CN104347219B - 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 PDFInfo
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- CN104347219B CN104347219B CN201410380178.3A CN201410380178A CN104347219B CN 104347219 B CN104347219 B CN 104347219B CN 201410380178 A CN201410380178 A CN 201410380178A CN 104347219 B CN104347219 B CN 104347219B
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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
Technical field
The present invention relates to include ε-Fe2O3With composite magnetic and its manufacturer containing rare earth element and the compound of ferrum
Method.
Background technology
Magnetic material has soft magnetic material and retentive material, and ferromagnetic material is categorized as retentive material.Particularly sinter
Magnet, due to its high magnetic characteristic, has been used for various magnetic loops.Wherein, NdFeB systems sintered magnet, is with Nd2Fe14B tyings are brilliant to be made
For the high-performance Magnet of principal phase, lead in the broad range of product such as automobile, generating equipment, household electrical appliances, medical apparatus and instruments, electronic machine
Used in domain, its consumption is increasing.
In NdFeB systems sintered magnet, in addition to the Nd of rare earth element, to guarantee thermostability, the costliness such as Dy, Tb can be used
Heavy rare earth element.The rare earth element is rare, produces area limitation and protects resource, therefore price is high, therefore rare earth element is used
The requirement that amount is cut down is raised.
On the other hand, rare earth element is not used to obtain the ε-Fe of high coercive force2O3, draw as hard magnetic material
Play concern, ε-Fe2O3And ε-Fe2O3A Fe sites part for crystallization Al displacements are disclosed in patent documentation 1.
However, ε-Fe2O3Due to saturated magnetization and remanent magnetization it is little, in order to as required magnetized material, it is necessary to have
High magnetized Fe systems magnetic is added with compound, as this kind of composite example disclosed in patent documentation 2.
Prior art literature
Patent documentation
Patent documentation 1：JP 2008-060293 publication
Patent documentation 2：JP 2011-032496 publication
The content of the invention
The invention problem to be solved
Patent documentation 1 and 2 is related to using silicon dioxide (SiO2) magnetic material record.
The particle surface coating in ferric hydroxide precipitate is generated by the hydrolysis of silane two have been recorded in patent documentation 1
Silicon oxide, by there is oxidation reaction in heat treatment (950～1150 DEG C) thereafter, silica dioxide coating, generates ε-Fe2O3。ε-
Fe2O3Demagnetizing curve (magnetization curve), as shown in Fig. 4 of patent documentation 1, coercive force reaches 20kOe, near magnetic field (H) zero
Bending point can be observed on curve, energy product is reduced.In patent documentation 1, ε-Fe2O3Fe sites replaced with a part of Al, such as specially
The result of Fig. 3 of sharp document 1 is it will be clear that by carrying out Al displacements in Fe sites, coercive force is reduced.In addition, in order to improve magnetic
Ferrum property, it is necessary to which the Fe system high saturation material big with magnetization value is combined.
The purpose of the present invention is using ε-Fe2O3Magnetic material in improve relict flux metric density and retentivity.
Means for solving the problems
The composite magnetic of the present invention, it is characterised in that it is included：- the Fe containing ε2O3And the iron oxide particles of metallic iron,
And the rare-earth iron series particle formed by the compound containing rare earth element and ferrum；The mean diameter of rare-earth iron series particle compares ferrum oxide
The mean diameter of particle is big, and the volume fraction of rare-earth iron series particle is bigger than the volume fraction of iron oxide particles.
Invention effect
According to the present invention, it is possible to increase using ε-Fe2O3Magnetic material relict flux metric density and retentivity.
Description of the drawings
Fig. 1 is the figure that the signal of one of the composite magnetic of expression present invention example is constituted.
Fig. 2 is the figure that the signal of the another example of composite magnetic for representing the present invention is constituted.
The explanation of symbol
1：Rare-earth iron series particle, 2：Binding agent, 3：ε-Fe2O3、4：α-Fe、5：Iron oxide particles.
Specific embodiment
As Magnet, in order to ensure more than the performance of ferrite magnet, it is necessary to meet following condition.
1) saturated magnetization and Curie temperature are than ε-Fe2O3High Fe based materials and ε-Fe2O3Magnetic knot is closed.
2) Fe based materials and ε-Fe2O3The powder that magnetic knot is closed mixes with rare-earth iron series powder, increases coercive force.
3) ε-Fe are made2O3Volume fraction it is bigger than Fe based material, and reduce coercive force.
4) more than 200 DEG C, the particle diameter of rare-earth iron series powder is than ε-Fe for Curie temperature2O3Particle diameter it is big.
