CN107010937A - One kind contains Cu2+W-type ferrite material and its preparation - Google Patents

One kind contains Cu2+W-type ferrite material and its preparation Download PDF

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CN107010937A
CN107010937A CN201710281749.1A CN201710281749A CN107010937A CN 107010937 A CN107010937 A CN 107010937A CN 201710281749 A CN201710281749 A CN 201710281749A CN 107010937 A CN107010937 A CN 107010937A
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type ferrite
ferrite material
bamg
sio
weight
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牛晓飞
纵榜峰
郝保明
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Suzhou University
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Suzhou University
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • C04B35/2625—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing magnesium
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    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead
    • C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
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    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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
    • H01F1/34—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 non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4
    • H01F1/348—Hexaferrites with decreased hardness or anisotropy, i.e. with increased permeability in the microwave (GHz) range, e.g. having a hexagonal crystallographic structure
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O

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Abstract

Contain Cu the invention discloses one kind2+W-type ferrite material and its preparation, its chemical structural formula be BaMg(2‑x)CuxFe16O27, wherein 0.001≤x≤1.6.It is of the present invention a kind of containing Cu2+W-type ferrite material can sintering temperature be 1150 DEG C~1350 DEG C when, Br value reaches 350mT~470mT, and Hcj value reaches 140kA/m~200kA/m.Beneficial effects of the present invention are：This kind contains Cu2+W-type ferrite material possess higher hard magnetic properties, its remanent magnetism and HCJ, diminish when sintered magnet volume, it is thinning after, remain to keep high residual magnetic flux density, its price is more cheap compared with traditional Ferrite Material of same type.

