CN106145917A - A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method - Google Patents

A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method Download PDF

Info

Publication number
CN106145917A
CN106145917A CN201610466910.8A CN201610466910A CN106145917A CN 106145917 A CN106145917 A CN 106145917A CN 201610466910 A CN201610466910 A CN 201610466910A CN 106145917 A CN106145917 A CN 106145917A
Authority
CN
China
Prior art keywords
ball
ball milling
sintered
dispersant
strontium ferrite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610466910.8A
Other languages
Chinese (zh)
Inventor
王寅岗
张胜安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Aeronautics and Astronautics
Original Assignee
Nanjing University of Aeronautics and Astronautics
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University of Aeronautics and Astronautics filed Critical Nanjing University of Aeronautics and Astronautics
Priority to CN201610466910.8A priority Critical patent/CN106145917A/en
Publication of CN106145917A publication Critical patent/CN106145917A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/2633—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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/2658—Other ferrites containing manganese or zinc, e.g. Mn-Zn ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/2691—Other ferrites containing alkaline metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • 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
    • H01F1/032—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 hard-magnetic materials
    • H01F1/10—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 hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Hard Magnetic Materials (AREA)
  • Magnetic Ceramics (AREA)

Abstract

The invention discloses a kind of cheap secondary and be combined adding method, the HCJ of material can be improved on the premise of not reducing remanent magnetism.Its concrete steps: 1. dispensing: on the basis of Strontium ferrite powder, carry out the compound interpolation of secondary, 2. ball milling, add dispersant during ball milling, and wherein dispersant includes C6H14O6、HCOOH、Ca(C6H11O7)2、C6H7NaO6In one or more materials；3. it is dehydrated；4. it is molded；5. sinter；6. mill processing and performance test.It is cheap that secondary disclosed by the invention is combined additive involved in interpolation, addition without expensive rare earth or metal oxide containing precious metals, on the premise of the remanent magnetism ensureing material is constant, official report coercivity about about 136～144kA/m can be improved, reach 336～344kA/m.

