CN101849268A - High-strength soft-magnetic composite material obtained by compaction/burning and process for producing the same - Google Patents

High-strength soft-magnetic composite material obtained by compaction/burning and process for producing the same Download PDF

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CN101849268A
CN101849268A CN200880114838A CN200880114838A CN101849268A CN 101849268 A CN101849268 A CN 101849268A CN 200880114838 A CN200880114838 A CN 200880114838A CN 200880114838 A CN200880114838 A CN 200880114838A CN 101849268 A CN101849268 A CN 101849268A
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oxide
soft
magnetic
compaction
burning
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CN101849268B (en
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田中义浩
宫原正久
森本耕一郎
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Diamet Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/33—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials mixtures of metallic and non-metallic particles; metallic particles having oxide skin

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

Abstract

A soft-magnetic composite material obtained by compaction/burning. The burned material is obtained by mixing soft-magnetic particles each coated with a magnesium-containing oxide with at least one of silicone resins, low-melting glasses, and metal oxides, compacting the mixture, burning the compact in a non-oxidizing atmosphere to form a precursor for the soft-magnetic composite compacted/burned material, and then heat-treating the precursor in an oxidizing atmosphere.

Description

High-strength soft-magnetic composite material obtained by compaction/burning and manufacture method thereof
Technical field
The present invention relates to as motor, actuator, reactor, transformer, choke core the employed high-strength soft-magnetic composite material obtained by compaction/burning of former material and the manufacture method thereof of various electromagnetic circuit parts such as Magnetic Sensor magnetic core.
The application here cites its content for application 2007-289774 number opinion priority of application on November 7th, 2007.
Background technology
Always, as the magnetic core material of motor, actuator, Magnetic Sensor etc., known to have iron powder, Fe-Al be that iron-base soft magnetic alloy powder, Fe-Ni are that iron-base soft magnetic alloy powder, Fe-Cr are that iron-base soft magnetic alloy powder, Fe-Si are that iron-base soft magnetic alloy powder, Fe-Si-Al are iron-base soft magnetic alloy powder (following it is referred to as the soft magnetic metal particle) sintering and the soft-magnetic sintered material that obtains.For this soft-magnetic sintered material, its magnetic flux density height is that resistivity is low but then, therefore has the such problem of high frequency characteristics difference.High frequency characteristics is improved, propose favourable with waterglass or low-melting glass (with reference to patent documentation 1 or patent documentations 2) such as press-powder soft magnetic materials in conjunction with the soft magnetic metal particle.
But with waterglass or the low-melting glass composite soft magnetic sintering material in conjunction with aforementioned soft magnetic metal particle, the tack of soft magnetic metal particle and waterglass or low-melting glass is poor.Therefore, if with waterglass or low-melting glass in conjunction with the soft magnetic metal particle and guarantee intensity, then must mix, to reach the degree that in waterglass or low-melting glass, is dispersed with the soft magnetic metal particle with a large amount of waterglass or low-melting glasses.The press-powder soft magnetic material resistivity that obtains though use waterglass or low-melting glass so in a large number becomes big, but magnetic flux density extremely reduces, and the problem that can not use as the material of the various electronic units such as magnetic core of motor, actuator, Magnetic Sensor is arranged.
Therefore, under the purpose of existing side by side that realizes high magnetic flux density and high resistivity, proposition has a kind of composite soft magnetic sintering material, it is made of with crystal boundary with its encirclement mutually mutually the soft magnetic metal particle, and described crystal boundary reaches glassy phase mutually by the ZnO type phase with hexagonal crystal structure, mixed oxide with cube brilliant Fe that constructs and Zn and constitutes (with reference to patent documentation 3).Described ZnO type with structure of hexagonal crystal contacts dispersion with described soft magnetic metal particle, the dispersion that contacts with described ZnO type of the mixed oxide of described Fe that has cube a brilliant structure and Zn.Described glassy phase contacts and is clipped in therebetween with described mixed oxide with cube Fe of brilliant structure and Zn and disperses.
On the other hand, the also known method that manufacturing press-powder magnetic material is arranged, it is method by chemical such as chemical platings or rubbing method etc. to be coated with the Mg iron oxide lining iron powder that contains that contains the Mg ferrite membrane mix with the low-melting glass powder, and heat treatment is also carried out in the shaping of compacting afterwards.
Patent documentation 1: the spy opens flat 5-258934 communique
Patent documentation 2: the spy opens clear 63-158810 communique
Patent documentation 3: the spy opens the 2004-253787 communique
Patent documentation 4: the spy opens the 2004-297036 communique
According to aforementioned patent document 3 described composite soft magnetic sintering materials, exist if the mixed oxide of Fe and Zn heats then resolvent problem with the temperature above 600 ℃.But, under the temperature of the degree that this decomposition can not take place, burn till, when for example burning till with 600 ℃, patent documentation 3 not fusions of described glass powder, therefore be difficult to improve the caking property between the soft magnetic metal particle phase, be difficult to obtain high-intensity soft-magnetic composite material obtained by compaction/burning.
In addition, if adding the hybrid glass powder in zinc oxide lining soft magnetic metal particle also is shaped, then glass powder-zinc oxide tunicle (insulating barrier) rubs, and the zinc oxide tunicle damages easily, therefore is difficult to obtain the soft-magnetic composite material obtained by compaction/burning of high resistivity.
On the other hand, to contain the compacting of Mg iron oxide lining iron powder burns till in the soft-magnetic composite material obtained by compaction/burning that forms, be that method by chemistry is in the surface-coated Mg of the containing ferrite membrane of soft magnetic metal particle, therefore ferrite membrane is unstable and change, insulating properties reduces, and it is insufficient for the tack on the surface of soft magnetic metal particle to contain the Mg ferrite membrane.Therefore, even burn till again after will containing Mg iron oxide film lining powder and low-melting glass extrusion molding, also possibly can't provide the soft-magnetic composite material obtained by compaction/burning of full intensity.
Summary of the invention
The present invention creates in view of the above-mentioned problems, the objective of the invention is to, a kind of high-strength soft-magnetic composite material obtained by compaction/burning is provided, have can be to surpass 600 ℃ temperature by becoming for it, the structure of the MgO tunicle of the excellent heat resistance that burns till of 700 ℃ temperature for example, can both keep high resistivity, can realize low coercive force by stress relief annealing again.In addition, another object of the present invention is to, a kind of high-strength soft-magnetic composite material obtained by compaction/burning is provided, it is by with containing with Fe 3O 4For the low-melting glass of the iron oxide of main body or the grain boundary layer of metal oxide are filled in conjunction with soft magnetic metal particle interface each other, thus can be powerful in conjunction with the soft magnetic metal particle each other, given play to high breaking strength.
Present inventors carry out the discovering of soft-magnetic sintered material of Fe system, even the material that also can not break as insulation tunicle when the extrusion molding has the soft magnetic powder that contains Mg oxide incrusting type.
In the present invention, by the soft magnetic powder that heating Fe is in oxidizing atmosphere in advance, the surface that is produced on soft magnetic powder is formed with the oxidation processes soft magnetic powder of the film of iron oxide.Then, in this oxidation processes soft magnetic powder, add the Mg powder, in inert gas atmosphere or vacuum atmosphere, after the mixed-powder that heating obtains with granulation rotation mixing stirring device mixing, be implemented in the oxidation processes that heats in the oxidizing atmosphere more as required.According to this technology, can access and be formed with on the surface of soft magnetic powder particle at general known Mg-FeO-Fe 2O 3(Mg, the Fe) O, (Mg, the Fe) that represent among the system 3O 4Among the various oxides of Mg-Fe-O ternary system, contain the soft magnetic powder of the Mg-Fe-O ternary system oxidate film of (Mg, Fe) O at least.
