CN104347219A - Composite magnetic material, method for manufacturing same and raw material components of composite magnetic material - Google Patents

Composite magnetic material, method for manufacturing same and raw material components of composite magnetic material Download PDF

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CN104347219A
CN104347219A CN201410380178.3A CN201410380178A CN104347219A CN 104347219 A CN104347219 A CN 104347219A CN 201410380178 A CN201410380178 A CN 201410380178A CN 104347219 A CN104347219 A CN 104347219A
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iron
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CN104347219B (en
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小室又洋
佐通祐一
丸山钢志
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Abstract

The objective of the invention is to increase the residual magnetic flux density and improve the retentivity of a magnetic material containing epsilon-Fe2O3. The composite magnetic material comprises iron oxides particles containing epsilon-Fe2O3 and metallic iron, and rare earth iron particles containing rare earth elements and iron compounds. The average grain diameter of the rare earth iron particles is larger than that of the iron oxides particles, and the volume fraction of the rare earth iron particles is larger than that of the iron oxides particles.

Description

The raw material group of composite magnetic and manufacture method and composite magnetic
Technical field
The present invention relates to and comprise ε-Fe 2o 3with composite magnetic and the manufacture method thereof of the compound containing rare earth element and iron.
Background technology
Magnetic material has soft magnetic material and retentive material, and ferromagnetic material is categorized as retentive material.Particularly sintered magnet, due to its high magnetic characteristic, for various magnetic loop.Wherein, NdFeB system sintered magnet is with Nd 2fe 14the brilliant high-performance magnet as principal phase of B tying, use in the arts of the broad range such as automobile, generating equipment, household electrical appliances, medicine equipment, electronic instrument, its consumption is in increase.
In NdFeB system sintered magnet, except the Nd of rare earth element, for guaranteeing thermal endurance, the heavy rare earth element that Dy, Tb etc. are expensive can be used.This rare earth element is rare, and produce area limitation and reserved resource, therefore price is high, therefore raises the requirement that rare earth element dosage is cut down.
On the other hand, rare earth element is not used can to obtain the ε-Fe of high coercive force 2o 3, cause concern as hard magnetic material, ε-Fe 2o 3and ε-Fe 2o 3a Fe site part for crystallization is open in patent documentation 1 with Al displacement.
But, ε-Fe 2o 3due to saturation magnetization and remanent magnetization little, in order to as required magnetized material, must with there is high magnetized Fe system Magnetic Phase in addition compound, the example as this kind of composite material is open in patent documentation 2.
Prior art document
Patent documentation
Patent documentation 1: JP 2008-060293 publication
Patent documentation 2: JP 2011-032496 publication
Summary of the invention
The problem that invention will solve
Patent documentation 1 and 2 has to relate to and adopts silicon dioxide (SiO 2) the record of magnetic material.
Describe in patent documentation 1 and be coated with at the particle surface of ferric hydroxide precipitate the silicon dioxide generated by the hydrolysis of silane, by heat treatment (950 ~ 1150 DEG C) thereafter, in silica dioxide coating, oxidation reaction occurs, generate ε-Fe 2o 3.ε-Fe 2o 3demagnetizing curve (magnetization curve), as shown in Fig. 4 of patent documentation 1, coercive force reaches 20kOe, near magnetic field (H) zero, curve can be observed bending point, energy product reduce.In patent documentation 1, ε-Fe 2o 3fe site replace with a part of Al, the result as Fig. 3 of patent documentation 1 is known known, by carrying out Al displacement in Fe site, coercive force reduce.In addition, in order to improve magnet performance, Fe system high saturation material that must be large with magnetization value carries out compound.
The object of the invention is at employing ε-Fe 2o 3magnetic material in improve relict flux metric density and confining force.
For solving the means of problem
Composite magnetic of the present invention, is characterized in that, it comprises: containing ε-Fe 2o 3and the iron oxide particles of metallic iron, and the rare-earth iron series particle formed by the compound containing rare earth element and iron; The average grain diameter of rare-earth iron series particle is larger than the average grain diameter of iron oxide particles, and the volume fraction of rare-earth iron series particle is larger than the volume fraction of iron oxide particles.
Invention effect
According to the present invention, can improve and adopt ε-Fe 2o 3the relict flux metric density of magnetic material and confining force.
Accompanying drawing explanation
Fig. 1 is the figure representing that the signal of one of composite magnetic of the present invention example is formed.
Fig. 2 is the figure representing that the signal of the another example of composite magnetic of the present invention is formed.
The explanation of symbol
1: rare-earth iron series particle, 2: adhesive, 3: ε-Fe 2o 3, 4: α-Fe, 5: iron oxide particles.
