CN111362686A - Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof - Google Patents

Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof Download PDF

Info

Publication number
CN111362686A
CN111362686A CN201911234047.3A CN201911234047A CN111362686A CN 111362686 A CN111362686 A CN 111362686A CN 201911234047 A CN201911234047 A CN 201911234047A CN 111362686 A CN111362686 A CN 111362686A
Authority
CN
China
Prior art keywords
molding
permanent magnetic
magnetic ferrite
ferrite material
particle size
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
CN201911234047.3A
Other languages
Chinese (zh)
Inventor
杨武国
申屠金昂
方盛翔
吴赛航
何震宇
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.)
Hengdian Group DMEGC Magnetics Co Ltd
Original Assignee
Hengdian Group DMEGC Magnetics Co Ltd
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 Hengdian Group DMEGC Magnetics Co Ltd filed Critical Hengdian Group DMEGC Magnetics Co Ltd
Priority to CN201911234047.3A priority Critical patent/CN111362686A/en
Publication of CN111362686A publication Critical patent/CN111362686A/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
    • C04B35/2633—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
    • C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead
    • 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
    • C04B35/265—Compositions containing one or more ferrites of the group comprising manganese or zinc and one or more ferrites of the group comprising nickel, copper or cobalt
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide 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
    • C04B2235/32—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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • 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
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Landscapes

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

Abstract

The invention relates to the technical field of ferrite material preparation, and discloses a hexa-magnetic plumbite permanent magnetic ferrite material and a preparation method thereof, wherein the general formula of the permanent magnetic ferrite material is A1‑x‑yCaxRyFe2n‑ zMzO19Wherein: a is Sr or Sr and Ba, R comprises La, and M comprises Co; x is 0.15 to0.4, y is 0.3 to 0.5, z is 0.25 to 0.45, and n is 5.3 to 5.7. The preparation method comprises the following steps: proportioning, presintering, ball milling, molding and sintering. The invention is based on hexagonal Sr ferrite and adopts La3+Ion and Ca2+Ion co-substitution of Sr2+The damage of the crystal structure of the magnet is avoided, and Co is effectively improved2+The substitution amount of ions enables the prepared permanent magnetic ferrite material to obtain high remanence and intrinsic coercive force at the same time.

Description

Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof
Technical Field
The invention relates to the technical field of ferrite material preparation, in particular to a hexagonal magnetoplumbite permanent magnetic ferrite material and a preparation method thereof.
Background
Permanent magnetic materials can keep constant magnetism once magnetized, and are also called hard magnetic materials. Commonly used permanent magnet materials are classified into alnico, ferrite permanent magnet, rare earth permanent magnet, and various composite permanent magnet materials.
The permanent magnetic ferrite magnet is one of key basic functional materials of a permanent magnetic direct current motor, has the characteristics of high residual magnetic flux density, high coercive force, high magnetic energy product and the like, can meet the use requirements of the motor in various environments such as a strong demagnetizing field, low temperature, high altitude and the like, has high sensitivity and stability, and can be widely applied to various motors with high power, high rotating speed and high torque, such as high-grade automobile motors (ABS motors, starting motors and the like), motorcycle starting motors, household appliances, electric tool motors and the like.
The original permanent magnetic ferrite material mainly adopts strontium ferrite (SrO.6Fe) with a magnetoplumbite hexagonal structure2O3) And barium ferrite (BaO.6Fe)2O3) To prepare the compound. Two main parameters that determine the magnetic properties of sintered permanent magnetic ferrite are residual magnetic flux density (Br) and intrinsic coercive force (Hcj). In recent years, with the application of an ion-exchange formulation technology represented by La-Co substitution, the performance of the permanent magnetic ferrite is greatly improved, and related researchers at home and abroad successively develop permanent magnetic ferrite materials with remanence of about 4500Gs and intrinsic coercivity of 5000Oe, such as Chinese application patents 200510006196.6, 200510118623.X, 200510023312.5 and the like. The three patents are based on the replacement of Sr ferrite by La-Co (also called Sr-La-Co ferrite), and the magnetic performance is approximately 4200-4500Gs, and the intrinsic coercive force is not more than 5000 Oe.