Contain Mg oxide lining soft magnetic powder for what the surface at the soft magnetic powder of Fe system was formed with this Mg-Fe-O ternary system oxidate film that contains (Mg, Fe) O at least, oxide-film for the tack of the soft magnetic powder of Fe system than the current material excellence many.Therefore, when containing the extrusion molding of Mg oxide lining soft magnetic powder, oxide-film as insulating coating seldom breaks, the soft magnetic powder that oxide-film positively is present in Fe system each other, therefore, burn till even carry out the high temperature destressing behind extrusion molding, the insulating properties of oxide-film can not reduce yet, can keep high resistivity, so the eddy current loss step-down.In addition, reduce coercive force,, therefore can access low-loss soft-magnetic composite material obtained by compaction/burning so very the lowland suppresses magnetic hysteresis loss owing to can also burn till the back in destressing.
Present inventors are conceived to this technology, and the staypak that research obtains the compacting shaping of the aforesaid Mg of containing oxide lining soft magnetic powder has been finished the present invention.
(1) high-strength soft-magnetic composite material obtained by compaction/burning of first form of the present invention, be contain Mg oxide lining soft-magnetic particles through grain boundary layer by the high-strength soft-magnetic composite material obtained by compaction/burning of a plurality of be combined intos, wherein,
The described Mg of containing oxide lining soft-magnetic particles have Fe be soft magnetic metal particle and the surface that is coated on this soft magnetic metal particle contain the Mg oxide-film,
Described high-strength soft-magnetic composite material obtained by compaction/burning has:
Described contain Mg oxide lining soft-magnetic particles through the face side grain boundary layer by the skin section of a plurality of be combined intos, wherein, described face side grain boundary layer will contain with Fe 3O 4Or FeO be main body iron oxide Si oxide and to contain in the ferriferous oxide of Mg any one above as main body;
Described contain Mg oxide lining soft-magnetic particles through the private side grain boundary layer by the internal layer portion of a plurality of be combined intos, wherein, described private side grain boundary layer is with Si oxide and contain more than in the ferriferous oxide of Mg any one as main body.
(2) high-strength soft-magnetic composite material obtained by compaction/burning of second form of the present invention, a plurality of combinations that contain Mg oxide lining soft-magnetic particles through the face side grain boundary layer described in its (1), be have described soft magnetic metal particle and be coated on the containing the Mg oxide-film of surface of this soft magnetic metal particle and constitute contain Mg oxide lining soft-magnetic particles, with at least a combination that obtains by mixed compaction heat treatment in silicones, low-melting glass, the metal oxide
The Fe that is present in the face side grain boundary layer between the described Mg of containing oxide lining soft-magnetic particles 3O 4Or FeO, be that the Fe composition is that the soft magnetic metal particle is separated out the formation oxide and disperseed growth and formation at crystal boundary from described Fe,
With described face side grain boundary layer adjacency contain the Mg oxide-film, be to be obtained by overlay film from the Mg oxide Mg oxide that contains that is had on the soft-magnetic particles that is covered that contains that described mixed compaction burns till before handling.
(3) high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention, the described Mg of the containing oxide-film of (1) or (2) constitutes based on (Mg, Fe) O, and described low-melting glass is by Bi 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Any one formation among the O-ZnO.
(4) high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention, each the described Mg of containing oxide-film constitutes based on (Mg, Fe) O in (1)～(3), and described metal oxide is by from Al 2O 3, B 2O 3, Sb 2O 3, MoO 3In one or more formations of selecting.
(5) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention, be will have Fe be the soft magnetic metal particle and be coated on the containing the Mg oxide-film of surface of this soft magnetic metal particle and constitute contain Mg oxide lining soft-magnetic particles, and silicones, low-melting glass, at least a mixed compaction in the metal oxide, after in non-oxidizing atmosphere, burning till the precursor of handling the formation soft-magnetic composite material obtained by compaction/burning, in oxidizing atmosphere, heat-treat, become sintered body therefrom with skin section and internal layer portion
Described skin section is that face side at described precursor is through containing with Fe at least 3O 4FeO be main body iron oxide Si oxide or contain the face side grain boundary layer that filler constituted of the ferriferous oxide of Mg at least, with the described a plurality of be combined intos of Mg oxide lining soft-magnetic particles that contain,
Described internal layer portion is the internal layer side at described precursor, through based on Si oxide with contain private side grain boundary layer more than in the ferriferous oxide of Mg any one, will describedly contain the Mg oxide a plurality of be combined intos of soft-magnetic particles that are covered.
(6) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention, the iron oxide that contains the grain boundary layer between Mg oxide lining soft-magnetic particles that is present in described skin section of (5) are that to make the Fe composition be that the soft magnetic metal particle is separated out at crystal boundary and formed oxide and make the scattered length of this divided oxide from described Fe.
(7) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention as (5) or (6) described non-oxidizing atmosphere, is inert gas atmosphere or hydrogen atmospheres such as nitrogen atmosphere, argon gas atmosphere.
(8) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention as each described oxidizing atmosphere in (5)～(7), is more than 400 ℃ and in the vapor atmosphere or atmosphere below 600 ℃.
(9) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention is to make in (5)～(8) each described temperature of burning till processing more than 550 ℃ and the scope below 750 ℃.
(10) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention, be by in (5)～(9), burning till processing in each described non-oxidizing atmosphere, by in described non-oxidizing atmosphere, burning till processing, the wustite of (Mg, the Fe) O that contains Mg and Fe is generated at grain boundary layer, become and contain Si oxide that contains iron oxide at least and any one the filler in the ferriferous oxide that contains Mg at least by in described oxidizing atmosphere, heat-treating, make the grain boundary layer that contains described wustite.
(11) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention as each described low-melting glass in (5)～(10), is used Bi 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Any one of O-ZnO.
(12) manufacture method of the high-strength soft-magnetic composite material obtained by compaction/burning of other forms of the present invention as each described metal oxide in (5)～(11), is used Al 2O 3, B 2O 3, Sb 2O 3, MoO 3Any one.
In the present invention, can with good tack form the soft magnetic metal particle of Fe system and overlayed on this soft magnetic metal particle the surface contain the Mg oxide by overlay film.In addition, contain the Mg oxide by the soft magnetic metal particles of the Fe of overlay film system, engaged with the face side grain boundary layer of any one composition of the silicones that contains the mixing that is present in its grain boundary layer, low-melting glass, metal oxide for having.And the crystal boundary in the bonding part makes iron oxide disperse growth, so face side grain boundary layer and to contain the Mg oxide also high by the adhesive force of overlay film, so can access high-intensity soft-magnetic composite material obtained by compaction/burning.
And, because the described Mg of containing oxide still can positively be present in after compacting is shaped by overlay film Fe system the soft magnetic metal particle around, so the soft magnetic metal particle that can make Fe system insulated separation positively respectively.Therefore, soft-magnetic composite material obtained by compaction/burning integral body can both obtain high resistivity, the soft-magnetic composite material obtained by compaction/burning of the eddy current loss that can be inhibited.
In addition, the part of skin section that engages the soft magnetic metal particle of Fe system with the face side grain boundary layer has high strength, and the having of the part of this skin section helps composite soft magnetic material obtained by compaction/burning integral intensity and improve.
The soft-magnetic composite material obtained by compaction/burning that obtains according to the present invention has high density, high strength, high resistivity and high magnetic flux density.Soft-magnetic composite material obtained by compaction/burning of the present invention is the material of excellence that has the characteristics of high strength and high magnetic energy density and the low iron loss of high frequency concurrently, can use as the material of the various electromagnetic circuit parts that will bring into play these features.
In soft-magnetic composite material obtained by compaction/burning of the present invention, use (Mg, Fe) O as main body as containing the Mg oxide-film, as low-melting glass, can use Bi 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Any one of O-ZnO as metal oxide, uses Al 2O 3, B 2O 3, Sb 2O 3, MoO 3Any one, thus, can obtain the soft-magnetic composite material obtained by compaction/burning of high density, high strength, high resistivity and high magnetic flux density particularly.
Manufacturing method according to the invention can access the soft-magnetic composite material obtained by compaction/burning of characteristic of the above-mentioned excellence of performance.Particularly under manufacture method of the present invention, by in oxidizing atmosphere, heat-treating, the skin section that helps intensity to improve can be generated, except high density, high resistivity and high magnetic flux density, high-intensity soft-magnetic composite material obtained by compaction/burning can also be obtained.