Embodiment
As magnet, in order to ensure the performance exceeding ferrite lattice, must meet the following conditions.
1) saturation magnetization and Curie temperature are than ε-Fe 2o 3high Fe based material and ε-Fe 2o 3magnetic knot closes.
2) Fe based material and ε-Fe 2o 3the powder that magnetic knot closes mixes with rare-earth iron series powder, and coercive force is increased.
3) ε-Fe is made 2o 3volume fraction larger than Fe based material, and do not make coercive force reduce.
4) Curie temperature is more than 200 DEG C, and the particle diameter of rare-earth iron series powder is than ε-Fe 2o 3particle diameter large.
ε-Fe 2o 3remanent magnetization little of about 10emu/g, Curie temperature is also low to 210 DEG C.But, ε-Fe 2o 3coercive force, at 20 DEG C greatly to 20kOe.For making the ε-Fe with this feature 2o 3be applicable to ferromagnetic material, must magnetization be strengthened.As α-Fe and ε-Fe 2o 3when merely magnetic knot closes, magnetization increases, and relict flux metric density also strengthens, and when making α-Fe increase, coercive force reduces, and is difficult to the feature utilizing high coercive force.
In order to utilize high coercive force, relative ε-Fe 2o 3100 parts by volume, α-Fe is below 50 parts by volume, preferably 5 ~ 40 parts by volume, more preferably 5 ~ 30 parts by volume.
When more than 50 parts by volume, ε-Fe 2o 3ratio reduce, due to ε-Fe 2o 3characteristic can not make full use of, be not preferred.In the scope of 5 ~ 30 parts by volume, can confirm that magnetization increases, and, reach 10 ~ 18kOe at the coercive force of 100 DEG C.Such α-Fe and ε-Fe 2o 3complex, remanent magnetization reaches the scope of 12 ~ 80emu/g, has the Maximum Energy Product equal with ferrite lattice.
Due to α-Fe and ε-Fe 2o 3complex, Maximum Energy Product can be made to increase further, therefore the volume fraction of α-Fe must be made to increase, and maintain high coercive force.α-Fe, because anisotropic energy is little, coercive force diminishes.Therefore, the light rare earth-iron system powder of low cost, with α-Fe and ε-Fe 2o 3the combination of complex be effective.
Low-cost rare earth element or light rare earth element, have Y, La, Ce, Pr, Nd and Sm.These element definitions are low-cost rare earth element.Low-cost rare earth element, compared with the heavy rare earth elements such as Dy, Tb, having abundant reserves, is the element that resource problem and environmental problem are little.Such low-cost rare earth element and α-Fe and ε-Fe 2o 3composite material, remanent magnetization or relict flux metric density raise becomes possibility.Its means realized as shown below.
Compound containing low-cost rare earth element, available R na mb lcomposition formula represents.In formula, R represents at least a kind of element among Y, La, Ce, Pr, Nd and Sm, and A is at least a kind of Fe and Co, and B is any a kind of boron (B), nitrogen (N), carbon (C) and phosphorus (P).In addition, n, m, l are positive number, meet m > n+l.
Compound R containing low-cost rare earth element na mb l, with α-Fe and ε-Fe 2o 33 kinds of ferromagnetism phases, if its volume fraction is R na mb l> ε-Fe 2o 3> α-Fe, then can suppress coercive force to reduce, and Maximum Energy Product increases.Curie temperature is Tc (α-Fe) > Tc (R na mb l) > Tc (ε-Fe 2o 3), ε-Fe 2o 3curie temperature minimum.α-Fe and R na mb lcompare, with ε-Fe 2o 3magnetic knot close strong.This is due to α-Fe and ε-Fe 2o 3interfacial area, than α-Fe and R na mb linterfacial area large, the ε-Fe near α-Fe 2o 3compare R na mb lnear α-Fe how caused by.
Below, composite magnetic, its manufacture method and the raw material group for making composite magnetic that embodiment of the present invention relate to are illustrated.
Above-mentioned composite magnetic comprises: containing ε-Fe 2o 3and the iron oxide particles of metallic iron, and, the rare-earth iron series particle that the compound containing rare earth element and iron is formed.
Metallic iron is preferably α-Fe.
Iron oxide particles preferably has ε-Fe 2o 3the structure of coating α-Fe.
Iron oxide particles preferably has α-Fe and is coated to ε-Fe 2o 3structure.
Rare earth element is preferably selected from least a kind in the group of Y, La, Ce, Pr, Nd and Sm formation.
Compound containing rare earth element and iron is preferably Sm 2fe 17n 3.
Relative ε-Fe 2o 3100 parts by volume, preferred α-Fe is 5 ~ 40 parts by volume.