With Ca asPermanent magnetic ferrite (also called Ca ferrite) with only CaO-Fe as main component2O3And CaO-2Fe2O3Is stable, like CaO-6Fe of typical Sr ferrite2O3And are not structurally stable. By La-Co substitution, the formed Ca-La-Co ferrite can be structurally stable and has magnetic properties comparable to that of the common Sr-La-Co ferrite. Japanese laid-open patent (Japanese laid-open patent No. 2000-223307) discloses a Ca-La-Co ferrite of which the higher magnetic property shown in the examples can be achieved with Br of 4490Gs and Hcj of 4540 Oe.
In recent years, other ion doping studies have been conducted on the Ca — La — Co ferrite system, and for example, chinese application 201611209131.6 has obtained a magnet with better magnetic properties of Br4300Gs, Hcj4450Oe by further using a small amount of F instead of O. The Chinese patent application 201710399787.7 further adds monovalent alkali metal lithium, sodium or potassium ions for substitution, and obtains a magnet with better magnetic properties of about Br4500Gs and Hcj5000 Oe.
However, both the Sr-La-Co ferrite system and the Ca-La-Co ferrite system in the prior art are difficult to obtain high remanence and higher intrinsic coercive force at the same time, and cannot meet the higher and higher use requirements.
Disclosure of Invention
The invention provides a hexaferrite permanent magnetic ferrite material and a preparation method thereof, aiming at overcoming the problems that the permanent magnetic ferrite in the prior art is difficult to obtain high remanence and higher intrinsic coercive force at the same time and cannot meet the higher and higher use requirements, and the hexaferrite permanent magnetic ferrite material is based on hexaferrite Sr and adopts La3+With Ca2+Together substituted for Sr2+And in addition, the remanence and intrinsic coercivity of the prepared sintered permanent magnetic ferrite material are both obviously improved compared with those of the permanent magnetic ferrite in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hexagonal magnetoplumbite permanent magnetic ferrite material is characterized in that the general formula is A1-x-yCaxRyFe2n-zMzO19Wherein: a is SrOr Sr and Ba, wherein R comprises La and M comprises Co; x is 0.15 to 0.4, y is 0.3 to 0.5, z is 0.25 to 0.45, and n is 5.3 to 5.7.
Preferably, R also comprises one or more of Pr, Nd and Bi.
Preferably, M further comprises Ni and/or Zn.
Preferably, z/y is 0.6 to 1.0.
The magnetic properties of Sr-La-Co ferrite cannot be further improved because the degree of La-Co substitution is limited. It is known that various magnetic properties of a magnet are improved from Sr ferrite to Sr-La-Co ferrite, mainly because of Co2+Ion partially substituting Fe3+Ions, while in order to maintain electrovalence balance, it is necessary to use part of La3+Ion substitution of Sr in hexagonal crystal structure2+Ions. But because of La3+Ionic radius (0.122nm) of Sr2+The ion (0.113nm) is slightly larger, so the magnet crystal structure is influenced along with the gradual increase of the La-Co substitution amount, and nonmagnetic LaFeO is easily generated3Thereby influencing the further improvement of the magnetic performance of the Sr-La-Co ferrite.
Therefore, the hexagonal Sr ferrite is used as the base, the more La-Co is added to ensure that the ferrite obtains more excellent magnetic property, and meanwhile, partial Ca is added to avoid the damage of the crystal structure of the magnet2+By using La3+Ion and Ca2+Jointly substituting Sr by ions (with the ionic radius of 0.099nm)2+Effectively improve Co2+The substitution amount of ions enables the prepared permanent magnetic ferrite material to obtain high remanence and intrinsic coercive force at the same time.
The invention also provides a preparation method of the hexagonal magnetoplumbite permanent magnetic ferrite material, which comprises the following steps:
(1) preparing materials: mixing raw material compounds containing each element according to the molar ratio of each element in the general formula, and crushing the mixture into mixed slurry with the average particle size of less than or equal to 0.8 mu m by a wet mixing process;
(2) pre-burning: drying the mixed slurry, and then pre-burning in air at 1150-1280 ℃ to obtain a pre-burnt material;
(3) ball milling: adding secondary additives and additives into the pre-sintered material, and grinding the mixture into particles with the average particle size of less than or equal to 0.65 mu m by a wet mixing process to obtain molding slurry;
(4) molding: adjusting the solid content of the molding slurry to 65-80 wt%, and then performing magnetic field molding to obtain a molding body, wherein the molding magnetic field intensity is more than or equal to 13000 Gs;
(5) and (3) sintering: the molded body is firstly subjected to heat preservation for 0.5-2 h at 100-600 ℃, and then is sintered in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air) to obtain the permanent magnetic ferrite material, wherein the sintering temperature is 1100-1300 ℃, and the sintering time is 0.1-3 h.