ε-Fe2O3Remanent magnetization it is little to about 10emu/g, Curie temperature is also low to 210 DEG C.But, ε-Fe2O3Magnetic remanence
Power, at 20 DEG C greatly to 20kOe.To make the ε-Fe with this feature2O3Suitable for ferromagnetic material, it is necessary to increase magnetization.As α-Fe
With ε-Fe2O3When merely magnetic knot is closed, magnetization increase, relict flux metric density is also increased, when α-Fe are increased, coercive force drop
It is low, it is difficult to using the feature of high coercive force.
In order to using high coercive force, with respect to ε-Fe2O3100 parts by volume, α-Fe are preferably 5～40 volumes below 50 parts by volume
Part, more preferably 5～30 parts by volume.
When more than 50 parts by volume, ε-Fe2O3Ratio reduce, due to ε-Fe2O3Characteristic can not make full use of, be not
Preferably.In the scope of 5～30 parts by volume, magnetization increase is can confirm that, also, 10 are reached in 100 DEG C of coercive force～
18kOe.Such α-Fe and ε-Fe2O3Complex, remanent magnetization reaches the scope of 12～80emu/g, with ferrite magnetic
The equal Maximum Energy Product of ferrum.
Due to α-Fe and ε-Fe2O3Complex, Maximum Energy Product can be made further to increase, therefore the volume of α-Fe must be made
Rate increases, and maintains high coercive force.α-Fe, because anisotropic energy is little, coercive force diminishes.Therefore, low cost is light dilute
Soil-ferrum system powder, with α-Fe and ε-Fe2O3The combination of complex be effective.
Low-cost rare earth element or LREE, there is Y, La, Ce, Pr, Nd and Sm.These element definitions are dilute for low cost
Earth elements.Low-cost rare earth element, compared with the heavy rare earth elements such as Dy, Tb, there is abundant reserves, is that resource problem and environment are asked
The little element of topic.Such low-cost rare earth element and α-Fe and ε-Fe2O3Composite, remanent magnetization or residual magnetic flux
Density is raised and is possibly realized.The means that it is realized are as shown below.
Compound containing low-cost rare earth element, can use RnAmBlComposition formula is represented.R represents Y, La, Ce, Pr, Nd in formula
And at least one element among Sm, A is at least one of Fe and Co, and B is any the 1 of boron (B), nitrogen (N), carbon (C) and phosphorus (P)
Kind.In addition, n, m, l are positive number, m ＞ n+l are met.
Compound R containing low-cost rare earth elementnAmBlWith α-Fe and ε-Fe2O33 kinds of ferromagnetism phases, such as its volume
Rate is RnAmBl＞ ε-Fe2O3＞ α-Fe, then can suppress coercive force to reduce, and Maximum Energy Product increases.Curie temperature is Tc (α-Fe)
＞ Tc (RnAmBl) ＞ Tc (ε-Fe2O3), ε-Fe2O3Curie temperature it is minimum.α-Fe and RnAmBlCompare, with ε-Fe2O3Magnetic knot
Close strong.This is due to α-Fe and ε-Fe2O3Interfacial area, than α-Fe and RnAmBlInterfacial area it is big, the ε-Fe near α-Fe2O3Than
RnAmBlHow caused neighbouring α-Fe are.
Hereinafter, the composite magnetic that embodiment of the present invention is related to, its manufacture method and for making compound magnetic
The raw material group of property material is illustrated.
Above-mentioned composite magnetic is included：- the Fe containing ε2O3And the iron oxide particles of metallic iron, and, containing rare earth element and ferrum
The rare-earth iron series particle that formed of compound.
Metallic iron is preferably α-Fe.
Iron oxide particles preferably have ε-Fe2O3The structure of coating α-Fe.
Iron oxide particles preferably have the coating ε-Fe of α-Fe2O3Structure.
Rare earth element is preferably selected from least one in the group of Y, La, Ce, Pr, Nd and Sm composition.
Compound containing rare earth element and ferrum is preferably Sm2Fe17N3。
With respect to ε-Fe2O3100 parts by volume, preferred α-Fe are 5～40 parts by volume.
Above-mentioned composite magnetic preferably also contains binding agent.
Constitute ε-Fe2O3And a part of the Fe of α-Fe, preferably by Zn, Mn, Co, Ni, Cu, Mg, Ba, Pb, Sr and Ca
Any element substitution.
When manufacturing above-mentioned composite magnetic, in the solution containing acid, alcohol and water silica precursor is added, add metal
Stirred after iron powder, made the gel containing iron ion, to the gel implement heat treatment, made silica containing solid, shaped
State, is crushed, and silicon dioxide is dissolved, is removed with Fluohydric acid., is dispersed in making serosity in alcoholic solvent, is starched with this
It is dried after liquid coated with rare earth ferrum system particle, being mixed into binding agent carries out molding.