Above-mentioned composite magnetic is preferably also containing adhesive.
Form ε-Fe 2o 3and a part of the Fe of α-Fe, preferably by any one element substitution in Zn, Mn, Co, Ni, Cu, Mg, Ba, Pb, Sr and Ca.
When manufacturing above-mentioned composite magnetic, silica precursor is added in the solution containing acid, alcohol and water, add that metal iron powder is last is stirred, make the gel containing iron ion, heat treatment is implemented to this gel, make silica containing solid state, pulverized, silicon dioxide is dissolved with hydrofluoric acid, removes, be dispersed in alcoholic solvent and make slurries, carry out drying with after this slurries coated with rare earth iron system particle, be mixed to carry out in adhesive shaping.
Acid is preferably nitric acid.
Silica precursor is preferably the oligomer of alkoxy silane.
When manufacturing above-mentioned composite magnetic, preparation comprises the solution of iron ion and siliceous gel precursors, is dried, makes containing ε-Fe 2o 3gel, reduction ε-Fe 2o 3a part, at ε-Fe 2o 3surface form metallic iron, it is mixed with alcohol, makes slurries, these slurries are coated with on rare-earth iron series particle, drying, to be mixed in adhesive and in addition shapingly also can.
Raw material group for the manufacture of above-mentioned composite magnetic contains: silica precursor, metallic iron powder and the powder be made up of rare-earth iron series particle.
Above-mentioned raw materials group both can comprise: containing the solution of the acid such as nitric acid and alcohol, may also be nital (Nital).
Above-mentioned raw materials group also can contain hydrofluoric acid.
Above-mentioned raw materials group comprises: siliceous gel precursors, the solution containing iron ion, the powder be made up of rare-earth iron series particle and reducing agent.
Siliceous gel precursors is preferably tetraethyl orthosilicate.
As reducing agent, be preferably adopted as MgF 2deng metal fluoride swelling gel and with amorphous reducing agent dispersion solution.
Fig. 1 illustrates the section of composite magnetic of the present invention (injection moulding magnet) exemplary.
Composite magnetic shown in this figure is rare-earth iron series particle 1 (such as Sm 2fe 17n 3), iron oxide particles 5 and adhesive 2 (such as nylon resin) mixing, shapingly to make.Iron oxide particles 5 has with ε-Fe 2o 3(3) structure on the surface of coating α-Fe (4).Iron oxide particles 5 is assembled at the near surface of rare-earth iron series particle 1.
Fig. 2 illustrates the section of composite magnetic of the present invention (injection moulding magnet) another example.
This figure with the difference of Fig. 1 is: the central portion of iron oxide particles 5 is by ε-Fe 2o 3(3) form, surface element is made up of α-Fe (4).
Embodiment is adopted to be illustrated below.
Embodiment 1
Add water in X% nital (adding the solution of X% nitric acid in methyl alcohol by volume: adopt 1% and 2% in the present embodiment) 49.1g 27.6g, stirs and make to reach evenly.Slowly SiO is added in this solution 2precursor (4 aggressiveness of tetramethoxy-silicane: Silicate 51 (industrial chemistry of rubbing (strain) system)) 30g more.
Adopt 4 aggressiveness of tetramethoxy-silicane as SiO 2the reason of precursor is as described below.
(1) due to SiO 2ethyoxyl in precursor changes to methoxyl group, therefore the solvent of generation during solgel reaction, evaporation changes to methyl alcohol from ethanol.By this operation, the boiling point of solvent is down to 65 DEG C from 78 DEG C, SiO 2concentrating of precursor is rapid, and its cross-linked polymer quantizes reaction to accelerate, and can shorten the gelation time of solution.
(2) SiO is generated from alkoxy silane 2time, when adopting the raw material of oligomer level of alkoxy silane, can amount of contraction be suppressed.Therefore, the charge weight (volume) of raw material can be suppressed.
(3) toward containing SiO 2when adding iron powder in the solution of precursor, for making iron powder even suspension in the solution, when containing SiO 2when the solution viscosity of precursor does not reach about 1 ~ 5Pas, easily produce iron powder sedimentation or uneven.In addition, when leaving standstill after iron powder interpolation, stirring, SiO 2the gelation of precursor solution if do not occurred within 1 point, then the iron powder generation sedimentation of more than 1 μm size.Now, SiO is worked as 2when precursor adopts 4 aggressiveness (Silicate 51) of tetramethoxy-silicane, gelation is faster than TEOS (tetraethoxysilane), can suppress the sedimentation of iron powder.This is due to except Silicate 51 is from being initially except 4 aggressiveness, and the methoxyl group combined with Si is caused by the energy of combination diminishes compared with ethyoxyl.