By using the method disclosed by the invention, the hexagonal magnetoplumbite permanent magnetic ferrite material with the general formula can be successfully prepared, and the average particle size of the mixed slurry after wet mixing in the step (1) is less than or equal to 0.8 mu M, so that the situation that the pre-sintering is insufficient and the content of generated M-phase ferrite is too low, which is easily caused in the pre-sintering process, due to overlarge particle size of the mixed slurry after mixing is avoided; the mixed slurry is dried and then pre-sintered in the step (2), so that the raw material compound can be fully subjected to solid phase reaction to generate a hexagonal crystal phase, and the obtained pre-sintered material has good quality characteristics and better meets the magnetic performance requirement of a subsequent process; the average particle size of the forming slurry in the step (3) is controlled to be below 0.65 mu m, so that the phenomenon that the average particle size of the slurry is too coarse, the grain size in a sintered body is too coarse after sintering, and the coercive force of the sintered body is influenced is avoided; in the step (4), proper forming magnetic field intensity is adopted to prevent the orientation degree of magnetic particles in the forming body from being too low due to too low forming magnetic field, so that the residual magnetism of the final magnet is influenced; in the step (5), the temperature is kept at 200-400 ℃ for 0.5-2 h to remove the water and additives in the molding material blank, and then the molding material blank is sintered in an oxygen-rich atmosphere, which is helpful for reducing Fe in the sintered body2+The content of the ions increases the specific saturation magnetization of the sintered body itself.
Therefore, the magnetic particles in the preparation process of the invention have good orientation and uniform grain size, and the prepared permanent magnetic ferrite material has high remanence and intrinsic coercive force.
Preferably, the raw material compound containing each element in the step (1) is: sr, Ba and Ca adopt carbonates thereof as raw material compounds; oxides or hydroxides of La, Pr and Nd are used as raw material compounds; fe. Co, Ni, Zn and Bi use their oxides as raw material compounds. The compound is used as a raw material compound, and ions in the raw material compound can effectively react with the hexagonal magnetoplumbite permanent magnetic ferrite material with the general formula in the invention in the preparation process.
Preferably, the average particle size of each starting compound in step (1) is 5 μm or less. The average particle size after wet mixing can meet the process requirements.
Preferably, the pre-sintering time in the step (2) is 0.1 to 3 hours. The solid phase reaction of the raw material compound can be fully carried out to generate a hexagonal crystal phase, so that the obtained pre-sintering material has good quality characteristics and better meets the magnetic performance requirement of the subsequent process.
Preferably, the secondary additive in step (3) comprises 0.05-2.0 wt% of SiO in terms of solid content20.4 to 2.0wt% of CaCO30 to 2.0wt% of Al2O30 to 1.5wt% of Cr2O30 to 0.6wt% of ZnO, 0.1 to 1.0wt% of SrCO3And 0 to 0.8wt% of H3BO3The average grain size of the secondary additive is less than or equal to 5 mu m. The addition of the secondary additives in the above components and contents is helpful to inhibit the grain expansion during sintering, increase the degree of compactness of the product, and improve the degree of orientation of the magnetic particles, thereby improving the remanence and intrinsic coercivity of the product.
Preferably, the additive in the step (3) comprises one or more of calcium gluconate, polyvinyl alcohol and sorbitol, and the addition amount is 0.2-1.2 wt% of the solid content. The additive can be added to improve the dispersibility of the molding slurry, so that the orientation of slurry particles during magnetic field molding is improved, and the remanence of a final product is improved; when the additive is added in an excessively large amount, insufficient discharge of organic substances is likely to occur in the subsequent sintering process, resulting in a decrease in the density of the sintered body. The average particle size of the molding slurry is controlled to 0.65 μm or less, and if the average particle size of the slurry is too coarse, the grain size in the sintered body after sintering tends to be too coarse, which affects the coercive force of the sintered body.
Therefore, the beneficial effects of the invention are as follows: based on hexagonal Sr ferrite and La3+Ion and Ca2+Ion co-substitution of Sr2+The damage of the crystal structure of the magnet is avoided, and Co is effectively improved2+The substitution amount of ions enables the prepared permanent magnetic ferrite material to obtain high remanence and intrinsic coercive force at the same time.