Intensity soft-magnetic composite material obtained by compaction/burning of the present invention, can be used as described electromagnetic circuit parts, for example utilizations such as magnetic core, motor core, generator magnetic core, solenoid core, igniting core, reactor magnetic core, magnetic core of transformer, choking-winding magnetic core or Magnetic Sensor magnetic core, no matter be in any, to use, the electromagnetic circuit of having given play to excellent specific property parts can both be provided.
And, in the electric equipment that is equipped with these electromagnetic circuit parts, comprise motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, transducer, transformer, relay, magnetic sensor system etc., the present invention has the high efficiency high performance that can carry out these electric equipments and the effect of miniaturization and.
Description of drawings
Figure 1A is the skeleton diagram of the cross-section structure of the high-strength soft-magnetic composite material obtained by compaction/burning test portion of the present invention that obtains among the embodiment of expression.
Figure 1B is the ideograph of enlarged photograph of the metal structure section of the high-strength soft-magnetic composite material obtained by compaction/burning test portion that obtains among the embodiment of expression.
Fig. 2 is the enlarged photograph of another routine metal structure of the high-strength soft-magnetic composite material obtained by compaction/burning test portion of the present invention that obtains among the embodiment of expression.
Fig. 3 is the X-ray diffractogram of the results of elemental analyses of 111 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 4 is the X-ray diffractogram of the results of elemental analyses of 112 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 5 is the X-ray diffractogram of the results of elemental analyses of 113 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 6 is the X-ray diffractogram of the results of elemental analyses of 114 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 7 is the X-ray diffractogram of the results of elemental analyses of 115 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 8 is the X-ray diffractogram of the results of elemental analyses of 116 positions on the test portion shown in the photo of presentation graphs 2.
Fig. 9 is the enlarged photograph of another routine metal structure of the high-strength soft-magnetic composite material obtained by compaction/burning test portion of the present invention that obtains among the embodiment of expression.
Figure 10 is an expression X-ray diffractogram of organizing 1 represented locational results of elemental analyses on the photo shown in Figure 9.
Figure 11 is an expression X-ray diffractogram of organizing 2 represented locational results of elemental analyses on the photo shown in Figure 9.
Figure 12 is the X-ray diffractogram of the expression locational results of elemental analyses of organizing the demonstration of 3 on the photo shown in Figure 9.
Figure 13 is the X-ray diffractogram of the expression locational results of elemental analyses of organizing the demonstration of 4 on the photo shown in Figure 9.
Figure 14 is the X-ray diffractogram of the expression locational results of elemental analyses of organizing the demonstration of 5 on the photo shown in Figure 9.
Figure 15 is the X-ray diffractogram of the expression locational results of elemental analyses of organizing the demonstration of 6 on the photo shown in Figure 9.
Figure 16 is the enlarged photograph of another routine metal structure of the high-strength soft-magnetic composite material obtained by compaction/burning test portion of the present invention that obtains among the embodiment of expression.
Symbol description
1Fe is the soft magnetic metal particle, and 2 contain the Mg oxide-film, and 3 contain Mg oxide lining soft-magnetic particles, 5 face side grain boundary layers, 10 soft-magnetic composite material obtained by compaction/burning, 10a skin section, 10b internal layer portion
Embodiment
Below, Yi Bian with reference to accompanying drawing, Yi Bian preferred embodiment describe for of the present invention.
In the present invention, at first make the Mg-Fe-O ternary system oxidate film contain (Mg, Fe) O overlayed on the surface of soft magnetic metal particle and form contain Mg oxide lining soft-magnetic particles (powder).
In order to obtain this lining soft magnetic metal particle, use following various material powders, any one that select the method described in (A)～(D) described later implemented to get final product.
The Fe of the material powder that uses in the manufacture method as the Mg of containing oxide lining soft magnetic metal particle of the present invention is the soft magnetic metal particle, and preferred always general known iron powder, insulation processing iron powder, Fe-Al is that iron-base soft magnetic alloy powder, Fe-Ni are that iron-base soft magnetic alloy powder, Fe-Cr are that iron-base soft magnetic alloy powder, Fe-Si are that iron-base soft magnetic alloy powder, Fe-Si-Al are that iron-base soft magnetic alloy powder, Fe-Co are that iron-base soft magnetic alloy powder, Fe-Co-V are that iron-base soft magnetic alloy powder or Fe-P are the iron-base soft magnetic alloy powder.
More particularly, preferred iron powder is a pure iron powder.The insulation processing iron powder preferably, the wet type solution of the sol gel solution of interpolation and mixed phosphate lining iron powder or silicon dioxide gel gel solution (silicate) or aluminium oxide etc., make it to be coated on after the iron powder surface, drying is burnt till and the silica that obtains or aluminium oxide lining iron powder.Fe-Al is that the iron-base soft magnetic alloy powder preferably contains more than the Al:0.1% and below 20%, the Fe-Al that surplus is made of Fe and unavoidable impurities is iron-base soft magnetic alloy powder (for example being to have the ア Le パ one system powder of forming that Fe-15%Al constitutes).
In addition, Fe-Ni be the iron-base soft magnetic alloy powder preferably contain Ni:35% above and 85% below, contain as required that Mo:5% is following, Cu:5% following, Cr:2% is following, Mn:0.5% one or more among following, the Ni-based soft magnetic alloy powder that surplus is made of Fe and unavoidable impurities (for example Fe-49%Ni powder).Fe-Cr be the iron-base soft magnetic alloy powder preferably contain Cr:1% above and 20% below, contain as required that Al:5% is following, Ni:15% one or both among following, the Fe-Cr that surplus is made of Fe and unavoidable impurities is the iron-base soft magnetic alloy powder.Fe-Si be the iron-base soft magnetic alloy powder preferably contain Si:0.1% above and 10% below, the Fe-Si iron-base soft magnetic alloy powder that surplus is made of Fe and unavoidable impurities.
In addition, Fe-Si-Al be iron-based soft magnetic powder preferably contain Si:0.1% above and 10% below, contain Al:0.1% above and 20% below, the Fe-Si-Al that surplus is made of Fe and unavoidable impurities is the iron-base soft magnetic alloy powder.Fe-C-V be iron-based soft magnetic powder preferably contain C:0.1% above and 52% below, contain V:0.1% above and 3% below, the Fe-Co-V that surplus is made of Fe and unavoidable impurities is the iron-base soft magnetic alloy powder.Fe-C is that iron-based soft magnetic powder preferably contains more than the C:0.1% and below 52%, the Fe-Co that surplus is made of Fe and unavoidable impurities is the iron-base soft magnetic alloy powder.Fe-P be the iron-base soft magnetic alloy powder preferably contain P:0.5% above and 1% below, the Fe-P that surplus is made of Fe and unavoidable impurities is iron-base soft magnetic alloy powder (more than, % represents quality %).
And the preferred average grain diameter of soft magnetic metal particle of these Fe systems is in more than the 5 μ m and the soft magnetic metal particle in the scope of 500 μ m.Its reason is, if average grain diameter is little than 5 μ m, then the compressibility of powder reduces, and the volume ratio step-down of soft magnetic metal particle so the value of magnetic flux density reduces, so is not preferred.On the other hand, if average grain diameter is bigger than 500 μ m, then the vortex flow of soft magnetic metal particle inside increases, and the permeability under the high frequency reduces.
(A) with any one of this various soft magnetic metal particles as material powder, be implemented in and remain on the above and oxidation processes below 500 ℃ of room temperature (25 ℃) in the oxidizing atmosphere., in this material powder, add the Mg powder and mixed thereafter, with the mixed-powder that so obtains with more than 150 ℃ and the temperature below 1100 ℃, pressure 1 * 10 -12MPa is above and 1 * 10 -1Heat in inert gas atmosphere that MPa is following or the vacuum atmosphere.If as required again in oxidizing atmosphere, with more than 50 ℃ and the temperature below 400 ℃ heat, then can access what the soft magnetic metal particle surface had the oxide isolated tunicle that contains Mg and contain Mg oxide lining soft-magnetic particles (powder).(following so-called room temperature is represented 25 ℃).