Here, so-called oligomer, means the polymer that 2 ~ 100 monomers (tetramethoxy-silicane etc.) are combined into.The oligomer of preferably 2 ~ 20 monomer combinations in the present invention.More preferably the oligomer of 2 ~ 10 monomer combinations.
In solution, the methyl alcohol of solvent and water are by slow evaporation, pass through SiO 2the concentration of precursor increases and macromolecule quantizes, and makes SiO 2the viscosity of precursor solution increases.SiO 2when the viscosity of precursor solution reaches about 1 ~ 5Pas, implement the interpolation (30 quality %) of α-Fe powder.Here, α-Fe powder, adopts the powder of average grain diameter 0.05 μm of (50nm) ~ 100 μm size.
Here, the assay method of average grain diameter is illustrated.
Adopt scanning electron microscope (SEM), observe with 50000 ~ 100000 times, can spherical particle be confirmed to be.From composition analysis, it is the particle using Fe as principal component.The diameter of this particle, measures from SEM image.To at least 10 particle assay diameters, get the mean value of this value as average grain diameter.Here, when measuring diameter, using the maximum gauge of an image direction (horizontal direction) as diameter.
Implement ultrasonic wave after interpolation immediately to stir.Here, the object using ultrasonic wave to stir not only makes α-Fe powder be dispersed in containing SiO 2in the solution of precursor, and by containing SiO 2nital in the solution of precursor, is etched the iron on iron powder surface, generates iron ion.This iron ion, eventually through the heat treatment of 1200 DEG C, becomes ε-Fe 2o 3.In addition, this iron ion, can think and become containing SiO 2the gelling catalyst of the solution of precursor.This is because when generating iron ion, result is containing SiO 2the gelation speed of the solution of precursor increases.Final generation SiO 2crosslinked, becomes solid.
Here, for making SiO 2cross-linked reach complete and after placing a few days, adopt mortar to pulverize, under the condition of 40 ~ 80 DEG C, 2 ~ 10 hours, carry out heat drying with vacuum drying oven (below 20hPa).Finally, by high temperature heat treatment furnace, be heated to 1200 DEG C with the programming rate of 240 DEG C/h, after keeping 3 hours in 1200 DEG C, be cooled to room temperature with the cooling rate of 120 DEG C/h.
Then, SiO is removed with hydrofluoric acid 2after, be dispersed in alcoholic solvent and obtain slurries.
Here, when the average grain diameter of α-Fe powder is 50nm, the ε-Fe of synthesis 2o 3the magnetic characteristic of powder 20 DEG C time is: remanent magnetization 8emu/g, coercive force 20.5kOe.
By by these slurries at Sm 2fe 17n 3powder is coated with on the surface, carries out drying, obtains binding magnet magnetic.Binding magnet magnetic mixes with nylon resin adhesive, injects the metal die being applied with 20kOe magnetic field in addition shaping, obtains the composite magnetic shown in Fig. 1.
The composite magnetic of the present embodiment, and only adopts Sm 2fe 17n 3compare during powder, coercive force increases by 1 ~ 5kOe, and the thermal endurance of binding magnet is increased to the high temperature side of 50 DEG C from 20 DEG C.
Table 1 illustrates formation magnetic powder and the magnetic characteristic of injection molding anisotropic bond magnet.
In this table, the scale of α-Fe is decided to be relative ε-Fe 2o 3the ratio of the α-Fe of 100 parts by volume, unit is parts by volume.
Table 1
In this table, when for not using example No.8 (comparative example) of iron oxide, the relict flux metric density of 20 DEG C is 0.68T, coercive force is 6.1kOe.Otherwise, when being use ε-Fe 2o 3example No.2 ~ No.6 (embodiment) time, confirmed ε-Fe 2o 3volume fraction when reaching more than 4%, coercive force increases.
In addition, from use α-Fe and ε-Fe 2o 3the example No.9 ~ No.15 (embodiment) of compound particle can confirm, when the volume fraction of α-Fe is more than 5 parts by volume, relict flux metric density increases.The relative ε of the α-Fe-Fe that both relict flux metric density and coercive force all increase 2o 3volume fraction be 5 ~ 40 parts by volume.When more than 40 parts by volume, adopt the iron of soft magnetism, easily can make Sm 2fe 17n 3magnetization inversion.
In addition, α-Fe and ε-Fe 2o 3compound particle, not only go for Sm 2fe 17n 3powder, and the rare-earth iron series compound shown in No.16 ~ 27 (embodiment) being applicable to table 1, can confirm that coercive force increases or relict flux metric density increases.