Description

One kind contains Cu2+W-type ferrite material and its preparation
Technical field
The present invention relates to a kind of W-type ferrite material and its preparation, more particularly to one kind are new containing Cu2+W sections oxygen Body material and its preparation.
Background technology
Current ferrite sintered body magnet and bonded permanent magnet are widely used in the every field of social life.As being applied to rub The startup motor of motorcycle, automobile, power window, ABS, fan etc..And ferrite permanent-magnet materials are even more to be widely used in audio, regard Frequency sound equipment, motor of office automation, sound equipment and video recorder etc. etc.；In addition, ferrite permanent-magnet materials can also be used to wash Clothing machine, micro-wave oven, the household appliances and electric tool such as refrigerator etc.；It is of particular importance that compared to other permanent-magnet materials such as neodymium iron Boron permanent magnet, samarium cobalt permanent magnet body equimagnetic material, with excellent cost performance.Therefore explore the ferrite permanent-magnet material of research and development novel high-performance Material has indispensable important function to improving daily life level, is all the emphasis of magnetic material research field all the time One of.
Traditional a few class Ferrite Materials have following several classes：
The first kind：Ba the or Sr ferrites of hexagonal structure, use AFe12O19Represent.It is typically Ba or Sr at A, or Person's both of which has.Add additive A l2O3, Cr2O3, B2O3, SiO2, CaCO3Deng, magnetic parameter is adjusted, but total amount is not More than AFe12O191.5wt%.
Equations of The Second Kind：Sr(Ba)1-xRxFe12-yCoyO19(atomic ratio) type ferrite.Wherein, element R is at least a kind of Y bag Capacitive rare earth element, and La must be included in element R.X, y meet following condition respectively：0<X≤0.5,0.01≤y≤1.0. Add additive A l2O3, Cr2O3, B2O3, SiO2, CaCO3Deng, magnetic parameter is adjusted, but total amount is no more than Sr (Ba)1-xRxFe12-yCoyO191.5wt%.
3rd class：By mandate patent of invention (ZL200910251673.3) new calcium permanent ferrite, its chemical structural formula For R1-x-yCaxLay·nFe2-zCoz/nO3, wherein, 0.01≤x≤0.4,0.1≤y≤0.75,0.07≤z≤0.82,5.0≤n ≤ 6.5,0≤1-x-y≤0.5, R be Ca, Ba, Sr or not include La group of the lanthanides Ce, Pr and Nd and Sm in one kind, two kinds and Three kinds；When R is Ba and Sr, Ba and Sr content≤0.2.Add additive A l2O3, Cr2O3, B2O3, SiO2, CaCO3Deng to magnetic Performance parameter is adjusted, but total amount is no more than Sr (Ba)1-xRxFe12-yCoyO191.5wt%.
The class of the above first and second is commonly referred to as Ba or Sr ferrites or part ion substitution (displacement) barium ferrite, strontium iron Oxysome, its shortcoming is be prepared into ferrite device at sintering temperature≤1150 DEG C, and Br be extremely difficult to 4.2~ 4.75kGs, HcjIt is extremely difficult to 4.5~5.0kOe.3rd class is referred to as calcium based permanent magnet oxysome, is characterized in that calcium turns into A mainly Occupy-place ion, compensate for the low shortcoming of the ferritic magnetic property of first and second class.
Permanent-magnet ferrite classification schemes above, for M type ferrites；At present to the hard magnetic of W-type ferrite Rare report is applied in the research of energy, and its soft magnet performance report is also less.Due to W-type ferrite A2+Me22+Fe16O27Satisfy with high With the intensity of magnetization and big magnetocrystalline anisotropy energy, it has broad application prospects and huge potential city as permanent-magnet material Field value.Patent of the present invention is by the ionic compartmentation to W-type ferrite, in unit cell, realizes permanent magnetism phase (R+S blocks) epitaxial growth The soft magnetism phase (S blocks) of high saturation and magnetic intensity.Optimized by composition, structure, crystal grain, to magnetic moment orientation, arrangement and one-domain structure Deng effective manual control is carried out, the permanent magnet with high remanent magnetism and high HCJ is prepared.
The content of the invention
The invention provides a kind of W-type ferrite material and its preparation, more particularly to one kind are new containing Cu2+W sections Ferrite and its preparation, W-type ferrite material of the present invention possess higher hard magnetic properties, remanent magnetism and HCJ And magnetic energy product reaches the industrial applications standard of hard ferrite material.
The technical scheme is that：
One kind contains Cu2+W-type ferrite material and its preparation, it is characterised in that：Preparation technology comprises the following steps：(1) Batch mixing：By chemical structural formula BaMg(2-x)CuxFe 16O27Composition requirement, by the corresponding oxidation raw material and carbon with contained component After the mixing of hydrochlorate material powder, with water, steel ball is according to material：Water：Ball=1：1：8 weight is mixed than proportioning；Then, addition addition Agent Al2O3、Cr2O3、B2O3And SiO2, its each component addition weight account for BaMg(2-x)CuxFe 16O27Construction weight percentage is respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤Cr2O3≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%, by above-mentioned institute Obtain dispensing and carry out ball milling mixing stirring 1~20 hour, obtain the batch mixing that suspended particulate average grain diameter is 0.1~2.0 μm；
(2) pre-burning：By gained batch mixing pre-burning 0.5~6 hour at 1000~1500 DEG C in step (1), W type permanent magnetism is prepared Ferrite Material Preburning material；
