and electronic industry, have superior effect.

Claims (55)

1. one kind contains the iron powder that the Mg oxide-film coats, be coated with at least on the surface of iron powder and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O is characterized in that,
In described Mg-Fe-O ternary system oxide deposited film, contain (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.
2. the iron powder that contains the coating of Mg oxide-film as claimed in claim 1 is characterized in that,
The described iron powder that contains the coating of Mg oxide-film, at iron powder and the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O has dense sulphur layer, the sulphur concentration height that the concentration ratio of the sulphur in this dense sulphur layer contains at the central part of iron powder.
3. the iron powder that contains the coating of Mg oxide-film as claimed in claim 1 or 2 is characterized in that,
Describedly contain at least that (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide deposited film of O.
4. as claim 1, the 2 or 3 described iron powder that contain the coating of Mg oxide-film, it is characterized in that,
Describedly contain (Mg, Fe) the most surperficial formation by MgO in fact of the Mg-Fe-O ternary system oxide deposited film of O at least.
5. composite soft magnetic material, it adopts the iron powder that each the described Mg of containing oxide-film coats in the claim 1～4 to make.
6. composite soft magnetic material as claimed in claim 5 is characterized in that,
Contain Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
7. one kind contains the iron powder that the Mg oxide-film coats, be coated with the atomic particle of metal Fe on the surface of iron powder and be distributed to Mg-Fe-O ternary system oxide deposited film in the blank, it is characterized in that, described Mg-Fe-O ternary system oxide deposited film has the MgO solid solution wustite phase of crystalline in blank.
8. the iron powder that contains the coating of Mg oxide-film as claimed in claim 7 is characterized in that,
Mg and O that the atomic particle of described metal Fe is distributed in the Mg-Fe-O ternary system oxide deposited film in the blank have the concentration slope that reduces towards inside from the surface, and Fe has the concentration slope that increases towards inside.
9. as claim 7 or the 8 described iron powder that contain the coating of Mg oxide-film, it is characterized in that,
Be distributed to Mg-Fe-O ternary system oxide deposited film in the blank and the borderline region of iron powder has dense sulphur layer at the atomic particle of described metal Fe, the sulphur concentration height that the concentration ratio of sulphur contains at the central part of iron powder in this dense sulphur layer.
10. as claim 7, the 8 or 9 described iron powder that contain the coating of Mg oxide-film, it is characterized in that,
The atomic particle of described metal Fe is distributed to Mg-Fe-O ternary system oxide deposited film in the blank, and to have the crystallization particle diameter be the following fine crystal tissue of 200nm.
11. as claim 7,8, the 9 or 10 described iron powder that contain the coating of Mg oxide-film, it is characterized in that,
The atomic particle of described metal Fe is distributed to the most surperficial the formation MgO in fact of the Mg-Fe-O ternary system oxide deposited film in the blank.
12. a composite soft magnetic material, it adopts the iron powder that each the described Mg of containing oxide-film coats in the claim 7～11 to make.
13. composite soft magnetic material as claimed in claim 12 is characterized in that,
Contain Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains MgO solid solution wustite phase mutually at described crystal boundary.
14. composite soft magnetic material as claimed in claim 13 is characterized in that,
Described MgO solid solution wustite is crystalline mutually.
15. iron powder that deposited film coats, be coated with the deposited film that constitutes by Mg, Fe, P and O on the surface of iron powder, it is characterized in that, described deposited film contains Mg-Fe-P-O quaternary system phosphate compounds that is made of Mg, Fe, P and O and the Mg-Fe-O ternary system oxide that is made of Mg, Fe and O, and the MgO solid solution wustite that contains crystalline in described Mg-Fe-P-O quaternary system phosphate compounds and the Mg-Fe-O ternary system oxide mutually.
16. the iron powder that deposited film as claimed in claim 15 coats is characterized in that,
Described deposited film is dispersed with the iron phosphide particulate in blank.