This contains Mg oxide lining soft-magnetic particles, compares with the Mg oxide lining soft-magnetic particles that contains of the existing Mg of being formed with ferrite membrane, and tack is especially excellent.Soft-magnetic particles is carried out extrusion molding and is made the press-powder body even this contains the lining of Mg oxide, and the insulation tunicle also seldom breaks and peels off.In addition, with more than 400 ℃ and the temperature below 1300 ℃ burn till for this press-powder body that contains Mg oxide lining soft-magnetic particles and the soft-magnetic composite material obtained by compaction/burning that obtains, contain the Mg oxide-film and disperse equably, can obtain to contain the Mg oxide-film and can the tissue that disperse not take place to concentrate at the crystal boundary triple point at crystal boundary.
Under the situation of aforesaid manufacture method, for will be through the soft magnetic metal particle of oxidation processes as material powder, in this material powder, add the Mg powder and mixed, with the mixed-powder that so obtains with more than 150 ℃ and the temperature below 1100 ℃, pressure 1 * 10 -12MPa is above and 1 * 10 -1Heat in inert gas atmosphere that MPa is following or the vacuum atmosphere, heat while preferably rotate described mixed-powder.
(B), become oxide lining soft magnetic powder by in oxidizing atmosphere, remaining on described soft magnetic metal particle more than the room temperature and below 500 ℃, can forming oxide on the surface of soft magnetic powder.After interpolation silicon monoxide powder is also mixed in oxide lining soft magnetic powder, while perhaps mix in vacuum atmosphere, to remain on more than 600 ℃ and the heating of the condition of the temperature below 1200 ℃.If after in oxide lining soft magnetic powder, adding Mg powder and mixing again, perhaps while mixing in vacuum atmosphere, to remain on more than 400 ℃ and the condition of the temperature below 800 ℃ heats, then can access be formed with on the surface of soft magnetic powder contain the Mg-Si oxide-film contain Mg-Si oxide tunicle soft magnetic powder.The composite soft magnetic that contains the making of Mg-Si oxide tunicle soft magnetic powder that use is made with this method burns till material, with the existing mixture compression molding that powder constituted that will generate compound and MgCO or the MgO of SiO, and carry out sintering and the composite soft magnetic sintering material that obtains is compared, its density, rupture strength, resistivity and magnetic flux density are all more excellent.
(C) by in oxidizing atmosphere, remaining on described soft magnetic metal particle more than the room temperature and below 500 ℃, can forming the oxide of iron, become oxide lining soft magnetic powder on the surface of soft magnetic metal particle.If after in oxide lining soft magnetic powder, adding silicon monoxide powder and Mg powder simultaneously and being mixed, perhaps while mixing in vacuum atmosphere, to remain on more than 400 ℃ and the condition of the temperature below 1200 ℃ heating, then can access be formed with on the surface of soft magnetic powder contain the Mg-Si oxidation film contain Mg-Si oxide tunicle soft magnetic powder.The composite soft magnetic that contains the making of Mg-Si oxide tunicle soft magnetic powder that use is made with this method burns till material, will generate SiO with existing 2Compound and MgCO 3Or the mixture compression molding that powder constituted of MgO, and carry out sintering and the composite soft magnetic sintering material that obtains is compared, can make density, rupture strength, resistivity and magnetic flux density excellence.
(D) by in oxidizing atmosphere, remaining on described soft magnetic metal particle more than the room temperature and below 500 ℃, can forming the oxide of iron, become oxide lining soft magnetic powder on the surface of soft magnetic metal particle.If after interpolation Mg powder is also mixed in oxide lining soft magnetic powder, perhaps while mixing in vacuum atmosphere, to remain on more than 400 ℃ and the condition of the temperature below 1200 ℃ heats, then can access be formed with on the surface of soft magnetic powder contain the Mg oxide-film contain Mg oxide tunicle soft magnetic powder.
This contain add the silicon monoxide powder in the Mg oxide lining soft magnetic powder again and mixed after, while or mix in vacuum atmosphere, to remain on more than 600 ℃ and the condition of the temperature below 1200 ℃ heats.If so, then can access be formed with on the surface of soft magnetic powder contain the Mg-Si oxidation film contain Mg-Si oxide lining soft magnetic powder.If use the composite soft magnetic made from the containing Mg-Si oxide lining soft magnetic powder of this method making to burn till material, then will generate SiO with existing 2Compound and the mixture compression molding that powder constituted of MgCO or MgO, and carry out sintering and the composite soft magnetic sintering material that obtains is compared, can make density, rupture strength, resistivity and magnetic flux density excellence.
The interpolation of described silicon monoxide powder preferably is in the scope that 0.01 quality % is above and 1 quality % is following, and the addition of described Mg powder preferably is in the scope that 0.05 quality % is above and 1 quality % is following.
Described vacuum atmosphere is preferably 1 * 10 -12MPa is above and 1 * 10 -1The vacuum atmosphere that MPa is following.
Being used for silicon monoxide (SiO) powder of described manufacture method, is the highest oxide of vapour pressure among silica.Therefore, by heating easy surperficial evaporation silica composition, even the silicon dioxide (SiO that mixed vapour forces down at the soft magnetic metal particle 2) the powder heating, also might form fully thick silicon oxide film on the surface of soft magnetic metal particle.By after in oxide lining soft magnetic powder, adding silica (SiO) powder and being mixed, or while mixing in vacuum atmosphere, remain on more than 600 ℃ and below 1200 ℃, the surface that can be created on the soft magnetic metal particle is formed with the silicon oxide film lining soft magnetic powder of SiOx (wherein x is more than 1 and is 2 following) film.If in this silicon oxide film lining soft magnetic powder, add the Mg powder again, heat while mixing in vacuum atmosphere, then can access the Mg-Si oxidation film that contains that constitutes by Mg-Si-Fe-O and be overlayed on and contain Mg-Si oxide lining soft magnetic powder on the soft magnetic powder.
Aforesaid oxide lining soft magnetic powder can be with soft magnetic metal particle (for example in atmosphere) in oxidizing atmosphere, remains under the above and temperature below 500 ℃ of room temperature, forms ferroelectric oxide film on the surface of soft magnetic powder thus and makes.And this ferroelectric oxide film has the effect of the lining raising that makes SiO and/or Mg.When making oxide lining soft magnetic powder, if heating in oxidizing atmosphere above 500 ℃, soft magnetic metal particle coacervation then, the aggregate of soft magnetic metal particle generates, and the surface oxidation of homogeneous can not take place through sintering, so be not preferred.Therefore, it is above and below 500 ℃ that the heating-up temperature the during manufacturing of oxide lining soft magnetic powder is decided to be room temperature.Preferred scope is more than the room temperature and below 300 ℃.The oxidizing atmosphere that oxidizing atmosphere is more preferably dry.
Contain in the Mg-Si oxide lining soft magnetic powder used in the present invention, the SiO amount of powder of adding in the oxide lining soft magnetic powder is defined as more than the 0.01 quality % and below the 1 quality %.When the addition of SiO powder is lower than 0.01 quality %, the thickness deficiency of the surperficial formed silicon oxide film of oxide lining soft magnetic powder, therefore the quantity not sufficient that contains the contained Si of Mg-Si oxidation film, therefore can not get resistivity high contain the Mg-Si oxidation film, be not preferred therefore.On the other hand, surpass 1 quality % if add the SiO powder, the thickness of then formed SiOx (x be more than 1 and 2 following) silicon oxide film is blocked up, with containing of obtaining, Mg-Si oxide lining soft magnetic metal particle press-powder burnt till and the density of the soft-magnetic composite material obtained by compaction/burning that obtains might reduce.
In addition, in the manufacture method that contains Mg-Si oxide lining soft magnetic powder of the present invention, it is above and below the 1 quality % that the addition of Mg powder is defined as 0.05 quality %.When the addition of Mg powder is lower than 0.05 quality %,, contain the quantity not sufficient of the contained Mg of Mg-Si oxidation film in the thickness deficiency of the surperficial formed Mg film of oxide lining soft magnetic powder.Therefore, can not get fully thick Mg-Si oxidation film, is not preferred therefore.On the other hand, surpass 1 quality % if add the Mg powder, the thickness of then formed Mg film is blocked up, with containing of obtaining, Mg-Si oxide lining soft magnetic powder press-powder burnt till and the density of the soft-magnetic composite material obtained by compaction/burning that obtains reduces, is not preferred therefore.