Detailed Description
The invention is further described with reference to specific embodiments.
The starting compounds used in the examples of the invention are as follows:
iron oxide red: wherein Fe2O3The content is more than or equal to 99.5wt percent, and Cl is added-The ion content is less than or equal to 0.1 wt%, and the original average particle size of the particles is 1.6 mu m;
strontium carbonate: wherein SrCO3More than or equal to 98.0 wt%, and the original average particle size of the particles is 2.1 mu m;
calcium carbonate: wherein CaCO3Not less than 99.0 wt%, and the original average particle size of the particles is 4.2 μm;
lanthanum oxide: wherein La2O3Not less than 99.0 wt%, and the original average particle size of the particles is 4.5 μm;
cobalt oxide: wherein Co2O3Not less than 99.0 wt%, and the original average particle size of the particles is 2.5 μm;
barium carbonate: wherein BaCO3More than or equal to 98.0 wt%, and the original average particle size of the particles is 3.1 mu m;
praseodymium oxide: wherein Pr2O3Not less than 99.0 wt%, and the original average particle size of the particles is 4.0 μm;
neodymium oxide: wherein Nd2O3Not less than 99.0 wt%, and the original average particle size of the particles is 4.0 μm;
nickel oxide: wherein NiO is more than or equal to 99.0 wt%, and the original average particle size of the particles is 3.5 mu m;
zinc oxide: wherein ZnO is more than or equal to 99.0 wt%, and the original average particle size of the particles is 3.5 μm.
Example 1:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.32Ca0.24La0.44Fe10.87Co0.34O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixing ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 2:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.33Ca0.22La0.35Pr0.10Fe10.91Co0.34O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, praseodymium oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixed ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering in air at 1150 ℃, and preserving heat for 2 hours to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 3:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.34Ca0.25La0.32Nd0.09Fe10.89Co0.35O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, neodymium oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixed ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then, 0.6wt% of glucose based on the solid content is addedAdding 680mL of deionized water serving as a ball milling medium, and performing wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 4:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.35Ca0.23La0.28Pr0.08Nd0.06Fe10.90Co0.3 4O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, praseodymium oxide, neodymium oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixed ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 5:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.33Ca0.22La0.45Fe10.91Co0.28Ni0.08O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, cobaltous oxide and nickel oxide into a wet ball mill according to the molar ratio of each element in the main phase type for mixing and ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 6:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.35Ca0.24La0.41Fe10.95Co0.25Zn0.09O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, cobaltous oxide and zinc oxide into a wet ball mill according to the molar ratio of each element in the main phase type for mixing and ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 7:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.34Ca0.23La0.43Fe10.93Co0.24Ni0.06Zn0.0 7O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide, cobaltous oxide, nickel oxide and zinc oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixed ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 8:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.4Ca0.2La0.4Fe10.3Co0.3O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixing ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1250 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.6 weight percent of the solid content is added20.8wt% of CaCO30.3 wt% of Cr2O30.3 wt% of ZnO, then 0.2 wt% of calcium gluconate, and then 680mL of deionized water is added as a ball milling medium, and wet grinding is carried out in a high-efficiency ball mill for 22h to obtain molding slurry with the average particle size of 0.62 μm;
(4) molding: adjusting the water content of the slurry for molding, adjusting the solid content of the slurry to 70%, then molding to obtain a molded body, and applying a molding magnetic field of 13000Oe in the pressing direction while pressing, wherein the obtained molded body is a cylinder with the diameter of 43.2mm and the height of 13mm, and the molding pressure is 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 100 ℃ for 2h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), raising the temperature at a speed of 150 ℃/h, and preserving the temperature at 1100 ℃ for 3h to obtain the permanent magnetic ferrite material.
Example 9:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.4Ca0.2La0.4Fe11.1Co0.3O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixing ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1280 ℃ in air, and preserving heat for 1h to obtain granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.6 weight percent of the solid content is added20.8wt% of CaCO30.3 wt% of Cr2O3Then adding calcium gluconate accounting for 1.2wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 22h in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.62 mu m;
(4) molding: adjusting the water content of the slurry for molding, adjusting the solid content of the slurry to 70%, then molding to obtain a molded body, and applying a molding magnetic field of 13000Oe in the pressing direction while pressing, wherein the obtained molded body is a cylinder with the diameter of 43.2mm and the height of 13mm, and the molding pressure is 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 0.5h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), raising the temperature at a speed of 150 ℃/h, and preserving the temperature at 1210 ℃ for 2h to obtain the permanent magnetic ferrite material.