17. the iron powder as claim 15 or 16 described deposited films coatings is characterized in that,
It is the following fine crystal tissue of 200nm that described deposited film has the crystallization particle diameter.
18. a composite soft magnetic material, it adopts iron powder making of claim 15,16 or 17 described deposited films coatings and has high resistivity.
19. composite soft magnetic material as claimed in claim 18 is characterized in that,
Contain oxide, this oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
20. iron Si powder that deposited oxide film coats, be formed with the Mg-Si-Fe-O quaternary system deposited oxide film that constitutes by Mg, Si, Fe and O on the surface of iron Si powder, it is characterized in that described Mg-Si-Fe-O quaternary system deposited oxide film contains the MgO solid solution wustite phase of crystalline.
21. the iron Si powder that deposited oxide film as claimed in claim 20 coats is characterized in that,
Described Mg-Si-Fe-O quaternary system deposited oxide film has towards surperficial Mg and O amount to be increased and towards the concentration slope that surperficial Fe amount reduces, and also has the concentration slope of the Si that increases more near surface the most surperficial approaching more Si amount.
22. the iron Si powder as claim 20 or 21 described deposited oxide films coatings is characterized in that,
Described Mg-Si-Fe-O quaternary system deposited oxide film contains metal Fe or Fe-Si alloy.
23. the iron Si powder as claim 20,21 or 22 described deposited oxide films coat is characterized in that,
It is the following fine crystal tissue of 200nm that described Mg-Si-Fe-O quaternary system deposited oxide film has the average crystallite particle diameter.
24. the iron Si powder as claim 20,21,22 or 23 described deposited oxide films coat is characterized in that,
Described iron Si powder has following composition,, contains the Si of 0.1～10 quality % that is, and all the other are made of Fe and unavoidable impurities.
25. a composite soft magnetic material is characterized in that, the press-powder fired body of the iron Si powder that is coated by claim 20,21,22,23 or 24 described deposited oxide films constitutes.
26. a composite soft magnetic material is characterized in that,
Constitute by the press-powder fired body, this press-powder fired body is to sandwich insulating materials to form between the particle of the iron Si powder that claim 20,21,22,23 or 24 described deposited oxide films coat, and this insulating materials is silicone resin, polyimide resin or PPS resin.
27. as claim 25 or 26 described composite soft magnetic materials, it is characterized in that,
Contain Mg-Si-Fe-O quaternary system oxide, this Mg-Si-Fe-O quaternary system oxide is made of with this iron silicon particle of encirclement crystal boundary mutually mutually mutually iron silicon particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
28. a reactor iron core is characterized in that,
Constitute by claim 25,26 or 27 described composite soft magnetic materials.
29. a reactor, it has the described iron core of claim 28.
30. the Fe-Si of a deposited oxide film coating is an iron-based soft magnetic powder, at Fe-Si is that the surface of iron-based soft magnetic powder is formed with the deposited oxide film that is made of Mg, Si, Fe and O, and described Fe-Si is that the superficial layer of iron-based soft magnetic powder is a high concentration Si diffusing surface layer, the concentration height that the Si that contains in the Si concentration ratio powder integral body in this high concentration Si diffusing surface layer forms, it is characterized in that the deposited oxide film that is made of Mg, Si, Fe and O contains the MgO solid solution wustite phase of crystalline.
31. the Fe-Si that deposited oxide film as claimed in claim 30 coats is an iron-based soft magnetic powder, it is characterized in that,
Described Fe-Si is that iron-based soft magnetic powder has following composition,, contains the Si of 0.1～10 quality % that is, and all the other are made of Fe and unavoidable impurities.
32. the Fe-Si as claim 30 or 31 described deposited oxide films coatings is an iron-based soft magnetic powder, it is characterized in that,
The described deposited oxide film that is made of Mg, Si, Fe and O has: towards surperficial Mg and O amount increase, towards surperficial Fe amount reduces, Si increases more at the near surface the most surperficial approaching more Si amount of deposited oxide film concentration slope.