Acid is preferably nitric acid.
Silica precursor is preferably the oligomer of alkoxy silane.
When manufacturing above-mentioned composite magnetic, the solution comprising iron ion and siliceous gel precursors is prepared, is dried,
Make-the Fe containing ε2O3Gel, reduce ε-Fe2O3A part, in ε-Fe2O3Surface formed metallic iron, it is mixed with alcohol,
Serosity is made, the serosity is coated with rare-earth iron series particle, is dried, be mixed in binding agent in addition molding and also may be used.
Raw material group for manufacturing above-mentioned composite magnetic contains：Silica precursor, metallic iron powder and by rare earth
The powder that ferrum system particle is constituted.
Above-mentioned raw materials group both can be included：Solution containing the acid such as nitric acid and alcohol, may also be nital (Nital).
Above-mentioned raw materials group can also contain Fluohydric acid..
Above-mentioned raw materials group is included：Siliceous gel precursors, the solution containing iron ion, the powder being made up of rare-earth iron series particle
And reducing agent.
Siliceous gel precursors are preferably tetraethyl orthosilicate.
As reducing agent, it is preferred to use for MgF2Deng metal fluoride swelling gel and with amorphous reducing agent dispersion
Solution.
Fig. 1 illustrates the section of composite magnetic (injection moulding Magnet) exemplary of the present invention.
Composite magnetic shown in this figure, is (such as Sm of rare-earth iron series particle 12Fe17N3), iron oxide particles 5 and
Binding agent 2 (such as nylon resin) mixing, molding and made by.Iron oxide particles 5 have with ε-Fe2O3(3) it is coated to α-Fe (4)
Surface structure.Iron oxide particles 5 are assembled in the near surface of rare-earth iron series particle 1.
Fig. 2 illustrates the section of composite magnetic (injection moulding Magnet) the another example of the present invention.
This figure is with the difference of Fig. 1：The central part of iron oxide particles 5 is by ε-Fe2O3(3) constitute, surface element is by α-Fe
(4) constitute.
It is illustrated using embodiment below.
Embodiment 1
X% nitals (add by volume the solution of X% nitric acid in methanol：In the present embodiment using 1% and
2%) add water 27.6g in 49.1g, and stirring is made up to uniformly.SiO is slowly added toward the solution2Precursor (the 4 of tetramethoxy-silicane
Aggressiveness：Silicate 51 (industrial chemistry of rubbing more (strain) system)) 30g.
Using 4 aggressiveness of tetramethoxy-silicane as SiO2The reasons why precursor, is as described below.
(1) due to SiO2Ethyoxyl in precursor is changed to methoxyl group, thus generate during solgel reaction, the solvent of evaporation
Methanol is changed to from ethanol.By this operation, the boiling point of solvent is down to 65 DEG C from 78 DEG C, SiO2The concentration of precursor is rapid, its
Cross-linked polymer quantifies reaction and accelerates, and can shorten the gelation time of solution.
(2) SiO is generated from alkoxy silane2When, when the raw material of the oligomer level using alkoxy silane, can press down
Controlling shrinkage mass.Therefore, it can suppress the charge weight (volume) of raw material.
(3) toward containing SiO2When adding iron powder in the solution of precursor, to make iron powder even suspension in the solution, when containing SiO2Before
When the solution viscosity of body does not reach 1～5Pas or so, iron powder sedimentation or uneven is also easy to produce.In addition, in iron powder addition, stirring
After when standing, SiO2The gelation of the precursor solution such as not generation within 1 point, then the iron powder of more than 1 μm size is settled.This
When, work as SiO2When precursor adopts 4 aggressiveness (Silicate 51) of tetramethoxy-silicane, gelation is than TEOS (tetraethoxy-silicanes
Alkane) it is fast, the sedimentation of iron powder can be suppressed.This is the methoxy combined with Si due to except Silicate 51 is in addition to be initially 4 aggressiveness
Caused by base energy of combination compared with ethyoxyl diminishes.
Here, so-called oligomer, it is intended that the polymer that 2～100 monomers (tetramethoxy-silicane etc.) are combined into.This
The oligomer that preferably 2～20 monomers are combined in bright.The oligomer that more preferably 2～10 monomers are combined.
The methanol and water of solvent is by slow evaporation in solution, by SiO2The concentration of precursor increases and molecular weight, makes
SiO2The viscosity of precursor solution increases.SiO2When the viscosity of precursor solution reaches 1～5Pas or so, implement the addition of α-Fe powder
(30 mass %).Here, α-Fe powder, using the powder of 0.05 μm of (50nm)～100 μm size of mean diameter.
Here, the assay method of mean diameter is illustrated.