Example 10:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.19Ba0.16Ca0.23La0.43Fe10.89Co0.35O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, barium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixed ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering in air at 1150 ℃, and preserving heat for 3 hours to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.05 wt% of the solid content is added20.4 wt% of CaCO32.0wt% of Al2O30.6wt% of ZnO, 0.1 wt% of SrCO3And 0.8wt% of H3BO3Then, adding calcium gluconate accounting for 1.0wt% of the solid content and polyvinyl alcohol accounting for 0.2 wt%, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 22h in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.62 mu m;
(4) molding: adjusting the water content of the slurry for molding, adjusting the solid content of the slurry to 70%, then molding to obtain a molded body, and applying a molding magnetic field of 13000Oe in the pressing direction while pressing, wherein the obtained molded body is a cylinder with the diameter of 43.2mm and the height of 13mm, and the molding pressure is 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 600 ℃ for 2h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1300 ℃ for 0.1h to obtain the permanent magnetic ferrite material.
Example 11:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.3Ca0.4La0.3Fe10.95Co0.25O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixing ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Example 12:
a hexagonal magnetoplumbite permanent magnetic ferrite material has a main phase formula as follows: sr0.35Ca0.15La0.5Fe10.75Co0.45O19The preparation method comprises the following steps:
(1) preparing materials: putting iron red, strontium carbonate, calcium carbonate, lanthanum oxide and cobaltous oxide into a wet ball mill according to the molar ratio of each element in the main phase formula, and carrying out mixing ball milling for 5 hours to obtain mixed slurry with the average particle size of 0.8 mu m;
(2) pre-burning: drying the mixed slurry in an oven, pelletizing, presintering at 1240 ℃ in air, and preserving heat for 1h to obtain a granular presintering material;
(3) ball milling: 450g of the pre-sintered material is weighed, and SiO accounting for 0.5 weight percent of the solid content is added20.75 wt% of CaCO30.4 wt% of Cr2O3Then adding calcium gluconate accounting for 0.6wt% of the solid content, then adding 680mL of deionized water as a ball milling medium, and carrying out wet grinding for 24 hours in a high-efficiency ball mill to obtain molding slurry with the average particle size of 0.64 mu m;
(4) molding: adjusting the water content of the slurry for molding to 70%, molding to obtain a molded body, and applying a molding magnetic field of 14000Oe in the pressing direction while pressing to obtain a cylindrical body with a diameter of 43.2mm and a height of 13mm and a molding pressure of 10 MPa;
(5) and (3) sintering: and (3) firstly, preserving the temperature of the formed body at 400 ℃ for 1h, then sintering the formed body in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air), wherein the heating rate is 150 ℃/h, and preserving the temperature at 1220 ℃ for 1.5h to obtain the permanent magnetic ferrite material.
Comparative example 1:
comparative example 1 differs from example 1 in that Sr in comparative example 1 is entirely replaced with Ca, i.e. the main phase formula of the permanent ferrite material in comparative example 1 is: ca0.56La0.44Fe10.87Co0.34O19The rest is the same as in example 1.
Comparative example 2:
comparative example 2 differs from example 1 in that the Ca in comparative example 2 is entirely replaced by Sr, i.e. the main phase formula of the permanent ferrite material in comparative example 2 is: sr0.56La0.44Fe10.87Co0.34O19The rest is the same as in example 1.
Comparative example 3:
comparative example 3 differs from example 8 in that n in comparative example 3 is 5.0, i.e. six in comparative example 2The main phase formula of the angle magnetoplumbite permanent magnetic ferrite material is as follows: sr0.4Ca0.2La0.4Fe9.7Co0.3O19Otherwise, the same as in example 8 was applied.
Comparative example 4:
comparative example 4 differs from example 8 in that n in comparative example 4 is 5.8, i.e. the main phase formula of the hexaferrite permanent magnetic material in comparative example 3 is: sr0.4Ca0.2La0.4Fe11.3Co0.3O19Otherwise, the same as in example 8 was applied.
The upper and lower surfaces of the hexagyromagnetite permanent magnetic ferrite materials prepared in the above examples and comparative examples were ground, and the residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), and maximum magnetic energy product (BH) max were measured, and the results are shown in table 1.