Description

A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method
Technical field
The invention belongs to the preparation field of permanent-magnet ferrite in functional material, be specifically related to a kind of raising permanently magnetic strontium ferrite Coercitive secondary is combined adding method.
Background technology
Currently, the demand of whole world permanent-magnet ferrite is increasing year by year, and China is as the use big country of permanent-magnet ferrite, Its demand keeps more quickly increasing.M type permanent-magnet ferrite industry has obtained quick development in recent decades, China Yield has increased to the prostatitis in the world, but the permanent-magnet ferrite that problem is domestic most enterprises production is still chronically at Relatively low level, and raw material utilization rate is low, production technology lags far behind other countries.Therefore the performance of improving product, improvement Production technologies etc. are also the research emphasis in permanent-magnet ferrite material field all the time.
Permanent-magnet ferrite is primarily referred to as hexaplanar M-type strontium ferrite or barium ferrite, and its magnetic property index mainly has surplus Magnetic (Br), coercivity (Hcb、Hcj), magnetic energy product (BH)max, wherein remanent magnetism BrWith official report coercivity Hcj, the more big then magnet magnetic energy of its value Better.
Remanent magnetism (the B of magnetr) depend on density, the degree of orientation and the saturation magnetization (4 π Is) being determined by lattice, by under Formula is expressed:
Br=4 π Is × degree of orientation × density
M-type strontium ferrite and barium ferrite have the 4 π Is values of about 4.65kG.Density and the degree of orientation are at most theoretical value 98%, even density value and the sintered magnet being orientated angle value Wet-pressing molding the highest are also such.
HcjWith anisotropy field (HA=2K1/ Is) and the ratio (f of single domain crystal grainc) product be directly proportional (HA× fc), Wherein K1Represent the magnetocrystalline anisotropy constant being determined by crystal structure.Known M-type strontium ferrite has the K of maximum1Value, is difficult to Improve again.And if ferrite particle is single domain state, then HcjMaximum can be desired for, because magnetization has to resist anisotropy Field rotates, so that reversal of magnetism.
According to above theoretical can be replaced by ion doping to enhance product performance improve Preburning material microstructure or Person carries out secondary adding technology process etc. on the basis of existing Preburning material.For secondary adding technology, CaCO3, CaO and portion Dividing the additives such as rare-earth oxidation while improving remanent magnetism, material coercivity and HCJ are also with decline；Al2O3、 SiO2、Cr2O3、SrCO3、H3BO3Deng additive while improving material coercivity and HCJ, remanent magnetism is also with drastically Decline.This is also the faced subject matter of current secondary adding technology.Chinese invention patent (publication No. is CN102408229A) Disclose and a kind of improve the coercitive method of permanent-magnet ferrite, improve serving certain effect to the magnetic property of magnet, but its The additive R of research and developmentxAlyFezOmComplicated process of preparation, wastes time and energy, and the additive being simultaneously introduced contains the rare earth such as cobalt and praseodymium unit Element causes cost to greatly increase.
Content of the invention
For above-mentioned existing problem, the present invention is by the selection of additive, the groping and addition manner of adding proportion Optimization, work out a kind of coercitive secondary of material that improves on the premise of keeping remanent magnetism not drop and be combined adding method.
For achieving the above object, the present invention is by the following technical solutions:
A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method, comprises the following steps:
Dispensing: on the basis of Strontium ferrite powder, carries out the compound interpolation of secondary, and secondary Compound Supplement first carries out pre-place Reason, the mass percent of shared gross weight are 1%～6%, and described secondary Compound Supplement is in A class, B class and C class material The mixture of one or more, described A class material is CaCO3、SiO2·nH2O、H3BO3, B class material is Al2O3、Cr2O3、 MgO、Mn2O3, C class material is NaCl, KCl；