Using scanning electron microscope (SEM), observed with 50000～100000 times, can confirm that it is pelletoid
Son.Knowable to composition analysis, it is the particle using Fe as main constituent.The diameter of the particle, is measured from SEM image.It is right
At least 10 particle assay diameters, take the meansigma methodss of the value as mean diameter.Here, when determining diameter, image one
The maximum gauge in direction (horizontal direction) is used as diameter.
Implement ultrasonic stirring after addition immediately.Here, it is not only to make α-Fe powder point using the purpose of ultrasonic stirring
It is dispersed in containing SiO2In the solution of precursor, and by containing SiO2Nital in the solution of precursor, iron powder surface
Ferrum is etched, and generates iron ion.The iron ion, eventually through 1200 DEG C of heat treatment, becomes ε-Fe2O3.In addition, the ferrum from
Son, it is believed that become containing SiO2The gelling catalyst of the solution of precursor.This is because, when iron ion is generated, as a result it is
Containing SiO2The gelation speed of the solution of precursor increases.Ultimately generate SiO2Crosslinked, becomes solid.
Here, to make SiO2Cross-linked reach completely and after placing a few days, crushed using mortar, dried with vacuum
Case (below 20hPa) is thermally dried under conditions of 40～80 DEG C, 2～10 hours.Finally, with high temperature heat treatment furnace, with
240 DEG C/h of programming rate is heated to 1200 DEG C, cold with 120 DEG C/h of cooling rate after being kept for 3 hours in 1200 DEG C
But to room temperature.
Then, SiO is removed with Fluohydric acid.2Afterwards, it is dispersed in alcoholic solvent and obtains serosity.
Here, when the mean diameter of α-Fe powder is 50nm, the ε-Fe of synthesis2O3Magnetic characteristic of the powder at 20 DEG C be：It is residual
Stay magnetization 8emu/g, coercive force 20.5kOe.
By by the serosity in Sm2Fe17N3It is coated with powder surface, is dried, obtains binding magnet magnetic powder.Bonding magnetic
Ferrum magnetic powder mixes with nylon resin binding agent, and injection is applied with the metal die in 20kOe magnetic fields in addition molding, obtains Fig. 1
Shown composite magnetic.
The composite magnetic of the present embodiment, and only with Sm2Fe17N3Compare during powder, coercive force increases by 1～5kOe, glue
The thermostability of knot Magnet is improved to 50 DEG C of high temperature side from 20 DEG C.
Table 1 illustrates the composition magnetic powder and magnetic characteristic of injection molding anisotropic bond Magnet.
In this table, the ratio of α-Fe is defined as relative ε-Fe2O3The ratio of the α-Fe of 100 parts by volume, unit is volume
Part.
Table 1
In this table, when for example No.8 (comparative example) for not using ferrum oxide when, 20 DEG C of relict flux metric density is
0.68T, coercive force are 6.1kOe.Conversely, it is using ε-Fe to work as2O3Example No.2～No.6 (embodiment) when, have confirmed that ε-
Fe2O3Volume fraction when reaching more than 4%, coercive force increases.
In addition, from using α-Fe and ε-Fe2O3Compound particle example No.9～No.15 (embodiment) it has been confirmed that work as
When the volume fraction of α-Fe is more than 5 parts by volume, relict flux metric density increases.Relict flux metric density and coercive force both of which increase
Plus the relative ε-Fe of α-Fe2O3Volume fraction be 5～40 parts by volume.When more than 40 parts by volume, using the ferrum of soft magnetism, can hold
Changing places makes Sm2Fe17N3Magnetization inversion.
In addition, α-Fe and ε-Fe2O3Compound particle, Sm not only can be applied to2Fe17N3Powder, and it is also applied for table
Rare-earth iron series compound shown in 1 No.16～27 (embodiment), can confirm that coercive force increases or relict flux metric density
Increase.
Embodiment 2
Add water 28g toward 5% nital (by volume, adding 5% nitric acid toward ethanol) 70g, stirring
Make to reach uniformly.SiO is slowly added toward the solution2Precursor (5 aggressiveness of tetraethoxysilane：(the works of rubbing more of Silicate 40
Industry chemistry (strain) system)) 35g.SiO2Precursor adopts the 5 aggressiveness (Silicate 40 of tetraethoxysilane：Rub industrial chemistry more
(strain) makes).Here, because for 5% nital, then concentration of nitric acid is high, SiO2The gelation of precursor is too fast, in order to
The inequality for suppressing α-Fe powder is homogenized, in alkoxyl, using compared with methoxyl group, and the big ethyoxyl of combination energy of Si.