In the manufacture method that contains Mg-Si oxide lining soft magnetic powder used in the present invention, in oxide lining soft magnetic powder, add the mixed-powder of SiO powder, Mg powder or SiO powder and Mg powder and the condition of being mixed, be temperature more than 600 ℃ and the vacuum atmosphere below 1200 ℃.To be lower than 600 ℃ temperature heating mixed-powder, because the SiO vapour pressure is little, so can not get abundant thickness SiO film or contain Mg-Si oxide tunicle.On the other hand, if surpass 1200 ℃ and mixed-powder is mixed, soft magnetic powder sintering then, what can not get expecting contains Mg-Si oxide lining soft magnetic powder, is not preferred therefore.In addition, heating atmosphere at this moment is preferably at pressure 1 * 10 -12MPa is above and 1 * 10 -1In the vacuum atmosphere below the MPa.In addition, while more preferably rotate and heat mixed-powder.
The soft magnetic metal particle that uses when making oxide lining soft magnetic powder preferably uses average grain diameter to be in more than the 5 μ m and the soft magnetic powder in the scope of 500 μ m.Its reason is, if average grain diameter is little than 5 μ m, then the compressibility of powder reduces, and the volume ratio step-down of soft magnetic metal particle so the value of magnetic flux density reduces, so is not preferred.On the other hand, if average grain diameter is bigger than 500 μ m, then the vortex flow of soft magnetic metal particle inside increases, and the permeability under the high frequency reduces.
The oxidation processes of soft magnetic metal particle has the effect of the lining raising that makes Mg.Oxidation processes is by in oxidizing atmosphere, keeps more than 150 ℃ and the temperature below 500 ℃ and carrying out, and perhaps in distilled water or pure water, keeps more than 50 ℃ and the temperature below 100 ℃ and carrying out.All lack efficient when at this moment, being lower than 50 ℃.On the other hand, if the maintenance above 500 ℃ in oxidizing atmosphere then sintering can take place, be not preferred therefore.The oxidizing atmosphere that oxidizing atmosphere is more preferably dry.
" deposited film " this term, the epithelium that the epithelium constituting atom of ordinary representation vacuum evaporation and sputter is deposited on substrate for example, but the so-called deposited film of Shi Yonging in the present invention is that Fe that expression has an iron oxide film is that the iron oxide (Fe-O) and the Mg of soft magnetic powder is deposited on the epithelium that this Fe is the soft magnetic metal particle surface along with reaction.For the back that is shaped at press-powder obtains the high magnetic flux density and the high resistivity of soft-magnetic composite material obtained by compaction/burning, be that the thickness of the surperficial formed Mg-Fe-O ternary system oxidate film of soft magnetic metal particle preferably is in the scope more than the 5nm and below the 500nm at this Fe.If this Film Thickness Ratio 5nm is thin, then the resistivity of the soft-magnetic composite material obtained by compaction/burning that is shaped through press-powder is insufficient, and eddy current loss increases, and is not preferred therefore.Thickness is when surpassing the thickness of 500nm, and the magnetic flux density of the soft-magnetic composite material obtained by compaction/burning that is shaped through press-powder reduces, and is not preferred therefore.In this scope in the scope of preferred thickness more than 5nm and below the 200nm.
Contain Mg oxide lining soft-magnetic particles by what aforesaid method was made, be formed with on its surface and contain the Mg oxide-film.This contains Mg oxide-film and silica and aluminium oxide reaction and forms composite oxides, finally can access soft-magnetic composite material obtained by compaction/burning with high resistivity, its crystal boundary at soft magnetic powder is situated between the composite oxides with high impedance is arranged, and being situated between has silica and aluminium oxide and is sintered, the soft-magnetic composite material obtained by compaction/burning of excellent strength that therefore can manufacturing machine.In this case, be sintered, therefore can keep coercive force tinily, therefore can make the few soft-magnetic composite material obtained by compaction/burning of magnetic hysteresis loss because silica and aluminium oxide become main body.Aforementioned burning till preferably in inert gas atmosphere or in the non-oxidizing gas atmosphere, with more than 400 ℃ and the temperature below 1300 ℃ carry out.Also have, so-called main body, the meaning are component ratio maximums in each constitutes.
" manufacturing of soft-magnetic composite material obtained by compaction/burning "
Use contains Mg oxide lining soft-magnetic particles according to what the method for above explanation was made as described above, makes soft-magnetic composite material obtained by compaction/burning.At first, what the former method of stating was made contains in the Mg oxide lining soft-magnetic particles, mixing is as after any one of silicones, low-melting glass or the metal oxide of the bonding material of insulating properties, carry out press-powder with usual way and be shaped, burn till in inert gas atmosphere or in the non-oxidizing atmosphere and make precursor.
Then, after this burns till, as described later in the oxidizing atmosphere of steam atmosphere, atmosphere etc., with more than 400 ℃ and the temperature in the scope below 600 ℃ the precursor of front is heat-treated, can access among the present invention soft-magnetic composite material obtained by compaction/burning thus as target.
In containing in the Mg oxide lining soft-magnetic particles of making according to aforesaid method, with ormal weight allotment low-melting glass, it is by silicones or Bi 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Any one formation of O-ZnO.
The allotment amount of silicones can be more than 0.2 quality % and in the scope below the 1.5 quality %.
The allotment amount of low-melting glass can be more than 0.05 quality % and in the scope below the 3.0 quality %.
Perhaps, the metal oxide of allotment ormal weight replaces the silicones or the low-melting glass of front with it in containing Mg oxide lining soft-magnetic particles.As metal oxide, can enumerate among aluminium oxide, boron oxide, vanadium oxide, bismuth oxide, antimony oxide and the molybdenum oxide one or more.These metal oxides are with Al 2O 3, B 2O 3, V 2O 5, Bi 2O 3, Sb 2O 3, MoO 3Convert, more than 0.05 quality % and in the scope below the 1 quality %, allocate, carry out press-powder after the mixing and be shaped.The press-powder formed body that obtains is more than 500 ℃ and the scope below 1000 ℃, preferably more than 550 ℃ and the temperature range below 750 ℃, in nonoxidizing atmosphere, burn till, make the precursor of soft-magnetic composite material obtained by compaction/burning, thereafter in oxidizing atmosphere by heat treatment, can make the compound binder of soft magnetism and burn till material.In addition, also can use zinc stearate as metal oxide.
As aforesaid firing atmosphere, for example can select non-oxidizing atmospheres such as inert gas atmospheres such as nitrogen atmosphere or hydrogen atmosphere.
In the present invention, under the purpose of the rupture strength of the precursor that improves aforesaid soft-magnetic composite material obtained by compaction/burning etc., in the oxidizing atmosphere of vapor atmosphere etc., implement to be heated to more than 400 ℃ and the temperature range below 600 ℃ in heat treatment.
By the heat treatment in this oxidizing atmosphere, make the Mg-Fe-O ternary system oxidate film lining of (Mg, the Fe) O of containing in the precursor be formed at the lining soft magnetic metal particle (powder) on the surface of soft magnetic metal particle, form with the Mg-Fe-O ternary system oxidate film that contains (Mg, Fe) O that is present in its interface, containing Mg oxide lining soft-magnetic particles becomes to be situated between and grain boundary layer is arranged and by the structure of a plurality of be combined intos, finally can access the soft-magnetic composite material obtained by compaction/burning as target.
Also have, contain Mg oxide lining soft-magnetic particles, have the soft magnetic metal particle and constitute with being coated on the containing the Mg oxide of surface of this soft magnetic metal particle.Grain boundary layer (for example contains with Fe with the Si oxide that contains iron oxide 3O 4Or FeO is the Si oxide of silicones etc. of the iron oxide of main body), contain the composition of low-melting glass oxide, contain among the ferriferous oxide of Mg any one and be main body.