Embodiment 2
Add water 28g in 5% nital (by volume, adding the nitric acid of 5% in ethanol) 70g, stirs and make to reach even.Slowly SiO is added in this solution 2precursor (5 aggressiveness of tetraethoxysilane: Silicate 40 (industrial chemistry of rubbing (strain) system)) 35g more.SiO 2precursor adopts 5 aggressiveness (Silicate 40: industrial chemistry of rubbing (strain) is made more) of tetraethoxysilane.Here, owing to being 5% nital, then concentration of nitric acid is high, SiO 2the gelation of precursor is too fast, in order to suppress the uneven homogenize of α-Fe powder, in alkoxyl, adopts compared with methoxyl group, with the ethyoxyl large in conjunction with energy of Si.
Make ethanol and the water slow evaporation of solvent in solution, pass through SiO 2the concentration of precursor increases and macromolecule quantizes, and makes SiO 2the viscosity of precursor solution increases.SiO 2when the viscosity of precursor solution reaches about 1 ~ 5Pas, implement the interpolation of α-Fe powder (30 quality %).Here, α-Fe powder adopts the powder of average grain diameter 50nm.Stir with ultrasonic wave after interpolation.Here, the object that the ultrasonic wave of use stirs not only makes α-Fe powder be dispersed in containing SiO 2in the solution of precursor, and by containing SiO 2the effect of the nital in the solution of precursor, makes the iron on iron powder surface etch, and generates iron ion.This iron ion, eventually through the heat treatment of 1200 DEG C, becomes ε-Fe 2o 3.In addition, can think and become this iron ion containing SiO 2the gelling catalyst of the solution of precursor, generates iron ion, then containing SiO 2the solution gels speed of precursor strengthens, but passes through SiO 2alkoxyl in precursor adopts ethyoxyl, regulates gelation speed.Final generation SiO 2crosslinked, becomes solid.
For making SiO 2cross-linked, after placing a few days, pulverized with mortar completely, use vacuum drying oven (below 20hPa), under the condition of 60 ~ 80 DEG C, 2 ~ 10 hours, carry out heat drying.Finally, use high temperature heat treatment furnace, with the programming rate of 240 DEG C/h, be heated to 1250 DEG C, at 1250 DEG C, maintenance is with the cooling rate of 120 DEG C/h after 3 hours, is cooled to room temperature.
The average grain diameter of α-Fe powder is 50nm, when shape of particle is spherical, and the ε-Fe of synthesis 2o 3powder the magnetic characteristic of 20 DEG C is: remanent magnetization 7emu/g, coercive force 21kOe.Adopt hydrofluoric acid removing SiO 2after, by disperseing 10 quality % in alcoholic solvent, obtain slurries.By these slurries at Sm 2fe 17n 3the surface of powder is carried out be coated with, dry, obtain binding magnet magnetic.Binding magnet magnetic is mixed with nylon resin adhesive, injects the metal die applying 20kOe magnetic field shaping.
Shaping magnet has anisotropy, has confirmed that coercive force is 10kOe, relict flux metric density is the magnetic characteristic of 0.9T.Because coercive force when not using iron oxide is 6kOe, because this increasing the coercive force of 4kOe.The increase of this coercive force, with thermal endurance rise 30 DEG C corresponding, can make rare earth element use amount reduce 10%.
Embodiment 3
Add water 28g in 5% nital (by volume, adding the nitric acid of 5% in ethanol) 70g, is stirred to evenly.Slowly SiO is added in this solution 2precursor (9 aggressiveness of tetraethoxysilane: Silicate 45 (industrial chemistry of rubbing (strain) system)) 31g more.SiO 2precursor adopts 9 aggressiveness (Silicate 45: industrial chemistry of rubbing (strain) is made more) of tetraethoxysilane.
Etoh solvent in slow evaporation solution and water, pass through SiO 2the increase of precursor concentration and macromolecule quantize, and make SiO 2the viscosity of precursor solution increases.SiO 2when the viscosity of precursor solution reaches about 1 ~ 5Pas, implement the interpolation (30 quality %) of Fe-5 quality %Zn powder.Here, Fe-5 quality %Zn powder, adopts the powder of average grain diameter 50nm.Implement ultrasonic wave after adding to stir.Here, the object adopting ultrasonic wave to stir is, is containing SiO 2fe-5 quality %Zn powder is not only disperseed in the solution of precursor, and by containing SiO 2the effect of the nital in the solution of precursor, is etched the iron on iron powder surface, generates iron ion.This iron ion, eventually through the heat treatment of 1200 DEG C, becomes ε-(Fe, Zn) 2o 3.In addition, can think that this iron ion becomes containing SiO 2the catalyst of the solution gels of precursor, when generating iron ion, then containing SiO 2the solution gels speed of precursor strengthens, by SiO 2alkoxyl in precursor adopts ethyoxyl, adjustment gelation speed.Final generation SiO 2crosslinked, becomes solid.