The ethanol of solvent and water slow evaporation in solution are made, by SiO2The concentration of precursor increases and molecular weight, makes
SiO2The viscosity of precursor solution increases.SiO2When the viscosity of precursor solution reaches about 1～5Pas, implement α-Fe powder (30 matter
Amount %) addition.Here, α-Fe powder adopts the powder of mean diameter 50nm.Ultrasonic stirring is used after addition.Here, use
The purpose of ultrasonic stirring be α-Fe powder is dispersed in containing SiO2In the solution of precursor, and by containing SiO2Precursor
The effect of the nital in solution, the ferrum for making iron powder surface is etched, and generates iron ion.The iron ion, finally
By 1200 DEG C of heat treatment, become ε-Fe2O3.Furthermore it is possible to think the iron ion, become containing SiO2The solution of precursor it is solidifying
Gel catalyst, generates iron ion, then containing SiO2The solution gels speed of precursor is increased, but by SiO2Alcoxyl in precursor
Base adopts ethyoxyl, adjusts gelation speed.Ultimately generate SiO2Crosslinked, becomes solid.
To make SiO2Cross-linked completely and after placing a few days, crushed with mortar, using vacuum drying oven (20hPa with
Under), it is thermally dried under conditions of 60～80 DEG C, 2～10 hours.Finally, using high temperature heat treatment furnace, with 240 DEG C/it is little
When programming rate, be heated to 1250 DEG C, with 120 DEG C/h of cooling rate after being kept for 3 hours at 1250 DEG C, be cooled to
Room temperature.
The mean diameter of α-Fe powder is 50nm, when shape of particle is spherical, the ε-Fe of synthesis2O3Magnetic characteristic of the powder at 20 DEG C
For：Remanent magnetization 7emu/g, coercive force 21kOe.SiO is removed using Fluohydric acid.2Afterwards, by disperseing 10 matter toward alcoholic solvent
Amount %, obtains serosity.By the serosity in Sm2Fe17N3It is coated on the surface of powder, is dried, obtains binding magnet magnetic
Powder.Binding magnet magnetic powder is mixed with nylon resin binding agent, molding in the metal die in injection applying 20kOe magnetic fields.
Molding Magnet has anisotropy, has confirmed that coercive force for 10kOe, the magnetic spy that relict flux metric density is 0.9T
Property.It is 6kOe due to not using coercive force during ferrum oxide, therefore increased the coercive force of 4kOe.The increase of the coercive force, with
Thermostability rises 30 DEG C of correspondences, and the usage amount that can make rare earth element reduces 10%.
Embodiment 3
Add water 28g toward 5% nital (by volume, adding 5% nitric acid toward ethanol) 70g, stirring
To uniform.SiO is slowly added toward the solution2Precursor (9 aggressiveness of tetraethoxysilane：(rub Silicate 45 industrialization more
Learn (strain) system)) 31g.SiO2Precursor adopts the 9 aggressiveness (Silicate 45 of tetraethoxysilane：Industrial chemistry of rubbing more (strain)
System).
Etoh solvent and water in slow evaporation solution, by SiO2The increase of precursor concentration and molecular weight, make SiO2
The viscosity of precursor solution increases.SiO2When the viscosity of precursor solution reaches about 1～5Pas, implement adding for Fe-5 mass %Zn powder
Plus (30 mass %).Here, Fe-5 mass %Zn powder, using the powder of mean diameter 50nm.Implement ultrasonic stirring after addition.
Here, it is using the purpose of ultrasonic stirring, containing SiO2Not only disperse Fe-5 mass %Zn powder in the solution of precursor, and
By containing SiO2The effect of the nital in the solution of precursor, etches the ferrum on iron powder surface, generate ferrum from
Son.The iron ion, eventually through 1200 DEG C of heat treatment, becomes ε-(Fe, Zn)2O3.Furthermore it is possible to think that the iron ion becomes
Containing SiO2The catalyst of the solution gels of precursor, when iron ion is generated, then containing SiO2The solution gels speed of precursor adds
Greatly, by SiO2Alkoxyl in precursor adopts ethyoxyl, adjusts gelation speed.Ultimately generate SiO2Crosslinked, becomes solid
Body.
Here, to make SiO2Cross-linked reach completely and after placing a few days, crushed with mortar, dried using vacuum
Case (below 20hPa), is thermally dried under conditions of 60～80 DEG C, 2～10 hours.Finally, using high temperature heat treatment furnace,
1250 DEG C are heated to 240 DEG C/h of programming rate, after being kept for 3 hours at 1250 DEG C, with 120 DEG C/h of cooling speed
Degree is cooled to room temperature.