33. the Fe-Si that coats as claim 30,31 or 32 described deposited oxide films is an iron-based soft magnetic powder, it is characterized in that,
The described deposited oxide film that is made of Mg, Si, Fe and O contains metal Fe or Fe-Si alloy.
34. the Fe-Si that coats as claim 30,31,32 or 33 described deposited oxide films is an iron-based soft magnetic powder, it is characterized in that,
It is fine crystal tissue below the 200nm that the described deposited oxide film that is made of Mg, Si, Fe and O has the average crystallite particle diameter.
35. one kind is used to make Fe-Si that claim 30,31,32,33 or 34 described deposited oxide films coat is that the surface oxidation Fe-Si of iron-based soft magnetic powder is the iron-base soft magnetic material powder, it is characterized in that, be that iron-based soft magnetic powder carries out oxidation processes and forms to Fe-Si.
36. one kind is used to make Fe-Si that claim 30,31,32,33 or 34 described deposited oxide films coat is that the surface oxidation Fe-Si of iron-based soft magnetic powder is the iron-base soft magnetic material powder, it is characterized in that,
At Fe-Si is the diffusion layer that the surface of iron-based soft magnetic powder is formed with high concentration Si, Si concentration ratio Fe-Si is the concentration height that the Si that contains of iron-based soft magnetic powder integral body forms in the diffusion layer of this high concentration Si, also is formed with oxide layer on the diffusion layer of this high concentration Si.
37. a composite soft magnetic material is characterized in that,
The Fe-Si that is coated by claim 30,31,32,33 or 34 described deposited oxide films is that the press-powder fired body of iron-based soft magnetic powder constitutes.
38. composite soft magnetic material as claimed in claim 37 is characterized in that,
It is made of the press-powder fired body, this press-powder fired body is to sandwich insulating materials to form between the Fe-Si that claim 30,31,32,33 or 34 described deposited oxide films coat is the particle of iron-based soft magnetic powder, and this insulating materials is silicone resin, polyimide resin or PPS resin.
39. composite soft magnetic material as claimed in claim 37 is characterized in that,
Contain oxide, this oxide is that the iron-base soft magnetic particle is that iron-base soft magnetic particle crystal boundary mutually constitutes mutually with surrounding this Fe-Si mutually by Fe-Si, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
40. a reactor iron core is characterized in that,
Constitute by claim 37,38 or 39 described composite soft magnetic materials.
41. a reactor is characterized in that,
Constitute by claim 37,38 or 39 described composite soft magnetic materials.
42. a composite soft magnetic powder also is coated with MgO-SiO on the surface of the iron powder that contains the coating of Mg iron oxide film 2System complex oxide film, the iron powder that the described Mg of containing iron oxide film coats coat on the surface of iron powder and contain (Mg, Fe) the Mg-Fe-O ternary system oxide deposited film of O, described MgO-SiO at least 2MgO/SiO in the system complex oxide film 2Molar ratio in 1.0～3.0 scope, it is characterized in that, contain in the described Mg-Fe-O ternary system oxide film deposition film (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.
43. a composite soft magnetic powder also is coated with MgO-SiO on the surface of the iron powder that contains the coating of Mg iron oxide film 2The system complex oxide film, the iron powder that the described Mg of containing iron oxide film coats coats on the surface of iron powder and contains (Mg at least, Fe) the Mg-Fe-O ternary system oxide deposited film of O, and at the described (Mg that contains at least, Fe) borderline region of the Mg-Fe-O ternary system oxide deposited film of O and iron powder has dense sulphur layer, the sulphur concentration height that sulphur concentration in this dense sulphur layer contains than the central part of iron powder, described MgO-SiO 2MgO/SiO in the system complex oxide film 2Molar ratio in 1.0～3.0 scope, it is characterized in that, contain in the described Mg-Fe-O ternary system oxide film deposition film (Mg, Fe) O is the MgO solid solution wustite phase of crystalline.
44. as claim 42 or 43 described composite soft magnetic materials, it is characterized in that,
Describedly contain at least that (Mg, Fe) to have the crystallization particle diameter be the following fine crystal tissue of 200nm to the Mg-Fe-O ternary system oxide film deposition film of O.