Ball milling: adding dispersant, carrying out secondary ball milling in ball mill, steel ball used is diameter 5.50～7.50mm Bearing steel ball, Ball-milling Time is >=18h；Material, ball, the mass percent of water are 1:(13～16): (1.6～1.9), secondary ball milling Rear Slurry Granularity≤0.9 μm；
Dehydration: the slip of secondary ball milling being transferred to dewaterer and being dehydrated, dewatering time is 5～12h, makes containing of slip Water rate reaches 34～45%；
Shaping: use Wet-pressing molding machine to be pressed the slip after dehydration under magnetic field, the size of compacting sample For: a diameter of 25mm, high 10mm, density >=5.20g/cm3；
Sintering: in tube furnace, sample formation blank is sintered；
Grinding and performance test: after the sample cooling after to be sintered, polish upper and lower surface, meet product requirement, use MATS-2010 permanent magnetism measurement apparatus carries out magnetism testing to prepared sample.
Further, the mass percent of gross weight shared by secondary Compound Supplement after pretreatment is respectively as follows: 0.2% ～1.4%CaCO3, 0.15%～0.4%Al2O3, 0.5%～1.3%Cr2O3, 0.1%～0.9%H3BO3, 0.05%～ 0.45%SiO2·nH2O, 0.3%～0.9%MgO, 0.25%～1.2%Mn2O3, 0.1%～0.8%NaCl, 0.05%～ 0.65%KCl.
Further, the preprocess method of secondary Compound Supplement is: by formula weighings → ball milling → sintering → crush → Fine grinding → sieve, the secondary additive powder after finally sieving is dissolved in organic solvent, prepares secondary Compound Supplement, its Middle organic solvent is (CH2OH)2、CH3COCH3、CH3CH2Two or more organic matter in OH or polyethylene glycol.
Further, the dispersant that step (2) is added in mechanical milling process is C6H14O6、HCOOH、Ca(C6H11O7)2、 C6H7NaO6In one or more materials, wherein the percentage by weight shared by dispersant is respectively 0.6%～1.3%.
Further, the compressing pressure described in step (4) is 0.35～0.5 ton/cm2, the electric current that magnetizes is 15.0A, externally-applied magnetic field is approximately 5～15KOe, pressurize 3.5s, and demagnetize 4s.Under magnetic field, oriented moulding is carried out to shaping slip.
Method according to claim 1, is characterized in that, step (5), in sintering process, is first 300～360 Being sintered at a temperature of DEG C, sintering time 2h, this stage is mainly draining and dispersant and decomposes, after with the intensification of 5 DEG C/min Speed is sintered to 1185～1205 DEG C, and sintering time is 4h, is incubated 2h.
Beneficial effect:
1.A class material has the effect carrying remanent magnetism, and B class material has the effect carrying HCJ, and NaCl, KCl are to this Two performances all have some improvement, and after carrying out the compound interpolation of secondary according to the formula dispensing of the present invention, can keep the surplus of material On the premise of magnetic does not drops, it is reported coercivity and is greatly improved (about 136～144kA/m), and to the shaping of product and burning Knot has no effect.
2. formula components is not necessarily to the interpolation of some noble heavy metal oxides or rare earth element, and price is more cheap, to performance To promote the effect that the secondary with some noble heavy metal oxides or rare earth element adds suitable, more meet big production requirement.
3. two compound additives adding are after pretreatment, and additive distribution more evenly and effectively inhibits and adds Add the loss of thing.
Brief description
The demagnetizing curve figure of Fig. 1 embodiment 2；
Fig. 2 is the cross-sectional scans Electronic Speculum figure that the embodiment of the present invention 2 prepares sample；
Fig. 3 is the cross-sectional scans Electronic Speculum figure that comparative example prepares sample.
Detailed description of the invention
Embodiment 1