The mean diameter of Fe-5 mass %Zn powder for 50nm it is spherical when, ε-(Fe, the Zn) of synthesis2O3Magnetic of the powder at 20 DEG C
Characteristic is：Remanent magnetization 15emu/g, coercive force 20kOe.SiO is removed with Fluohydric acid.2Afterwards, 10 mass % are disperseed in alcoholic solvent,
Obtain serosity.By the serosity in Sm2Fe17N3It is coated with powder surface, is dried, obtains binding magnet magnetic powder.Bonding magnetic
Ferrum magnetic powder mixes with nylon resin binding agent, and injection is applied with the metal die in 20kOe magnetic fields in addition molding.
The Magnet of molding has anisotropy, can confirm that coercive force for 10kOe, the magnetic that relict flux metric density is 1.0T
Characteristic.Because the coercive force when ferrum oxide is not used is 6kOe, therefore coercive force increased 4kOe.The coercive force increases, right
30 DEG C should be risen in thermostability, relict flux metric density is increased, the use of rare earth element by the Zn displacements in Fe atom sites
Amount reduces 20%.
In addition to Zn, ε-Fe are capable of achieving2O3Magnetization increase Fe atom sites substitutional element be Mn, Co, Ni, Cu, Mg, Ba,
Any one element of Pb, Sr and Ca.Send out in the direction that 3～20 mass %, Fe atoms or O atom square are replaced to Fe by these elements
Changing, magnetization increase 1～30%.
Embodiment 4
The mixing of ferric nitrate, tetraethyl orthosilicate and water, so that relative SiO2, Fe2O3Quality reach 80 mass %.It is molten
When the viscosity of liquid reaches about 1～5Pas, the matter of Fe-10 mass %Co nanoparticle 20 of particle diameter 50nm is added toward the solution
After amount %, implement ultrasonic stirring.When the viscosity of solution reaches about more than 20Pas, in the magnetic field of 1kOe gelation is made.Put
After putting a few days, crushed with mortar, after 1200 DEG C of heating are kept for 3 hours, cooled down with 2 DEG C/min of rate of cooling.
By heat treatment, ε-Fe2O3Grow up in Fe-10 mass %Co nanoparticle surface, from Fe-10 mass %Co particles
Center to surface, Fe-10 mass %Co of bcc (body-centered cubic crystallographic system) structure, rhombic ε-Fe2O3, with a part
The SiO of amorphous various crystalline textures2Growing up.
The SiO made of above-mentioned condition2, in α-Fe-Co and ε-(Fe, Co)2O3Compound particle bonding material in, use
Hydrofluoric acid solution removes SiO2, only extract α-Fe-Co and ε-(Fe, Co)2O3Compound particle.The particle is mixed with ethanol
Close, obtain the ethanol containing mass % of particle 20 as the serosity of solvent.By the serosity and Nd2Fe14B powder is mixed, is done
It is dry, solvent is removed, in Nd2Fe14The surface of B powder, formation is coated with α-Fe-Co and ε-(Fe, Co)2O3The state of compound particle.
Coating weight is with respect to Nd2Fe14Injection moulding Magnet characteristic when B powder reaches 20 mass % is relict flux metric density
1.0T, coercive force 16.5kOe.This be due to it is uncoated when (1.1T, 13kOe) compare, coercive force increase 3.5kOe, thermostability
Improve 30 DEG C.
Embodiment 5
By tetraethyl orthosilicate, water and ethanol with 1:6:After 6 mixed in molar ratio, mixed nitrate ferrum is so that Fe2O3Quality
Reach 30 mass %.To add after mass % of aluminum ethoxide 1 toward solution, carry out gelation reaction, the viscosity for making solution reaches 1～
5Pas or so.Add mass % of Fe particles 10 of 1 μm of particle diameter toward the solution, implement ultrasonic stirring.And, in gelation
Afterwards, it is dried in 80 DEG C.Then, in the magnetic field of 30kOe, kept for 10 hours in 150 DEG C.Then, in 1200 DEG C of air
Middle heating is kept for 10 hours.Thereafter, cooled down with 2 DEG C/min of rate of cooling.
To the sample for obtaining, evaluate magnetic characteristic as a result, having obtained relict flux metric density after 60kOe magnetization
The anisotropic magnet of 0.9T, coercive force 16kOe.On the demagnetizing curve of 20 DEG C of measure, in magnetic field of the coercive force below 1/2
It was found that bending point.
Meet as in order to obtain the present embodiment more than relict flux metric density 0.9T, the magnetic of more than coercive force 15kOe
The Magnet of characteristic, it is necessary to reach following condition.
1) using having used tetraethyl orthosilicate, water, ethanol and ferric nitrate, and with the addition of containing beyond Si element it is organic
The gelation technique of the solution of metal.
2) before gelation the ferromagnetism particle with more than 100emu/g saturated magnetizations is mixed, is disperseed.