Here, for making SiO 2cross-linked reach complete and after placing a few days, pulverize with mortar, adopt vacuum drying oven (below 20hPa), under the condition of 60 ~ 80 DEG C, 2 ~ 10 hours, carry out heat drying.Finally, adopt high temperature heat treatment furnace, be heated to 1250 DEG C with the programming rate of 240 DEG C/h, keep, after 3 hours, being cooled to room temperature with the cooling rate of 120 DEG C/h at 1250 DEG C.
When the average grain diameter of Fe-5 quality %Zn powder is 50nm spherical, ε-(Fe, the Zn) of synthesis 2o 3powder the magnetic characteristic of 20 DEG C is: remanent magnetization 15emu/g, coercive force 20kOe.SiO is removed with hydrofluoric acid 2after, in alcoholic solvent, disperse 10 quality %, obtain slurries.By these slurries in Sm 2fe 17n 3powder is coated with on the surface, drying, obtains binding magnet magnetic.Binding magnet magnetic is mixed with nylon resin adhesive, injects the metal die being applied with 20kOe magnetic field in addition shaping.
Shaping magnet has anisotropy, can confirm that coercive force is 10kOe, relict flux metric density is the magnetic characteristic of 1.0T.Because the coercive force when not using iron oxide is 6kOe, therefore coercive force adds 4kOe.This coercive force increases, and rises 30 DEG C, relict flux metric density corresponding to thermal endurance, and increased by the Zn displacement at Fe atom site, the consumption of rare earth element reduces 20%.
Except Zn, ε-Fe can be realized 2o 3the Fe atom site substitutional element that magnetization increases is any one element of Mn, Co, Ni, Cu, Mg, Ba, Pb, Sr and Ca.By these elements, the direction that Fe replaces 3 ~ 20 quality %, Fe atom or O atom square is changed, magnetization increase 1 ~ 30%.
Embodiment 4
The mixing of ferric nitrate, tetraethyl orthosilicate and water, to make relative SiO 2, Fe 2o 3quality reach 80 quality %.When the viscosity of solution reaches about 1 ~ 5Pas, add the Fe-10 quality %Co nano particle 20 quality % of particle diameter 50nm in this solution after, implement ultrasonic wave and stir.When the viscosity of solution reaches about more than 20Pas, in the magnetic field of 1kOe, make gelation.After placing a few days, pulverize with mortar, after 3 hours, cool with the cooling rate of 2 DEG C/min in 1200 DEG C of heating maintenances.
By heat treatment, ε-Fe 2o 3grow up in Fe-10 quality %Co nanoparticle surface, from the center of Fe-10 quality %Co particle to surface, the Fe-10 quality %Co of bcc (body-centered cubic crystallographic system) structure, rhombic ε-Fe 2o 3, have a part amorphous multiple crystalline texture SiO 2in growth.
With the SiO that above-mentioned condition makes 2, at α-Fe-Co and ε-(Fe, Co) 2o 3compound particle bonding material in, remove SiO with hydrofluoric acid solution 2, only extract α-Fe-Co and ε-(Fe, Co) 2o 3compound particle.This particle mixes with ethanol, obtains ethanol containing particle 20 quality % as the slurries of solvent.By these slurries and Nd 2fe 14b powder carries out mixing, dry, except desolventizing, at Nd 2fe 14the surface of B powder, is formed and is coated with α-Fe-Co and ε-(Fe, Co) 2o 3the state of compound particle.
The relative Nd of coating weight 2fe 14injection moulding magnet characteristic when B powder reaches 20 quality % is relict flux metric density 1.0T, coercive force 16.5kOe.This is owing to comparing with (1.1T, 13kOe) time uncoated, and coercive force increases 3.5kOe, and thermal endurance improves 30 DEG C.
Embodiment 5
By tetraethyl orthosilicate, water and ethanol with after the mixed in molar ratio of 1:6:6, mixed nitrate iron is to make Fe 2o 3quality reach 30 quality %.Add aluminum ethoxide 1 quality % in solution after, carry out gelation reaction, make the viscosity of solution reach about 1 ~ 5Pas.In this solution, add the Fe particle 10 quality % of particle diameter 1 μm, implement ultrasonic wave and stir.And, after gelling, carry out drying in 80 DEG C.Then, in the magnetic field of 30kOe, keep 10 hours in 150 DEG C.Then, in the air of 1200 DEG C, maintenance 10 hours is heated.Thereafter, cool with the cooling rate of 2 DEG C/min.