(3) powder processed：First by gained W-type ferrite material Preburning material in step (2), being milled to average grain diameter with ball mill is 0.1~5.0 μm of powder, then adds surfactant, and the weight of the surfactant accounts for BaMg(2-x)CuxFe 16O27Knot Structure percentage by weight is 0.5~10%, finally, is mixed into additive A l2O3, Cr2O3, B2O3(or H3BO3), SiO2(or H2SiO3), Additive each component accounts for BaMg(2-x)CuxFe 16O27Construction weight percentage is respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤ Cr2O3≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%；Further adjustment is formulated, with BaMg(2-x)CuxFe 16O27Match somebody with somebody Material, it is 0.01~10.0% additive total amount is accounted for Preburning material percentage by weight.Then weight ratio is used for water：Material：Ball=1： 1：8, with ball mill (or sand mill), are milled to average grain diameter for 0.08~0.8 μm；
(4) green compact are suppressed：According to actual operation requirements, the size of mold shape is controlled, compacting green compact are carried out in magnetic field, Pressing pressure is 0.1~0.5ton/cm2, pulsed magnetic field intensity is 5.0~15.0kOe；
(5) sinter：By green compact at 900~1500 DEG C, be sintered in atmospheric oxidising atmosphere device (such as tiles and Ring-type etc.), sintering time is 0.5~8 hour, and temperature rise rate is 30~500 DEG C/h；
(6) grinding and measurement：The magnetic patch that room temperature is cooled to after sintering is cut and is ground, according to GB/T3217-92 National standard is tested, measured.
It is preferred that, the oxide raw material wherein described in step (1) is CuO, Fe2O3、Fe3O4, MgO, carbonated starting material is BaCO3And MgCO3, the surfactant wherein described in step (3) is calcium gluconae, glucose, sorbierite, ascorbic acid With 2 kinds in oleic acid or mixture of more than two kinds.
It is preferred that, described W-type ferrite material is hexaplanar, and its chemical molecular formula is BaMg(2-x)CuxFe 16O27, Wherein, 0.001≤x≤1.6.
It is preferred that, BaMg is removed in described W-type ferrite material(2-x)CuxFe 16O27Outside, also include additive, add The component of agent is Al2O3、Cr2O3、B2O3、SiO2, its each component accounts for BaMg(2-x)CuxFe 16O27Construction weight percentage is respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤Cr2O3≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%.
It is preferred that, Preburning material is incubated 1~4 hour at 1200~1450 DEG C, and green compact are at 950~1500 DEG C, during sintering Between be 1~6 hour, magnet rate of temperature fall after sintering is 30~50 DEG C/h.
It is of the present invention a kind of containing Cu2+W-type ferrite material can sintering temperature be 1150 DEG C~1300 DEG C when, Br's Value reaches 350mT~470mT, and Hcj value reaches 140kA/m~200kA/m.One kind of the present invention contains Cu2+W-type ferrite material Material possesses higher hard magnetic properties, its remanent magnetism and HCJ, diminish when sintered magnet volume, it is thinning after, remain to keep high Residual magnetic flux density.
To reach above-mentioned purpose, the present invention determines thing phase composition, X fluorescence spectrum analysis sample by X-ray diffractometer (XRD) The content of element in block, vibrating specimen magnetometer (VSM) measures the specific magnetization of material, and the ratio table of magnetic is measured with BET method Area, permanent magnetism characteristic parameter is measured with B-H magnetic properties measuring instrument.
Brief description of the drawings
Fig. 1 is to contain Cu obtained by preparation2+W-type ferrite material XRD diffraction patterns, wherein x is respectively 0,0.2,0.4, 0.6。
Fig. 2 is to contain Cu obtained by preparation2+W-type ferrite material XRD diffraction patterns, wherein x is respectively 0.8,1.0, 1.2,1.4.
Fig. 3 is is molded with alignment magnetic field, containing Cu2+The scanning electron microscope (SEM) photograph vertical with C direction of principal axis of W-type ferrite material.
Fig. 4 is that isotropism contains Cu2+Scanning electron microscope (SEM) photograph of the W-type ferrite material along C direction of principal axis.
Fig. 5 be embodiment 1 in 1350 DEG C of sintering temperature PROCESS FOR TREATMENTs, gained contains Cu2+W-type ferrite material remanent magnetism with Coercivity schematic graph.
Fig. 6 be embodiment 4 in 1310 DEG C of sintering temperature PROCESS FOR TREATMENTs, gained contains Cu2+W-type ferrite material remanent magnetism, Coercivity and maximum magnetic energy product schematic graph.
Embodiment
To further describe the present invention, novel ferrite material of the present invention is made further specifically with reference to embodiment It is bright：
Embodiment 1
Primary raw material is CuO, Fe2O3、BaCO3And MgCO3, a small amount of BaO, Al2O3、Cr2O3、B2O3、SiO2, after sintering Main constituents meet following molecular formula：
BaMg(2-x)CuxFe 16O27, wherein x=0.2.Material powder is immersed in the water according to above-mentioned molecular formula proportioning, Mixed 3 hours in ball mill, the batch mixing that suspended particulate particle diameter is 0.1~2.0 μm is obtained, in 1300 DEG C of pre-burnings in nitrogen atmosphere 3 hours, XRD analysis determined the W phases containing 75wt% in thing phase, and its primary grain size is 9 μm.
Ground in ball mill until average particle diameter size is less than or equal to 5.0 μm, obtain the specific surface area of grounds travel (BET method acquisition) is 7m2/g。
It is 700 DEG C in temperature, is heat-treated under nitrogen atmosphere, is incubated 5 hours, obtains a preburning powdered material.
Additive is subsequently added, additive each component addition is with a preburning powdered material weight than as follows respectively：1%wt CaCO3, 0.6wt%SiO2, 0.7wt%Al2O3, 0.5wt% Ga2O3, surfactant 1.6wt% calcium gluconaes are added, 10wt% adds oleic acid.The powder that average grain diameter is 0.7 μm is milled to sand mill, the specific surface area (BET method) of grounds travel is obtained For 20m2/ g, the sand powder-grinding time is 10 hours.
Compacting green compact processing is carried out in 15kOe magnetic fields, the pressure of compacting is 0.5ton/cm2。