3) ferrum oxide for making high coercive force is grown up in ferromagnetism particle surface, is grown up from surface to ferromagnetism inside particles.
4) principal phase for constituting Magnet is (Si, Al) O2、ε-Fe2O3And α-Fe, ε-Fe2O3Have in magnetic direction each to different
Property.
SiO in the present embodiment2Si sites a part with other elements replace, having confirmed that can improve adding for magnetic characteristic
Added elements are Al, Mg, Zr, Ti, Ca and Ba.In addition, in SiO2/ε-Fe2O3Near interface is (from interface center within 10nm
Region), the element beyond Fe, Si and O locally lies in, with suppression ε-Fe2O3Magnetization inversion effect.
Such as iron nitrate concentration hour in the solution before gelation, then the core generation number of sites reduction of ferrum oxide, the Fe of mixing
Particle surface is difficult to fully be coated to ferrum oxide.To make relict flux metric density reach more than 0.9T, the surface of preferred ferrum oxide
Covering rate reaches more than 30%.
Embodiment 6
The Fe powder and Nd of flat pattern2Fe14B is with mass ratio 1:10 ratio insertion metal die, in the magnetic field of 10kOe
In, make long axis direction and the magnetic direction abreast molding of flat powder.Compression stress is 5t/cm2, form density 6g/cm3Pressure
Powder molded body.In press-powder molded body, the long axis direction of the Fe powder of flat pattern is aligned substantially parallel with magnetic direction, has confirmed that
The magnetic anisotropy of shape.It is continuously introduced into after bubble toward the press-powder molded body, steeping liq.The liquid of dipping, by tetraethyl
Former silane, water and ethanol are with 1:6:After 6 mixed in molar ratio, mixed nitrate ferrum, so that Fe2O3Quality reach 30 mass %.Very
Sky impregnates and is dried after the liquid.And, after heating is kept for 10 hours in 1100 DEG C of vacuum, with 2 DEG C/min of cooling
Speed is cooled down.
Apply 60kOe magnetic fields to it, magnetic direction identical direction when with making press-powder molded body carries out magnetized
As a result, obtaining coercive force 17kOe, the Magnet of relict flux metric density 1.1T.Magnet is had confirmed that as α-Fe, Fe2O3And SiO2,
Fe2O3In SiO2Grow up between α-Fe.SiO2It is formed continuously to opposite side surfaces from the surface of Magnet, Fe2O3Also continuously grow up.
In Fe2O3Between α-Fe, exchange or magnetostatic combination are produced, because mutually magnetization suppresses its to move, therefore demagnetizing curve list
Adjust, the coercive force of 5～20kOe is presented.
Embodiment 7
ε-Fe with rhombohedral structure2O3, made using sol-gal process.
Tetraethyl orthosilicate (TEOS：Si(OC2H5)4)、H2O and ethanol mix, and add mass % of ferric nitrate 40, place 1
All left and right, make generation gelation.Here, tetraethyl orthosilicate, is one of siliceous gel precursors example.
The gel compound is in 80 DEG C, heat drying 10 hours.It is heated in an atmosphere 1100 DEG C, after being kept for 1 hour,
1000 DEG C are slowly cooled to 1 DEG C/min rate of cooling.Then, with 100 DEG C/min of maximum rate of cooling, 700 DEG C are chilled to.It is anxious
It is cold and make ε-Fe2O3Coercive force, reach 21～28kOe at 27 DEG C.
ε-Fe2O3Surface forms MgF using solution process2, by heating, ε-Fe2O3A part occur deoxidation (reduction),
α-Fe grow up.Thus obtained composite magnetic, with the structure shown in Fig. 2.
To make bcc Stability Analysis of Structures, toward ε-Fe2O30.1～10 mass %Co of middle addition.Thus, bcc-FeCo systems particle from ε-
(Fe, Co)2O3Growth, structure stabilization and magnetization increase up to satisfactory to both parties.
When Co is less than 0.1 mass %, structure can reach to be stablized, but magnetization is increased without contribution.When Co is more than 10 matter
During amount %, due to the Co using costliness, and raw material cost is set to increase, applicable product is limited to.When Co is more than 50 mass %,
ε-Fe2O3Coercive force decrease below 20kOe.
Bcc-FeCo systems particle from ε-(Fe, Co)2O3The powder of growth, with methanol mixed, makes serosity.By the way that this is starched
Liquid is in Sm2Fe17N3About 5 mass % are coated with powder surface, are dried, the coercive force after magnetization with it is uncoated when compared with, increase
Plus 2kOe.This is equivalent to about 20 DEG C of heat resisting temperature increase.