A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method, specifically comprises the following steps that at strontium ferrite On the basis of Preburning material, carrying out that secondary is compound to be added, secondary Compound Supplement first carries out pre-processing, the quality of shared gross weight Percentage is 1%, and secondary Compound Supplement after pretreatment includes 0.2%CaCO3, 0.15%Al2O3, 0.5%Cr2O3、 0.1%H3BO3, 0.05%SiO2·nH2O.Add dispersing agent C6H14O6, HCOOH and Ca (C6H11O7)2Mixture shared by weight Percentage is 7%.Carrying out secondary ball milling in ball mill, steel ball used is the bearing steel ball of diameter 5.50～7.50mm, ball Time consuming is >=18h；Material, ball, the mass percent of water are 1:(13-16): (1.6-1.9), Slurry Granularity after secondary ball milling≤ 0.9μm.The slip of secondary ball milling being transferred to dewaterer be dehydrated, dewatering time is 5～12h, uses Wet-pressing molding machine pair Slip after dehydration is pressed under magnetic field, and briquetting pressure is 0.35～0.5 ton/cm2, the electric current that magnetizes is 15.0A, outward Adding magnetic field and being approximately 5～15KOe, pressurize 3.5s, demagnetize 4s, and the size of compacting sample is: a diameter of 25mm, high 10mm, and density >= 5.20g/cm3.Sample formation blank is sintered by tube furnace, is sintered at a temperature of 300～360 DEG C, during sintering Between 2h, after be sintered to 1185～1205 DEG C with the programming rate of 5 DEG C/min, sintering time is 4h, is incubated 2h.After to be sintered Sample cooling after, polish upper and lower surface, meet product requirement, use MATS-2010 permanent magnetism measurement apparatus to enter prepared sample Row magnetism testing.
The magnetic property of embodiment 1 is: Br=401.5mT, Hcb=301.6kA/m, Hcj=328.2kA/m, (BH)max= 31.7kJ/m3.Embodiment 2
Compared with Example 1, the percentage by weight of secondary compound additive is 3%, and secondary after pretreatment is compound to be added Add thing and include 1.0%CaCO3, 0.15%Al2O3, 0.6%Cr2O3, 0.25%H3BO3, 0.2%SiO2·nH2O, 0.3% MgO, 0.2%Mn2O3, 0.3%NaCl.
Fig. 1 is the demagnetizing curve figure of the present embodiment, and thus figure is it can be seen that the magnetic property of embodiment 2 is: Br= 412.7mT, Hcb=310.6kA/m, Hcj=338.6kA/m, (BH)max=33.9kJ/m3。
Embodiment 3
Compared with Example 1, the percentage of secondary compound additive is 5%, secondary Compound Supplement after pretreatment Include 1.0%CaCO3, 0.4%Al2O3, 1.0%Cr2O3, 0.6%H3BO3, 0.6%SiO2·nH2O, 0.4%MgO, 0.5%Mn2O3, 0.5%KCl.The magnetic property of embodiment 3 is: Br=390.8mT, Hcb=300.3kA/m, Hcj=319.2kA/ M, (BH)max=30.4kJ/m3。
Comparative example
On the basis of Preburning material of strontium ferrite, do not carry out any interpolation, add dispersing agent C6H14O6、HCOOH、Ca (C6H11O7)2Percentage by weight shared by mixture is 7%, carries out secondary ball milling in ball mill, and steel ball used is diameter 5.50 The bearing steel ball of～7.50mm, Ball-milling Time is >=18h；Material, ball, the mass percent of water are 1:(13-16): (1.6-1.9), Slurry Granularity≤0.9 μm after secondary ball milling.The slip of secondary ball milling to be transferred to dewaterer be dehydrated, dewatering time is 5～ 12h, uses Wet-pressing molding machine to be pressed the slip after dehydration under magnetic field, and briquetting pressure is 0.35～0.5 ton/ cm2, the electric current that magnetizes is 15.0A, and externally-applied magnetic field is approximately 5～15KOe, pressurize 3.5s, and demagnetize 4s, and the size of compacting sample is: straight Footpath is 25mm, high 10mm.Sample formation blank is sintered by tube furnace, is sintered at a temperature of 300～360 DEG C, Sintering time 2h, after be sintered to 1185～1205 DEG C with the programming rate of 5 DEG C/min, sintering time is 4h, is incubated 2h.Treat After sample cooling after sintering, polish upper and lower surface, meet product requirement, use MATS-2010 permanent magnetism measurement apparatus to preparing Sample carries out magnetism testing.
The magnetic property of comparative example is: Br=420.6mT, Hcb=168.9kA/m, Hcj=178.0kA/m, (BH)max= 34.1kJ/m3。
By contrast, the strontium ferrite sample remanent magnetism that embodiment prepares quite and coercivity apparently higher than comparative example.Fig. 2 with Fig. 3 embodiment of comparing is more tiny than comparative example even particle distribution and fine and close.
The above is only the preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art For Yuan, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (6)