Green compact are in the case where sintering temperature is 1350 DEG C, and nitrogen protective atmosphere encloses middle sintering and obtains finished product in 3 hours, and temperature rise rate is 30 ℃/h.The W phases of finished product account for 91wt%, remanent magnetism Br=370mT, magnetic induction coercivity H b=170kA/m, HCJ Hcj= 187kA/m, magnetic energy product (BH) max reaches 3.51MGOe.
Embodiment 2
Primary raw material is CuO, Fe3O4, BaO and MgCO3, a small amount of BaCO3、Al2O3、Cr2O3、B2O3、SiO2, after sintering Main constituents meet following molecular formula：
BaMg(2-x)CuxFe 16O27, wherein x=0.4.Material powder is immersed in the water according to above-mentioned molecular formula proportioning, Mixed 3 hours in ball mill, the batch mixing that suspended particulate particle diameter is 0.1~2.0 μm is obtained, in 1310 DEG C of pre-burnings in nitrogen atmosphere 3 hours, XRD analysis determined the W phases containing 79wt% in thing phase, and its primary grain size is 10 μm.
In ball mill grinding, until average grain diameter turns into the powder less than or equal to 5.0 μm, the specific surface area of grounds travel is obtained (BET method acquisition) is 9m2/g。
It is heat-treated in nitrogen atmosphere, temperature is 1000 DEG C, is incubated 3 hours, obtains a preburning powdered material.
Additive is subsequently added, additive each component addition is with a preburning powdered material weight than as follows respectively：1%wt CaCO3, 0.8wt%SiO2, 0.9wt%Al2O3, 0.5wt% SnO2, surfactant 1.6wt% calcium gluconaes are added, 8wt% adds oleic acid.Average grain diameter is milled to sand mill for 0.6 μm, the specific surface area (BET method) for obtaining grounds travel is 22m2/ G, the powder time processed is 10 hours.
15000Oe carries out compacting green compact in magnetic field, and the pressure of compacting is about 0.5ton/cm2。
Green compact sinter 2.5 hours to obtain finished product, temperature rise rate is about 40 in the case where sintering temperature is 1200 DEG C in nitrogen atmosphere DEG C/h.The W phases of finished product are 96wt%, remanent magnetism Br=375mT, magnetic induction coercivity H b=178kA/m, HCJ Hcj=189kA/m, magnetic energy product (BH) max reaches 3.31MGOe.
Embodiment 3
Primary raw material is CuO, Fe3O4, BaO and MgO, a small amount of BaCO3、Al2O3、Cr2O3、B2O3、SiO2、MgCO3, burning Main constituents after knot meet following molecular formula：
BaMg(2-x)CuxFe 16O27, wherein x=0.6.Material powder is immersed in the water according to above-mentioned molecular formula proportioning, Mixed 3 hours in ball mill, the batch mixing that suspended particulate particle diameter is 0.1~2.0 μm is obtained, in 1330 DEG C of pre-burnings in nitrogen atmosphere 3 hours, XRD analysis determined the W phases containing 72wt% in thing phase, and its primary grain size is 10 μm.
In ball mill grinding, until average grain diameter turns into the powder less than or equal to 5.0 μm, the specific surface area of grounds travel is obtained (BET method acquisition) is 9m2/g。
It is heat-treated in a nitrogen atmosphere, temperature is 950 DEG C, is incubated 2 hours, obtains a preburning powdered material.
Additive is subsequently added, additive each component addition is with a preburning powdered material weight than as follows respectively：1wt% CaCO3, 0.4wt%SiO2, 1.0wt%Al2O3, 5wt%La2O3, 3.0wt%Fe2O3With 0.7wt% In2O3, add surface Activating agent 2wt% calcium gluconaes, 1.0wt% ascorbic acid, 8wt% add oleic acid, and it is 0.5 that average grain diameter is milled to sand mill μm, the specific surface area (BET method) for obtaining grounds travel is 22m2/ g, the powder time processed is 12 hours.
15kOe carries out compacting green compact in magnetic field, and the pressure of compacting is about 0.5ton/cm2。
Green compact are that finished product is sintered 2 hours to obtain in nitrogen atmosphere at 1240 DEG C in sintering temperature, temperature rise rate is about 40 DEG C/ h.The W phases of finished product are 91%, remanent magnetism Br=372mT, magnetic induction coercivity H b=165kA/m, HCJ Hcj= 172kA/m, magnetic energy product (BH) max reaches 3.45MGOe.
Embodiment 4
Primary raw material is CuO, Fe2O3, BaO and MgO, a small amount of BaCO3、Al2O3、Cr2O3、B2O3、SiO2、MgCO3, burning Main constituents after knot meet following molecular formula：
BaMg(2-x)CuxFe 16O27, wherein x=0.8.Material powder is immersed in the water according to above-mentioned molecular formula proportioning, Mixed 3 hours in ball mill, the batch mixing that suspended particulate particle diameter is 0.1~2.0 μm is obtained, in 1312 DEG C of pre-burnings in nitrogen atmosphere 3 hours, XRD analysis determined the W phases containing 71wt% in thing phase, and its primary grain size is 10 μm.In ball mill grinding, directly Turn into the powder less than or equal to 6.0 μm to average grain diameter, the specific surface area (BET method acquisition) for obtaining grounds travel is about 10m2/ g。
It is heat-treated in a nitrogen atmosphere, temperature is 1000 DEG C, is incubated 3 hours, obtains a Preburning material.
Additive is subsequently added, additive each component addition is with a preburning powdered material weight than as follows respectively：1.0wt% CaCO3, 0.4wt%SiO2, 1.0wt%Al2O3With 0.4wt% ZrO2, surfactant 2.0wt% calcium gluconaes are added, 1.0wt% ascorbic acid, 8.0wt% adds oleic acid, and average grain diameter is milled to sand mill for 0.6 μm, the ratio table of grounds travel is obtained Area (BET method) is 25m2/ g, the powder time processed is 15 hours.
13000Oe carries out compacting green compact in magnetic field, and the pressure of compacting is about 0.5ton/cm2。
Green compact are that finished product is sintered 2 hours to obtain in nitrogen atmosphere at 1310 DEG C in sintering temperature, temperature rise rate is about 35 DEG C/ h.The M phases of finished product are 100%, remanent magnetism Br=400mT, magnetic induction coercivity H b=150kA/m, HCJ Hcj= 135kA/m, magnetic energy product (BH) max reaches 3.41MGOe.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic. Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's Within protection domain.