Claims (13)
1. composite magnetic, it is characterised in that it is included：- the Fe containing ε2O3And the iron oxide particles of metallic iron, and by containing dilute
The rare-earth iron series particle that the compound of earth elements and ferrum is formed；The mean diameter of above-mentioned rare-earth iron series particle is than above-mentioned oxidation abrasive grit
The mean diameter of son is big, and the volume fraction of above-mentioned rare-earth iron series particle is bigger than the volume fraction of above-mentioned iron oxide particles,
Above-mentioned metallic iron is α-Fe,
Above-mentioned iron oxide particles have above-mentioned ε-Fe2O3The structure or above-mentioned α-Fe for being coated to above-mentioned α-Fe is coated to above-mentioned ε-Fe2O3's
Structure,
Above-mentioned rare-earth iron series particle is ferromagnetism rare-earth iron series particle.
2. according to the composite magnetic described in claim 1, it is characterised in that above-mentioned rare earth element be selected from Y, La, Ce,
At least one in the group that Pr, Nd and Sm are constituted.
3. according to the composite magnetic described in claim 1 or 2, it is characterised in that above-claimed cpd is Sm2Fe17N3。
4. according to the composite magnetic described in claim 1 or 2, it is characterised in that relatively above-mentioned ε-Fe2O3100 parts by volume,
Above-mentioned α-Fe are 5～40 parts by volume.
5. according to the composite magnetic described in claim 3, it is characterised in that relatively above-mentioned ε-Fe2O3100 parts by volume, it is above-mentioned
α-Fe are 5～40 parts by volume.
6. according to the composite magnetic described in claim 1 or 2, it is characterised in that also contain binding agent.
7. according to the composite magnetic described in claim 3, it is characterised in that also contain binding agent.
8. according to the composite magnetic described in claim 4, it is characterised in that also contain binding agent.
9. according to the composite magnetic described in claim 5, it is characterised in that also contain binding agent.
10. according to the composite magnetic described in claim 1, it is characterised in that constitute above-mentioned ε-Fe2O3And above-mentioned α-Fe
An any one of part of Fe available Zn, Mn, Co, Ni, Cu, Mg, Ba, Pb, Sr and Ca element substitution.
The manufacture method of 11. composite magnetics, it is the manufacture method of the composite magnetic described in claim 1, its
It is characterised by, add silica precursor toward the solution containing acid, alcohol and water, the powder for adding above-mentioned metallic iron is stirred,
The gel containing iron ion is made, to above-mentioned gel implement heat treatment, silica containing solid state is made, is crushed, used
Hydrofluoric acid dissolution, the above-mentioned silicon dioxide of removing, are dispersed in making serosity in alcoholic solvent, above-mentioned serosity in above-mentioned Rare-earth Iron
Be be coated with particle, be dried after, be mixed carries out molding in binding agent.
12. according to the composite magnetic described in claim 11 manufacture method, it is characterised in that before above-mentioned silicon dioxide
Body 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, its
It is characterised by, prepares the solution containing iron ion and siliceous gel precursors, be dried, makes-the Fe containing ε2O3Gel, reduction
Above-mentioned ε-Fe2O3A part, in above-mentioned ε-Fe2O3Surface form above-mentioned metallic iron, it is mixed with alcohol, make serosity,
Above-mentioned serosity is coated with above-mentioned rare-earth iron series particle, and after being dried, be mixed carries out molding in binding agent.
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| JP6856196B2 (en) * | 2016-12-28 | 2021-04-07 | 国立研究開発法人産業技術総合研究所 | Magnetic particles and their manufacturing method |
| CN107068318A (en) * | 2017-03-24 | 2017-08-18 | 合肥羿振电力设备有限公司 | It is a kind of for magnetic material of transformer and preparation method thereof |
| US11657935B2 (en) | 2018-07-17 | 2023-05-23 | Korea Institute Of Materials Science | Iron oxide magnetic powder and manufacturing method therefor |
| KR102243111B1 (en) * | 2019-07-12 | 2021-04-23 | 한국재료연구원 | An magnetic powder and a method of producing of the same |
| KR102045771B1 (en) * | 2018-07-17 | 2019-11-18 | 한국기계연구원 | An magnetic powder and a method of producing of the same |
| KR102277528B1 (en) * | 2019-09-10 | 2021-07-15 | 나한길 | Manufacturing method of Molecular group composite |
| JP2021054711A (en) * | 2019-09-30 | 2021-04-08 | 国立大学法人 東京大学 | Iron-based oxide magnetic powder and method for producing the same |
| CN117501393A (en) * | 2021-06-10 | 2024-02-02 | 日亚化学工业株式会社 | SmFeN anisotropic magnetic powder, bonded magnet, and method for producing same |
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