1. the raising coercitive secondary of permanently magnetic strontium ferrite is combined adding method, it is characterised in that comprise the following steps:
1) dispensing: on the basis of Strontium ferrite powder, carries out the compound interpolation of secondary, and secondary Compound Supplement first carries out pre-place Reason, the mass percent of shared gross weight are 1%～6%, and described secondary Compound Supplement is in A class, B class and C class material The mixture of one or more, described A class material is CaCO3、SiO2·nH2O、H3BO3, B class material is Al2O3、Cr2O3、 MgO、Mn2O3, C class material is NaCl, KCl；
2) ball milling: adding dispersant, carrying out secondary ball milling in ball mill, steel ball used is the axle of diameter 5.50～7.50mm Holding steel ball, Ball-milling Time is >=18h；Material, ball, the mass percent of water are 1:(13～16): (1.6～1.9), after secondary ball milling Slurry Granularity≤0.9 μm；
3) it is dehydrated: the slip of secondary ball milling being transferred to dewaterer and being dehydrated, dewatering time is 5～12h, makes the aqueous of slip Rate reaches 34～45%；
4) being molded: use Wet-pressing molding machine to be pressed the slip after dehydration under magnetic field, the size of compacting sample is: A diameter of 25mm, high 10mm, density >=5.20g/cm3；
5) sinter: in tube furnace, sample formation blank is sintered；
6) grinding and performance test: after the sample cooling after to be sintered, polish upper and lower surface, meet product requirement, use MATS- 2010 permanent magnetism measurement apparatus carry out magnetism testing to prepared sample.
2. method according to claim 1, it is characterised in that gross weight shared by secondary Compound Supplement after pretreatment Mass percent be respectively as follows: 0.2%～1.4%CaCO3, 0.15%～0.4%Al2O3, 0.5%～1.3%Cr2O3, 0.1% ～0.9%H3BO3, 0.05%～0.45%SiO2·nH2O, 0.3%～0.9%MgO, 0.25%～1.2%Mn2O3, 0.1% ～0.8%NaCl, 0.05%～0.65%KCl.
3. method according to claim 1, it is characterised in that the preprocess method of secondary Compound Supplement is: by formula Weighing → ball milling → sintering → broken → fine grinding → sieve, the secondary additive powder after finally sieving is dissolved in organic solvent In, prepare secondary Compound Supplement, wherein organic solvent is (CH2OH)2、CH3COCH3、CH3CH2In OH or polyethylene glycol two kinds Or two or more organic matter.
4. method according to claim 1, is characterized in that, the dispersant that step (2) is added in mechanical milling process is C6H14O6、HCOOH、Ca(C6H11O7)2、C6H7NaO6In one or more materials, the wherein percentage by weight shared by dispersant It is respectively 0.6%～1.3%.
5. method according to claim 1, is characterized in that, the compressing pressure described in step (4) is 0.35～0.5 Ton/cm2, the electric current that magnetizes is 15.0A, and externally-applied magnetic field is approximately 5～15KOe, pressurize 3.5s, and demagnetize 4s.
6. method according to claim 1, is characterized in that, step (5), in sintering process, is first at 300～360 DEG C At a temperature of be sintered, sintering time 2h, this stage is mainly draining and dispersant and decomposes, after with the intensification speed of 5 DEG C/min Degree is sintered to 1185～1205 DEG C, and sintering time is 4h, is incubated 2h.
CN201610466910.8A 2016-06-23 2016-06-23 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method Pending CN106145917A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610466910.8A CN106145917A (en) 2016-06-23 2016-06-23 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610466910.8A CN106145917A (en) 2016-06-23 2016-06-23 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method