Claims (6)

1. one kind contains Cu2+W-type ferrite material, it is characterised in that be prepared for a kind of containing Cu first with china-clay method2+W sections oxygen Body powder, described W-type ferrite material is hexaplanar, and its chemical molecular formula is BaMg(2-x)CuxFe16O27, wherein, 0.001≤x≤1.6。
2. one kind contains Cu2+W-type ferrite material preparation, it is characterised in that：Preparation technology comprises the following steps：
(1) batch mixing：By chemical structural formula BaMg(2-x)CuxFe16O27Composition requirement, the corresponding oxide with contained component is former After material and the mixing of carbonated starting material powder, with water, steel ball is according to material：Water：Ball=1：1：8 weight is mixed than proportioning；Then, add Doping Al2O3、Cr2O3、B2O3And SiO2, its each component addition weight account for BaMg(2-x)CuxFe16O27Construction weight percentage Respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤Cr2O3≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%, will Above-mentioned gained dispensing carries out ball milling mixing and stirred 1~20 hour, obtains the batch mixing that suspended particulate average grain diameter is 0.1~2.0 μm；
(2) pre-burning：By gained batch mixing pre-burning 0.5~6 hour at 1000~1500 DEG C in step (1), W type permanent magnet oxygen is prepared Body material Preburning material；
(3) powder processed：First by gained W-type ferrite material Preburning material in step (2), it is 0.1 that average grain diameter is milled to ball mill ~5.0 μm of powder, then adds surfactant, and the weight of the surfactant accounts for BaMg(2-x)CuxFe16O27Structure weight It is 0.5~10% to measure percentage, finally, is mixed into additive A l2O3, Cr2O3, B2O3(or H3BO3), SiO2(or H2SiO3), addition Agent each component accounts for BaMg(2-x)CuxFe16O27Construction weight percentage is respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤Cr2O3 ≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%；Further adjustment is formulated, with BaMg(2-x)CuxFe16O27Dispensing, makes It is 0.01~10.0% that additive total amount, which accounts for Preburning material percentage by weight,.Then weight ratio is used for water：Material：Ball=1：1：8 use Ball mill (or sand mill), is milled to average grain diameter for 0.08~0.8 μm；
(4) green compact are suppressed：According to actual operation requirements, the size of mold shape is controlled, compacting green compact, compacting are carried out in magnetic field Pressure is 0.1~0.5ton/cm2, pulsed magnetic field intensity is 5.0~15.0kOe；
(5) sinter：By green compact at 900~1500 DEG C, device (such as tiles and ring-type are sintered to obtain in atmospheric oxidising atmosphere Deng), sintering time is 0.5~8 hour, and temperature rise rate is 30~500 DEG C/h；
(6) grinding and measurement：The magnetic patch that room temperature is cooled to after sintering is cut and is ground, according to GB/T3217-92 countries Standard is tested, measured.
3. one kind according to claim 2 contains Cu2+W-type ferrite material preparation, wherein described in step (1) Oxide raw material is CuO, Fe2O3、Fe3O4, MgO, carbonated starting material is BaCO3And MgCO3, the table wherein described in step (3) Face activating agent is 2 kinds or mixture of more than two kinds in calcium gluconae, glucose, sorbierite, ascorbic acid and oleic acid.
4. one kind according to claim 2 contains Cu2+W-type ferrite material preparation, it is characterised in that：Described W BaMg is removed in type ferrite material(2-x)CuxFe16O27Outside, additive is also included, the component of additive is Al2O3、Cr2O3、 B2O3、SiO2, its each component accounts for BaMg(2-x)CuxFe16O27Construction weight percentage is respectively 0.1%≤Al2O3≤ 2.0%, 0.1%≤Cr2O3≤ 2.0%, 0≤B2O3≤ 1.5%, 0≤SiO2≤ 1.6%.
5. one kind according to claim 2 contains Cu2+W-type ferrite material preparation, it is characterised in that：Preburning material exists 1~4 hour is incubated at 1200~1450 DEG C, green compact are at 950~1500 DEG C, and sintering time is 1~6 hour.
6. it is according to claim 2 a kind of containing Cu2+W-type ferrite material preparation, it is characterised in that：Magnetic after sintering Body rate of temperature fall is 30~50 DEG C/h.
CN201710281749.1A 2017-04-26 2017-04-26 One kind contains Cu2+W-type ferrite material and its preparation Pending CN107010937A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836148A (en) * 2019-02-22 2019-06-04 横店集团东磁股份有限公司 One kind is without La, Co element permanent-magnet ferrite material and preparation method thereof
CN112939590A (en) * 2021-03-12 2021-06-11 电子科技大学 Hexahexaferrite material for X-band quasi-planar device and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006135238A (en) * 2004-11-09 2006-05-25 Dowa Mining Co Ltd Magnetic powder, manufacturing method therefor, and bonded magnet using the same
CN103172360A (en) * 2013-01-04 2013-06-26 安徽大学 Plumbite type yttrium permanent magnetic ferrite material and preparation method thereof
CN103467082A (en) * 2013-09-02 2013-12-25 电子科技大学 W-type ferrite absorbent for millimeter waves
CN103964830A (en) * 2014-05-07 2014-08-06 宿州学院 Method for preparing permanent magnetic ferrite by low-temperature sintering
CN105253918A (en) * 2015-09-24 2016-01-20 南京工业大学 Preparation method of easy-dispersible hexagonal-plate shaped W-type ferrite BaZn2Fe16O27