45. as claim 42,43 or 44 described composite soft magnetic materials, it is characterized in that,
Describedly contain (Mg, Fe) the most surperficial formation by MgO in fact of the Mg-Fe-O ternary system oxide film deposition film of O at least.
46. a composite soft magnetic material is characterized in that,
Contain Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
47. a composite soft magnetic powder also is coated with MgO-SiO on the surface of the iron powder that contains the coating of Mg iron oxide film 2The system complex oxide film, the described iron powder that contains the coating of Mg iron oxide film coats Mg-Fe-O ternary system oxide deposited film, dispersed metal Fe particulate in the blank of this Mg-Fe-O ternary system oxide deposited film, described MgO-SiO on the surface of iron powder 2MgO/SiO in the system complex oxide film 2Molar ratio in 1.0～3.0 scope, it is characterized in that described Mg-Fe-O ternary system oxide deposited film has the MgO solid solution wustite phase of crystalline in blank.
48. a composite soft magnetic powder also is coated with MgO-SiO on the surface of the iron powder that contains the coating of Mg oxide-film 2The system complex oxide film, the iron powder that the described Mg of containing oxide-film coats is coated with the Mg-Fe-O ternary system oxide deposited film of metal Fe microparticulate in blank on the surface of iron powder, this Mg-Fe-O ternary system oxide deposited film has the concentration slope that Mg and O reduce towards inside from the surface and Fe increases towards inside, described MgO-SiO 2MgO/SiO in the system complex oxide film 2Molar ratio in 1.0～3.0 scope, it is characterized in that described Mg-Fe-O ternary system oxide deposited film has the MgO solid solution wustite phase of crystalline in blank.
49. as claim 47 or 48 described composite soft magnetic powder, it is characterized in that,
The iron powder that the described Mg of containing oxide-film coats is to contain the iron powder that Mg iron oxide film coats, and has dense sulphur layer at the borderline region of Mg-Fe-O ternary system oxide deposited film and iron powder, the sulphur concentration height that sulphur concentration contains than the central part of iron powder in this dense sulphur layer.
50. as claim 47,48 or 49 described composite soft magnetic powder, it is characterized in that,
It is the following fine crystal tissue of 200nm that described Mg-Fe-O ternary system oxide deposited film has the crystallization particle diameter.
51. as claim 47,48,49 or 50 described composite soft magnetic powder, it is characterized in that,
The most surperficial formation by MgO in fact of described Mg-Fe-O ternary system oxide deposited film.
52. a composite soft magnetic material is characterized in that,
Contain Mg-Fe-O ternary system oxide, this Mg-Fe-O ternary system oxide is made of with this iron particle of encirclement crystal boundary mutually mutually mutually iron particle, contains the MgO solid solution wustite phase of crystalline mutually at described crystal boundary.
53. electromagnetic circuit parts that constitute by claim 5,6,12,13,14,18,19,25,26,27,37,38,39,46 or 52 described composite soft magnetic materials.
54. electromagnetic circuit parts as claimed in claim 53 is characterized in that,
Described electromagnetic circuit parts are: magnetic core, iron core of electric motor, generator core, solenoid plunger, igniter iron core, reactor, transformer, choke core or magnetic sensor iron core.
55. an electric equipment, it is assembled with claim 53 or 54 described electromagnetic circuit parts.
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JP2005155206A JP4761835B2 (en) 2005-01-25 2005-05-27 Mg-containing iron oxide coated iron powder
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JP2005155207A JP4761836B2 (en) 2005-01-25 2005-05-27 Mg-containing iron oxide coated iron powder
JP2005158892A JP2006324612A (en) 2005-04-20 2005-05-31 Composite soft magnetic material consisting of deposited oxide film-coated iron/silicon powder and sintered green compact of its powder
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JP2005158893A JP5027390B2 (en) 2005-03-28 2005-05-31 Deposited film-coated iron powder
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