As aforesaid oxidizing atmosphere, preferably can select more than 400 ℃ and the vapor atmosphere below 600 ℃, but in addition, in the medium oxidizing atmosphere of atmosphere, the condition of heat-treating in aforesaid temperature range is also passable.
As the heat treated condition in the aforesaid vapor atmosphere, if be lower than 400 ℃ temperature, then Fe 3O 4Formation can not get promoting that the problem that can not represent intensity is arranged.If otherwise surpass 600 ℃ heating condition, then because formation and the decomposition (4FeO → Fe of FeO 3O 4+ Fe), might can not represent intensity.
In aforesaid vapor atmosphere, with Fe 3O 4For why the iron oxide of main body grows up in the diffusion inside of silicones, it may be that small be full of cracks that generates when being shaped and the intergranular that constitutes the crystal grain of MgO film have the Fe diffusion that its reason is considered to.And think Fe oxidation in the heat treated process of oxidizing atmosphere of this diffusion, with Fe 3O 4For the iron oxide of main body is grown up and the filling crystal boundary, or except Fe 3O 4Some iron oxide that contains FeO is filled grain boundary layer in addition, and intensity is improved.
The soft-magnetic composite material obtained by compaction/burning that obtains according to the method for above explanation, via described a plurality of combinations that contain the face side grain boundary layer of Mg oxide lining soft-magnetic particles, be have described soft magnetic metal particle and be coated on the containing the Mg oxide-film of surface of this soft magnetic metal particle and constitute contain the combination that Mg oxide lining soft-magnetic particles and aforesaid low-melting glass or metal oxide obtain by mixed compaction heat treatment.And, be present in the iron oxide of the face side grain boundary layer between the described Mg of containing oxide lining soft-magnetic particles, being the Fe composition precipitate into crystal boundary and becomes oxide and disperse the iron oxide of growth from described soft magnetic metal particle.With aforementioned surfaces side grain boundary layer adjacency contain the Mg oxide-film, be to obtain by the Mg oxide lining Mg oxide-film that contains that soft-magnetic particles contained that contains that aforementioned mixed compaction burns till before handling.
In surrounding the described face side grain boundary layer that contains Mg oxide-film lining soft-magnetic particles, the Si oxide that has to contain iron oxide (for example contains with Fe 3O 4Or FeO is the Si oxide of silicones etc. of the iron oxide of main body), contain the composition of low-melting glass oxide, contain among the ferriferous oxide of Mg any one and be the tissue of main body.
Figure 1A represents the profile construction of an example of this soft-magnetic composite material obtained by compaction/burning.This routine soft-magnetic composite material obtained by compaction/burning 10 is discoideus, is following two-layer structure: be formed with skin section 10a (density 7.5g/cm more than the thick 2mm and below the 4mm in its top layer side 3The time), portion's side is formed with interior layer 10b within it.Also have, the thickness of skin section 10a can be subjected to the density influence as the soft-magnetic composite material obtained by compaction/burning of goods.As described above, at density 7.5g/cm 3Situation under, its thickness is that 2mm is above and below the 4mm, but density 7.0g/cm 3The time, the thickness maximum increases to about 15mm, and density improves or can become thickness about 0.3mm according to the heat-treat condition difference.This be because, each the elemental diffusion reaction that takes place when heat treatment described later is subjected to the influence of oxidizing atmospheres such as vapor atmosphere, consequently oxidizing atmosphere exerts an influence on depth direction when heat treatment, and this will be subjected to the density influence as the soft-magnetic composite material obtained by compaction/burning of goods.
Figure 1B represents to amplify the figure of a part of skin section 10a of the soft-magnetic composite material obtained by compaction/burning 6 of above-mentioned example.In 1B, containing Mg oxide-film 2 forms in the mode on the surface of the soft magnetic metal particle 1 that covers Fe system, formation contains Mg oxide lining soft-magnetic particles, and side grain boundary layer 5 is engaged a plurality of Mg of containing oxide lining soft-magnetic particles via table, constitutes soft-magnetic composite material obtained by compaction/burning.
Also have, soft-magnetic composite material obtained by compaction/burning 10 as described above, be by soft-magnetic particles compacting that a plurality of Mg of containing oxides are covered, and implement to burn till to make with heat treatment, therefore it is amorphous to contain Mg oxide lining soft-magnetic particles, and preferred whole face on its surface all forms and contains Mg oxidation film 2.But also consider,, have part ground on the surface that contains Mg oxide lining soft-magnetic particles and can't form the position existence that contains Mg oxide-film 2 according to the state of compacting and shaping.Preferably respectively contain Mg oxide lining soft-magnetic particles and contained Mg oxide 2 and cover, the resistivity when major general's soft-magnetic composite material obtained by compaction/burning is considered as integral body is not reduced.
If from then on see on the meaning, shown in Figure 1B, interface at the crystal boundary triple point of three soft-magnetic particles 1 set, even there be grain boundary layer 5 situation thicker than the grain boundary layer 5 of other parts, or part ground contains the discrepant situation of thickness of Mg oxide-film 2, or the part ground situation that has the not enough part of lining to produce, if it is as the generally resistivity height of soft-magnetic composite material obtained by compaction/burning of the present invention, so then no problem.
Be used for making the vapor atmosphere of aforesaid soft-magnetic composite material obtained by compaction/burning 10 or the heat treatment time of atmosphere, can suit to adjust, but excessively prolong the tendency that the processing time can cause intensity raising effect to be satisfied in the scope more than several minutes and below a few hours.
Also have as described above, become via (containing with Fe to contain the iron oxide Si oxide 3O 4Or FeO is the Si oxide of silicones etc. of the iron oxide of main body), contain the composition of low-melting glass oxide, contain among the ferriferous oxide of Mg any one for the face side grain boundary layer of main body by the structure of a plurality of be combined intos, be not the integral thickness of precursor.Forming the part of this structure, is under aforesaid common heat-treat condition, density 7.5g/cm 3The time, apart from more than the most surperficial 2mm of precursor and the part of the following left and right thickness of 4mm.
This be because, oxidizing atmospheres such as vapor atmosphere exert an influence to the generation of grain boundary layer, rather than at the thickness direction integral body of precursor, but are limited to the most surperficial to a certain degree thick zone apart from precursor.That is, because oxide is generated at crystal boundary, make the common obstruction of oxidizing atmosphere, so the supply of oxidizing atmosphere can't reach private side, the formation of oxide can only be apart from limited zone, surface.
For example, if in oxidizing atmosphere, heat-treat for precursor with the thickness more than the above-mentioned thickness range, then heart portion can not be subjected to from the influence or the influence of the oxidizing atmosphere of vapor atmosphere etc. very little yet therein, the result who heat-treats with this state is, the private side grain boundary layer that the Mg lining soft magnetic alloy powder of Fe system is produced in conjunction with and generate internal layer portion.
In this internal layer portion, because oxidizing atmospheres such as vapor atmosphere can not impact, the therefore aforesaid Mg of containing oxide lining soft-magnetic particles is not by containing with Fe 3O 4Or FeO is the face side grain boundary layer joint of the iron oxide of main body, but become the state that engages by inner grain boundary layer, this inside grain boundary layer is by the SiO that has carried out heat treated grain boundary layer for the Mg-Fe-O ternary system oxidate film that contains (Mg, Fe) O and carried out for silicones burning till 2Grain boundary layer formation for main component.
In this internal layer portion side, because the aforesaid Mg of containing oxide lining soft-magnetic particles is not to be exerted one's influence and the face side grain boundary layer combination that generates by oxidizing atmospheres such as vapor atmosphere, but by the grain boundary layer of heat treatment Mg-Fe-O ternary system oxidate film and the private side grain boundary layer combination that burned material constituted of silicones, so can become the tissue of the weak state of strength ratio skin section side.