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006135238A (en) * 2004-11-09 2006-05-25 Dowa Mining Co Ltd Magnetic powder, manufacturing method therefor, and bonded magnet using the same
CN103172360A (en) * 2013-01-04 2013-06-26 安徽大学 Plumbite type yttrium permanent magnetic ferrite material and preparation method thereof
CN103467082A (en) * 2013-09-02 2013-12-25 电子科技大学 W-type ferrite absorbent for millimeter waves
CN103964830A (en) * 2014-05-07 2014-08-06 宿州学院 Method for preparing permanent magnetic ferrite by low-temperature sintering
CN105253918A (en) * 2015-09-24 2016-01-20 南京工业大学 Preparation method of easy-dispersible hexagonal-plate shaped W-type ferrite BaZn2Fe16O27

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
牛晓飞: "掺杂W型铁氧体的制备、结构和磁性能的研究", 《万方数据，博士论文》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109836148A (en) * 2019-02-22 2019-06-04 横店集团东磁股份有限公司 One kind is without La, Co element permanent-magnet ferrite material and preparation method thereof
CN109836148B (en) * 2019-02-22 2021-04-20 横店集团东磁股份有限公司 Permanent magnetic ferrite material without La and Co elements and preparation method thereof
CN112939590A (en) * 2021-03-12 2021-06-11 电子科技大学 Hexahexaferrite material for X-band quasi-planar device and preparation method thereof
CN112939590B (en) * 2021-03-12 2022-10-14 电子科技大学 Hexahexaferrite material for X-band quasi-planar device and preparation method thereof

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Application publication date: 20170804