To the sample obtained, evaluate 60kOe magnetization after magnetic characteristic as a result, obtain the anisotropic magnet of relict flux metric density 0.9T, coercive force 16kOe.On 20 DEG C of demagnetizing curves measured, in the magnetic field of coercive force less than 1/2, do not find bending point.
In order to obtain the such magnet of magnetic characteristic meeting more than relict flux metric density 0.9T, coercive force more than 15kOe of the present embodiment, following condition must be reached.
1) employing employs tetraethyl orthosilicate, water, ethanol and ferric nitrate, and with the addition of the gelation technique of the organometallic solution containing element beyond Si.
2) before gelation, the ferromagnetism particle with more than 100emu/g saturation magnetization is mixed, disperseed.
3) make the iron oxide of high coercive force grow up at ferromagnetism particle surface, grow up from surface to ferromagnetism inside particles.
4) principal phase forming magnet is (Si, Al) O 2, ε-Fe 2o 3and α-Fe, ε-Fe 2o 3at magnetic direction, there is anisotropy.
SiO in the present embodiment 2other element substitutions of a part in Si site, the Addition ofelements having confirmed to improve magnetic characteristic is Al, Mg, Zr, Ti, Ca and Ba.In addition, at SiO 2/ ε-Fe 2o 3near interface (region from center, interface within 10nm), the element local beyond Fe, Si and O exists, and has suppression ε-Fe 2o 3magnetization inversion effect.
As iron nitrate concentration hour in the solution before gelation, then the core generation number of sites of iron oxide reduces, and the Fe particle surface of mixing is difficult to iron oxide fully coating.For making relict flux metric density reach more than 0.9T, the surface-coated rate of preferential oxidation iron reaches more than 30%.
Embodiment 6
The Fe powder of flat pattern and Nd 2fe 14b inserts metal die with the ratio of mass ratio 1:10, in the magnetic field of 10kOe, makes the long axis direction of flat powder and magnetic direction shaping abreast.Compression stress is 5t/cm 2, form density 6g/cm 3press-powder formed body.In press-powder formed body, the long axis direction of the Fe powder of flat pattern aligns substantially in parallel with magnetic direction, has confirmed the magnetic anisotropy of shape.Import bubble continuously in this press-powder formed body after, steeping liq.The liquid of dipping, by former for tetraethyl silane, water and ethanol with after the mixed in molar ratio of 1:6:6, mixed nitrate iron, to make Fe 2o 3quality reach 30 quality %.Drying is carried out after this liquid of vacuum impregnation.And, in the vacuum of 1100 DEG C, heat maintenance after 10 hours, cool with the cooling rate of 2 DEG C/min.
60kOe magnetic field is applied to it, carries out magnetized as a result, obtain the magnet of coercive force 17kOe, relict flux metric density 1.1T in the direction identical with magnetic direction when making press-powder formed body.Magnet has confirmed as α-Fe, Fe 2o 3and SiO 2, Fe 2o 3at SiO 2and grow up between α-Fe.SiO 2formed continuously from the surface of magnet to opposite side surfaces, Fe 2o 3also grow up continuously.At Fe 2o 3and between α-Fe, produce exchange or magnetostatic combination, suppress it to move owing to magnetizing mutually, therefore demagnetizing curve is dull, presents the coercive force of 5 ~ 20kOe.
Embodiment 7
There is the ε-Fe of rhombohedral structure 2o 3, adopt sol-gal process to make.
Tetraethyl orthosilicate (TEOS:Si (OC 2h 5) 4), H 2o and ethanol mixing, add ferric nitrate 40 quality %, place about 1 week, make generation gelation.Here, tetraethyl orthosilicate is one of siliceous gel precursors example.
This gel compound is in 80 DEG C, heat drying 10 hours.It is heated to 1100 DEG C in an atmosphere, keeps after 1 hour, slowly cool to 1000 DEG C with 1 DEG C/min cooling rate.Then, with maximum cooling rate 100 DEG C/min, 700 DEG C are chilled to.Chilling and the ε-Fe made 2o 3coercive force, reach 21 ~ 28kOe at 27 DEG C.
ε-Fe 2o 3surface adopts solution-treated to form MgF 2, by heating, ε-Fe 2o 3part generation deoxidation (reduction), α-Fe grows up.The composite magnetic obtained thus, has the structure shown in Fig. 2.
For making bcc Stability Analysis of Structures, toward ε-Fe 2o 3middle interpolation 0.1 ~ 10 quality %Co.Thus, bcc-FeCo system particle is from ε-(Fe, Co) 2o 3grow up, structure stabilization and magnetization increase reach satisfactory to both parties.