But the density of precursor is 7.5g/cm 3The time, apart from more than the most surperficial 2mm of the skin section of precursor and the part of the following left and right thickness of 4mm become and show high-intensity skin section 10a, can obtain high strength fully as the soft-magnetic composite material obtained by compaction/burning 10 that finally obtains thus.In addition, no matter be at skin section 10a and the 10b of internal layer portion, contain Mg oxide lining soft-magnetic particles around all be by serve as face side grain boundary layer basic and that generate thus or the covering of private side grain boundary layer with Mg-Fe-O ternary system oxidate film.Therefore, exist to contain the lining of Mg oxide around soft-magnetic particles, magnetic interdicts each soft-magnetic particles, therefore can form resistivity height, soft-magnetic composite material obtained by compaction/burning that eddy current loss is few.
The soft-magnetic composite material obtained by compaction/burning 10 that obtains according to above manufacture method has high density, high strength, high resistivity and high magnetic flux density.This soft-magnetic composite material obtained by compaction/burning 10 can be brought into play the material use of the various electromagnetic circuit parts of this characteristic as needs thus owing to have the characteristic of the low iron loss of high frequency under high magnetic flux density.
In addition, in the soft-magnetic composite material obtained by compaction/burning 10 that obtains according to above manufacture method, have the combined skin section 10a of soft-magnetic particles, this soft-magnetic particles contains with Fe via comprising 3O 4For the face side grain boundary layer of the composition of the low-melting glass of the iron oxide of main body, perhaps to contain with Fe 3O 4As the metal oxide of the iron oxide of main body is that the face side grain boundary layer of main body is combined.(these face side grain boundary layers by in oxidizing atmosphere for the Mg-Fe-O ternary system oxidate film that contains (Mg, Fe) O be present in the low-melting glass at its interface or metal oxide burns till and makes it to grow up.) therefore, the joint that particularly contains between the Mg oxide lining soft-magnetic particles is good, can further improve rupture strength, can access high-strength soft-magnetic composite material obtained by compaction/burning.Therefore, by the soft-magnetic composite material obtained by compaction/burning that this manufacture method obtains, has this advantage of the characteristic that under high magnetic flux density, has the low iron loss of high frequency concurrently.
Also have, in soft-magnetic composite material obtained by compaction/burning 10, the minimum value of the thickness of skin section 10a is subjected to the influence of the size and the density of goods, does not therefore do regulation without exception, but when being limited to test portion about 5mm for wall thickness, preferably more than 0.3mm.In addition, the density as goods is 7.5g/cm 3The time, even parameters such as the temperature the during heat treatment in the controlled oxidation atmosphere, times, the thickness of skin section 10a still can reach about maximum 4mm.
Embodiment 1
Soft magnetic powder (pure iron powder) for average grain diameter 100 μ m carries out more than 0 minute and the heat treatment below 60 minutes with 220 ℃ in atmosphere.At this, the thickness of oxidation film that generates through heat treated in 220 ℃ of atmosphere of MgO film and leading portion is proportional.Therefore, the addition of Mg can be required Min., allocates the Mg powder of 0.1 quality % with respect to iron powder, rotates mixing stirring device with granulation and rotate this allotment powder in argon gas atmosphere, makes thus to contain the Mg oxide soft-magnetic particles that is covered.
Be determined at the Mg-Fe-O ternary system oxidate film (brief note is the MgO film in the table 1) of (Mg, the Fe) O of formed containing of outer peripheral face that contains Mg oxide lining soft-magnetic particles, its result is presented in the table 1.Because the thickness of oxidation film that generates through heat treated in the thickness of this film and the aforesaid atmosphere is proportional, so use the MgO thickness to be the test of the conduct more than the 20nm and below 80nm test portion.
For the test portion of aforementioned each MgO thickness, as shown in table 1 in quality % at the interpolation of the scope more than 0.3% and below 1.5% silicones, burn till with the forming pressure shown in the table 1, firing condition.In addition, also prepare not add the test portion of silicones.
[table 1]
Figure GPA00001131152800201
With the firing condition shown in the table 1 each test portion is burnt till, contained the Mg-Fe-O ternary system oxidate film of (Mg, Fe) O and the precursor (size 60mm * 10mm * 5mm's is tabular) of the soft-magnetic composite material obtained by compaction/burning of the silicones formation that is present in its interface thus., again in vapor atmosphere or atmosphere, promptly in oxidizing atmosphere, with temperature conditions table 2 shown in, processing time precursor heat-treated, obtain the soft-magnetic composite material obtained by compaction/burning of target thereafter.
Burn till in each test portion of material at the compound binder of the soft magnetism that obtains, measure rupture strength, resistivity, density, coercive force, magnetic flux density, the result is presented in the table 2.
[table 2]
Figure GPA00001131152800211
According to the result shown in the table 2, after burning till shown in the table 2, do not implement the test portion of heat treated No.1～3, rupture strength is the scope that 52MPa is above and 94MPa is following.On the other hand, in nitrogen atmosphere or in the medium non-oxidizing atmosphere of hydrogen atmosphere, surpassing 550 ℃ temperature and after burning till below 650 ℃, with more than 400 ℃ and implementing heat treated No.4～12, No.5,17～26 test portion below 560 ℃, rupture strength all increases.
But, in atmosphere, promptly not the test portion that the No.13 of processing is burnt till in enforcement in non-oxidizing atmosphere but in oxidizing atmosphere, rupture strength is 83, does not improve.In addition, with 750 ℃ of test portions that carried out burning till the No.16 of processing, resistivity is extremely low value.In addition, the test portion of No.6 is because of the thick 80nm that reaches of thickness of MgO, so magnetic flux density reduces.
Distinguish that by above result the thickness of MgO is preferably in the scope more than 20nm and below the 80nm.
Distinguish that by above result heat-treat condition is more preferably more than 400 ℃ and the scope below 560 ℃.
Then, distinguish by the value of the skin section thickness shown in the table 2, in the compound staypak of soft magnetism, high-intensity test portion from more than the surface element 0.1mm and the part about below the 4mm generate the face side grain boundary layer,
Also have, the thickness of the skin section that generates by the heat treatment in heat treatment in atmosphere or the vapor atmosphere, can carry out some adjustment by heat treatment temperature and time, even still condition has some to change, the thickness that generates also is more than the 2mm and about below the 4mm mostly.For skin section is generated to the zone darker than this scope, need to improve heat treatment temperature or significant prolongation processing time, it is unfavorable that this brings aspect productivity ratio easily.
Fig. 2 is the enlarged photograph of metal structure of the surface portion (apart from the part of the dark 1mm of surface location) of the high-strength soft-magnetic composite material obtained by compaction/burning test portion No.8 of the present invention that obtains among the embodiment of expression.
Energy dispersion type x-ray fluorescence analysis (EDX) is carried out in 111 positions on this metal structure shown in Figure 2,112 positions, 113 positions, 114 positions, 115 positions, 116 positions.Its result is presented among Fig. 3～Fig. 8.
The analysis result of 111 positions shown in Figure 3 is analysis results of the part of soft magnetic metal particle.The analysis result of 112 positions shown in Figure 4 is analysis results of the outer peripheral portion of soft magnetic metal particle.The analysis result of 113 positions shown in Figure 5 be the soft magnetic metal particle foreign side be considered to contain this part analysis result of Mg oxide-film.The analysis result of 114 positions shown in Figure 6 be the soft magnetic metal particle foreign side be considered to this part analysis result of boundary layer.The analysis result of 115 positions shown in Figure 7 is this part this part analysis results that are considered to contain the Mg oxide-film of the foreign side of soft magnetic metal particle.The analysis result of 116 positions shown in Figure 8 is analysis results of the outer peripheral portion of soft magnetic metal particle.
According to Fig. 2～result shown in Figure 8, in the analysis result of the private side of Fig. 3, Fig. 4 and soft magnetic metal particle shown in Figure 8, have only the peak value of Fe to represent very by force.With respect to this, Fig. 5 and shown in Figure 7 being considered to contain in the analysis result at Mg oxide-film position partly, except the peak value of Fe, are also shown in the big peak value of Mg, Si.Therefore as can be known, the metal structure of the surface portion of high-strength soft-magnetic composite material obtained by compaction/burning test portion No.8 (apart from the part of the dark 1mm of surface location) is the tissue of purpose among the present invention.