Publications (1)

Publication Number Publication Date
CN106145917A true CN106145917A (en) 2016-11-23

Family

ID=57349205

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610466910.8A Pending CN106145917A (en) 2016-06-23 2016-06-23 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method

Country Status (1)

Country Link
CN (1) CN106145917A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699155A (en) * 2016-12-21 2017-05-24 马鞍山起劲磁塑科技有限公司 Strontium ferrite magnetic powder additive
CN107117954A (en) * 2017-04-27 2017-09-01 横店集团东磁股份有限公司 A kind of preparation method of high-performance permanent-magnet ferrite
CN110204326A (en) * 2019-05-16 2019-09-06 横店集团东磁股份有限公司 A kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure
CN110511012A (en) * 2019-07-22 2019-11-29 横店集团东磁股份有限公司 A kind of preparation method of the ferrite permanent-magnet materials with ultra-fine grained structure

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6994797B2 (en) * 2001-02-07 2006-02-07 Neomax Co., Ltd. Permanent magnet and method for preparation thereof
CN103058641A (en) * 2011-12-14 2013-04-24 南京梅山冶金发展有限公司 Method for preparing non-rare-earth high-magnetism permanent magnetic ferrite material
CN103304230A (en) * 2013-06-13 2013-09-18 东阳市金砖磁业有限公司 Permanent magnetic ferrite low-temperature pre-sintering powder and preparation method thereof
CN103724004A (en) * 2013-11-13 2014-04-16 横店集团东磁股份有限公司 High-coercivity permanent magnetic ferrite material and preparation method thereof
CN103964829A (en) * 2014-05-07 2014-08-06 宿州学院 Preparation and sintering of single-aperture blank of oxygen self-supported permanent magnetic ferrite pre-sintering material
CN104496444A (en) * 2014-09-15 2015-04-08 横店集团东磁股份有限公司 Low-cost sintered permanent magnet ferrite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6994797B2 (en) * 2001-02-07 2006-02-07 Neomax Co., Ltd. Permanent magnet and method for preparation thereof
CN103058641A (en) * 2011-12-14 2013-04-24 南京梅山冶金发展有限公司 Method for preparing non-rare-earth high-magnetism permanent magnetic ferrite material
CN103304230A (en) * 2013-06-13 2013-09-18 东阳市金砖磁业有限公司 Permanent magnetic ferrite low-temperature pre-sintering powder and preparation method thereof
CN103724004A (en) * 2013-11-13 2014-04-16 横店集团东磁股份有限公司 High-coercivity permanent magnetic ferrite material and preparation method thereof
CN103964829A (en) * 2014-05-07 2014-08-06 宿州学院 Preparation and sintering of single-aperture blank of oxygen self-supported permanent magnetic ferrite pre-sintering material
CN104496444A (en) * 2014-09-15 2015-04-08 横店集团东磁股份有限公司 Low-cost sintered permanent magnet ferrite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
毕见强等: "《特种陶瓷工艺与性能》", 31 March 2008, 哈尔滨工业大学出版社 *
王自敏等: "《铁氧体生产工艺技术》", 31 January 2013, 重庆大学出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699155A (en) * 2016-12-21 2017-05-24 马鞍山起劲磁塑科技有限公司 Strontium ferrite magnetic powder additive
CN107117954A (en) * 2017-04-27 2017-09-01 横店集团东磁股份有限公司 A kind of preparation method of high-performance permanent-magnet ferrite
CN110204326A (en) * 2019-05-16 2019-09-06 横店集团东磁股份有限公司 A kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure
CN110511012A (en) * 2019-07-22 2019-11-29 横店集团东磁股份有限公司 A kind of preparation method of the ferrite permanent-magnet materials with ultra-fine grained structure
CN110511012B (en) * 2019-07-22 2020-09-01 横店集团东磁股份有限公司 Preparation method of ferrite permanent magnetic material with ultra-fine grain structure

Similar Documents

Publication Publication Date Title
CN103964828A (en) High-performance permanent magnet ferrite material and preparing method thereof
CN106145917A (en) A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method
CN101552069A (en) Magnetoplumbite permanent magnetic ferrite and method of producing the same
CN104230323A (en) M-type calcium-lanthanum-cobalt permanent magnetic ferrite and preparation method thereof
CN104692785A (en) High performance strontium-calcium permanent magnetic ferrite magnet and preparation method thereof
CN109400139A (en) A kind of preparation process of low cost permanent-magnet ferrite material
CN103172360A (en) Plumbite type yttrium permanent magnetic ferrite material and preparation method thereof
CN104609843A (en) Preparation method for non-rare-earth high-remanent-magnetism permanent-magnetism ferrite
CN105060870A (en) Preparation method for hexagonal strontium ferrite with high coercivity
CN110372365A (en) A kind of preparation method of permanent-magnet ferrite material
CN107293398A (en) A kind of preparation method of permanent-magnet ferrite material
CN104230325A (en) Preparation method of permanent magnetic ferrite pre-sintering material and preparation method of permanent magnetic ferrite
CN104496457A (en) Rare earth-containing permanent magnetic ferrite and manufacturing method thereof
CN101599332B (en) Method for preparing magnetic material of rare-earth permanent magnet ferrite
JP4820312B2 (en) Ferrite magnetic powder for bonded magnet, method for producing the same, and bonded magnet
CN103964829A (en) Preparation and sintering of single-aperture blank of oxygen self-supported permanent magnetic ferrite pre-sintering material
CN103232232B (en) Permanent magnetic ferrite preparation method
CN114804847B (en) Permanent magnetic ferrite and preparation method thereof
CN108285348A (en) A kind of manufacturing method of dry-pressing opposite sex permanent-magnet ferrite magnetic powder
CN109836147A (en) A kind of permanent-magnet ferrite and preparation method thereof
CN102129906B (en) Permanent ferrite material additive and preparation method and application thereof
CN102731080B (en) Processing method for preparing powder used for ferrite magnetic material
CN107445607A (en) A kind of high-performance permanent-magnet ferrite with extremely low Hcj temperatures coefficient and preparation method thereof
CN106083022A (en) A kind of permanent-magnet ferrite material and preparation method thereof
CN115385676B (en) Method for preparing middle-high grade permanent magnetic ferrite by taking iron concentrate powder as raw material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20161123

RJ01 Rejection of invention patent application after publication