When Co is less than 0.1 quality %, structure can reach stable, but increases not contribution to magnetization.When Co is more than 10 quality %, owing to using expensive Co, and make raw material cost increase, the goods be suitable for are limited.When Co is more than 50 quality %, ε-Fe 2o 3coercive force be reduced to and be less than 20kOe.
Bcc-FeCo system particle from ε-(Fe, Co) 2o 3the powder of growing up, mixes with methyl alcohol, makes slurries.By these slurries in Sm 2fe 17n 3powder is coated with about 5 quality % on the surface, carries out drying, and the coercive force after magnetization, compared with time uncoated, increases 2kOe.This is equivalent to heat resisting temperature increase about 20 DEG C.

Claims (15)

1. composite magnetic, is characterized in that, it comprises: containing ε-Fe 2o 3and the iron oxide particles of metallic iron, and the rare-earth iron series particle formed by the compound containing rare earth element and iron; The average grain diameter of above-mentioned rare-earth iron series particle is larger than the average grain diameter of above-mentioned iron oxide particles, and the volume fraction of above-mentioned rare-earth iron series particle is larger than the volume fraction of above-mentioned iron oxide particles.
2. according to the composite magnetic described in claim 1, it is characterized in that, above-mentioned metallic iron is α-Fe.
3. according to the composite magnetic described in claim 2, it is characterized in that, above-mentioned iron oxide particles has above-mentioned ε-Fe 2o 3the structure of coating above-mentioned α-Fe.
4. according to the composite magnetic described in claim 2, it is characterized in that, above-mentioned iron oxide particles has above-mentioned α-Fe and is coated to above-mentioned ε-Fe 2o 3structure.
5. according to the composite magnetic described in any one in Claims 1 to 4, it is characterized in that, above-mentioned rare earth element is be selected from least a kind in the group of Y, La, Ce, Pr, Nd and Sm formation.
6. according to the composite magnetic described in any one in Claims 1 to 4, it is characterized in that, above-claimed cpd is Sm 2fe 17n 3.
7. according to the composite magnetic described in any one in claim 2 ~ 6, it is characterized in that, relatively above-mentioned ε-Fe 2o 3100 parts by volume, above-mentioned α-Fe is 5 ~ 40 parts by volume.
8. according to the composite magnetic described in any one in claim 1 ~ 7, it is characterized in that, also containing adhesive.
9. according to the composite magnetic described in claim 2, it is characterized in that, form above-mentioned ε-Fe 2o 3and any one element substitution in a part available Zn, Mn, Co, Ni, Cu, Mg, Ba, Pb, Sr and Ca of the Fe of above-mentioned α-Fe.
10. the manufacture method of composite magnetic, it is the manufacture method of the composite magnetic described in claim 1, it is characterized in that, toward containing acid, silica precursor is added in the solution of alcohol and water, the powder adding above-mentioned metallic iron stirs, make the gel containing iron ion, heat treatment is implemented to above-mentioned gel, make silica containing solid state, pulverized, with hydrofluoric acid dissolution, remove above-mentioned silicon dioxide, be dispersed in alcoholic solvent and made slurries, above-mentioned slurries are coated with on above-mentioned rare-earth iron series particle, after carrying out drying, be blended in carry out in adhesive shaping.
11. according to the manufacture method of the composite magnetic described in claim 10, and it is characterized in that, above-mentioned metallic iron is α-Fe.
12. according to the manufacture method of the composite magnetic described in claim 10 or 11, and it is characterized in that, above-mentioned silica precursor is the oligomer of alkoxy silane.
The manufacture method of 13. composite magnetics, it is the manufacture method of the composite magnetic described in claim 1, it is characterized in that, preparation contains the solution of iron ion and siliceous gel precursors, is dried, makes containing ε-Fe 2o 3gel, reduce above-mentioned ε-Fe 2o 3a part, at above-mentioned ε-Fe 2o 3surface form above-mentioned metallic iron, it is mixed with alcohol, makes slurries, above-mentioned slurries are coated with on above-mentioned rare-earth iron series particle, after carrying out drying, be blended in carry out in adhesive shaping.
The raw material group of 14. composite magnetics, it is the raw material for the manufacture of the composite magnetic described in claim 1, it is characterized in that, this raw material group contains: the powder of silica precursor, above-mentioned metallic iron and the powder be made up of above-mentioned rare-earth iron series particle.
The raw material group of 15. composite magnetics, it is the raw material for the manufacture of the composite magnetic described in claim 1, it is characterized in that, this raw material group contains: siliceous gel precursors, the solution containing iron ion, the powder be made up of above-mentioned rare-earth iron series particle and reducing agent.
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