Fig. 9 is the enlarged photograph of metal structure of the surface portion (apart from the part of the dark 0.5mm of surface location) of the compound staypak test portion of the high-strength soft-magnetic of the present invention No.8 that obtains among the embodiment of expression.
X-ray diffraction analysis is carried out in 1 position on this metal structure shown in Figure 9,2 position, 3 position, 4 position, 5 position, 6 position.Its result is presented among Figure 10～Figure 15.
The analysis result of three crystal boundary point positions on three borders that contain Mg oxide-film lining soft-magnetic particles is represented to constitute in 1 position and 2 position in Fig. 9.The analysis result of other three crystal boundary point positions is represented in 3 position.Two analysis results that contain the boundary member of Mg oxide-film lining soft-magnetic particles are represented in 4 position and 5 position.The analysis result of adjacent locations of three crystal boundary points on three borders that contain Mg oxide-film lining soft-magnetic particles is represented to constitute in 6 position.
By the result shown in each figure as can be known, there are Fe and O and Mg in the boundary layer part, can be interpreted as that the metal structure of the surface portion of high-strength soft-magnetic composite material obtained by compaction/burning test portion No.8 (apart from the part of the dark 0.5mm of surface location) is the tissue of purpose among the present invention.
Also have, Figure 14, Mn shown in Figure 15 are considered to the impurity in the iron powder, since big with the affinity of oxygen, so selected oxidation in oxidizing thermal treatment is exposed on the iron powder surface.
Figure 16 is the enlarged photograph of the metal structure of the high-strength soft-magnetic composite material obtained by compaction/burning test portion No.8 of the present invention that obtains among the embodiment of expression.
As shown in figure 16, can confirm following situation: at the outer peripheral portion of soft magnetic metal particle, contain the Mg oxidation film and exist, have the wide thin face side boundary layer of equal extent betwixt with the thickness more than the 30nm and about below the 50nm.
More than, preferred implementation of the present invention has been described, but the present invention is not limited by above-mentioned execution mode.In the scope that does not break away from aim of the present invention, what can constitute adds, omits, replaces and other changes.The present invention is not limited by above stated specification, and the scope of the claim of only being enclosed limits.
Utilize possibility on the industry
Intensity soft-magnetic composite material obtained by compaction/burning of the present invention (soft magnetism material), can be used as the electromagnetic circuit parts, utilizations such as magnetic core, motor core, generator magnetic core, solenoid core, igniting core, reactor magnetic core, magnetic core of transformer, choking-winding magnetic core or Magnetic Sensor magnetic core, no matter be in any, to use, can both obtain having given play to the electromagnetic circuit parts of excellent specific property.
And, in the electrical equipment that is equipped with these electromagnetic circuit parts, comprise motor, generator, solenoid, injector, Electromagnetically driven valve, inverter, converter, transformer, relay, magnetic sensor system etc. can realize high efficiency high performance and the miniaturization and of these electrical equipments.

Claims (12)

1. high-strength soft-magnetic composite material obtained by compaction/burning, be contain Mg oxide lining soft-magnetic particles through grain boundary layer by the high-strength soft-magnetic composite material obtained by compaction/burning of a plurality of be combined intos, wherein,
The described Mg of containing oxide lining soft-magnetic particles have Fe be soft magnetic metal particle and the surface that is coated on this soft magnetic metal particle contain the Mg oxide-film,
Described high-strength soft-magnetic composite material obtained by compaction/burning has:
Described contain Mg oxide lining soft-magnetic particles through the face side grain boundary layer by the skin section of a plurality of be combined intos, wherein, described face side grain boundary layer will contain with Fe 3O 4Or FeO be main body iron oxide Si oxide and to contain in the ferriferous oxide of Mg any one above as main body;
Described contain Mg oxide lining soft-magnetic particles through the private side grain boundary layer by the internal layer portion of a plurality of be combined intos, wherein, described private side grain boundary layer is with Si oxide and contain more than in the ferriferous oxide of Mg any one as main body.
2. high-strength soft-magnetic composite material obtained by compaction/burning according to claim 1, wherein, described a plurality of combination that contains Mg oxide lining soft-magnetic particles through the face side grain boundary layer, be have described soft magnetic metal particle and be coated on the containing the Mg oxide-film of surface of this soft magnetic metal particle and constitute contain Mg oxide lining soft-magnetic particles, with at least a combination that obtains by mixed compaction heat treatment in silicones, low-melting glass, the metal oxide
The Fe that is present in the face side grain boundary layer between the described Mg of containing oxide lining soft-magnetic particles 3O 4Or FeO, be that the Fe composition is that the soft magnetic metal particle is separated out the formation oxide and disperseed growth and formation at crystal boundary from described Fe,
With described face side grain boundary layer adjacency contain the Mg oxide-film, be to be obtained by overlay film from the Mg oxide Mg oxide that contains that is had on the soft-magnetic particles that is covered that contains that described mixed compaction burns till before handling.
3. high-strength soft-magnetic composite material obtained by compaction/burning according to claim 2, wherein, the described Mg of containing oxide-film constitutes based on (Mg, Fe) O, and described low-melting glass is by Bi 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Any one formation among the O-ZnO.
4. high-strength soft-magnetic composite material obtained by compaction/burning according to claim 2, wherein, the described Mg of containing oxide-film constitutes based on (Mg, Fe) O, and described metal oxide is by from Al 2O 3, B 2O 3, Sb 2O 3, MoO 3In one or more formations of selecting.
5. the manufacture method of a high-strength soft-magnetic composite material obtained by compaction/burning, wherein, to have Fe and be the soft magnetic metal particle and be coated on the containing the Mg oxide-film of surface of this soft magnetic metal particle and constitute contain Mg oxide lining soft-magnetic particles, and silicones, low-melting glass, at least a mixed compaction in the metal oxide, after in non-oxidizing atmosphere, burning till the precursor of handling the formation soft-magnetic composite material obtained by compaction/burning, in oxidizing atmosphere, heat-treat, become sintered body therefrom with skin section and internal layer portion
Described skin section is that face side at described precursor is through containing with Fe at least 3O 4FeO be main body iron oxide Si oxide or contain the face side grain boundary layer that filler constituted of the ferriferous oxide of Mg at least, with the described a plurality of be combined intos of Mg oxide lining soft-magnetic particles that contain,
Described internal layer portion is the internal layer side at described precursor, through based on Si oxide with contain private side grain boundary layer more than in the ferriferous oxide of Mg any one, will describedly contain the Mg oxide a plurality of be combined intos of soft-magnetic particles that are covered.
6. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5, wherein, the iron oxide that contains the grain boundary layer between Mg oxide lining soft-magnetic particles that is present in described skin section is that to make the Fe composition be that the soft magnetic metal particle is separated out at crystal boundary and formed oxide and make the scattered length of this divided oxide from described Fe.
7. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5 wherein, is inert gas atmosphere or hydrogen atmospheres such as nitrogen atmosphere, argon gas atmosphere as described non-oxidizing atmosphere.
8. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5 wherein, is more than 400 ℃ and in the vapor atmosphere or atmosphere below 600 ℃ as described oxidizing atmosphere.
9. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5 wherein, makes described temperature of burning till processing more than 550 ℃ and the scope below 750 ℃.
10. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5, wherein, by in described non-oxidizing atmosphere, burning till processing, the wustite of (Mg, the Fe) O that contains Mg and Fe is generated at grain boundary layer, become and contain Si oxide that contains iron oxide at least and any one the filler in the ferriferous oxide that contains Mg at least by in described oxidizing atmosphere, heat-treating, make the grain boundary layer that contains described wustite.
11. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5 wherein, is used Bi as described low-melting glass 2O 3-B 2O 3, SnO-P 2O 3, SiO 2-B 2O 3-ZnO, SiO 2-B 2O 3-R 2O, Li 2Among the O-ZnO any one.
12. the manufacture method of high-strength soft-magnetic composite material obtained by compaction/burning according to claim 5 wherein, is used Al as described metal oxide 2O 3, B 2O 3, Sb 2O 3, MoO 3In any one.
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