Table 1: and (5) testing the magnetic performance of the permanent ferrite material.
Numbering Br(Gs) Hcb(Oe) Hcj(Oe) (BH)max(MGOe)
Example 1 4720 4268 5216 5.39
Example 2 4710 4055 5027 5.28
Example 3 4730 4049 5079 5.32
Example 4 4700 4095 5132 5.25
Example 5 4740 4102 5154 5.39
Example 6 4720 4098 5012 5.30
Example 7 4710 4058 5064 5.23
Example 8 4710 3975 5098 5.36
Example 9 4720 4254 5085 5.45
Example 10 4760 4089 5012 5.48
Example 11 4710 4194 5012 5.39
Example 12 4690 3989 5140 5.25
Comparative example 1 4480 3567 4650 4.86
Comparative example 2 4490 3624 4455 4.84
Comparative example 3 4550 3273 4676 5.08
Comparative example 4 4580 3754 4522 5.05
As can be seen from table 1, the residual magnetic induction of the permanent magnetic ferrite materials prepared by the formula proportion and the method in the invention in examples 1 to 12 can reach about 4700Gs, and the intrinsic coercivity can reach over 5000Oe, so that the permanent magnetic ferrite materials have good magnetic properties.
The Ca-La-Co ferrite and the Sr-La-Co ferrite prepared in the comparative examples 1 and 2 have obviously reduced magnetic properties compared with the example 1; in comparative examples 3 and 4, the value of n is changed to be outside the range of the invention, the magnetic performance of the prepared permanent magnetic ferrite is also obviously reduced, and the proportion of each element is proved to be not the conventional choice.

Claims (10)

1. A hexagonal magnetoplumbite permanent magnetic ferrite material is characterized in that the general formula is A1-x-yCaxRyFe2n-zMzO19Wherein: a is Sr or Sr and Ba, R comprises La, and M comprises Co; x is 0.15 to 0.4, y is 0.3 to 0.5, z is 0.25 to 0.45, and n is 5.3 to 5.7.
2. The hexaferrite permanent magnet material of claim 1, wherein R further comprises one or more of Pr, Nd, and Bi.
3. The hexaferrite material of claim 1, wherein M further comprises Ni and/or Zn.
4. The hexaferrite permanent magnet material of claim 1, wherein z/y is 0.6-1.0.
5. The method for preparing the hexagonal magnetoplumbite permanent magnetic ferrite material according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparing materials: mixing raw material compounds containing each element according to the molar ratio of each element in the general formula, and crushing the mixture into mixed slurry with the average particle size of less than or equal to 0.8 mu m by using a wet mixing process;
(2) pre-burning: drying the mixed slurry, and then pre-burning in air at 1150-1280 ℃ to obtain a pre-burnt material;
(3) ball milling: adding secondary additives and additives into the pre-sintered material, and grinding the mixture into particles with the average particle size of less than or equal to 0.65 mu m by using a wet mixing process to obtain formed slurry;
(4) molding: adjusting the solid content of the molding slurry to 65-80 wt%, and then performing magnetic field molding to obtain a molding body, wherein the molding magnetic field intensity is more than or equal to 13000 Gs;
(5) and (3) sintering: the molded body is firstly subjected to heat preservation for 0.5-2 h at 100-600 ℃, and then is sintered in an oxygen-rich atmosphere (namely, the oxygen content is higher than that of air) to obtain the permanent magnetic ferrite material, wherein the sintering temperature is 1100-1300 ℃, and the sintering time is 0.1-3 h.
6. The method for preparing a hexagonal magnetoplumbite permanent magnetic ferrite material according to claim 5, wherein the raw material compound containing each element in the step (1) is: sr, Ba and Ca adopt carbonates thereof as raw material compounds; oxides or hydroxides of La, Pr and Nd are used as raw material compounds; fe. Co, Ni, Zn and Bi use their oxides as raw material compounds.
7. The method for preparing the hexagonal magnetoplumbite permanent magnetic ferrite material according to claim 5 or 6, wherein the average particle size of each raw material compound in the step (1) is less than or equal to 5 μm.
8. The method for preparing the hexagonal magnetoplumbite permanent magnetic ferrite material according to claim 5, wherein the pre-sintering time in the step (2) is 0.1-3 h.
9. The method for preparing a hexagonal magnetoplumbite permanent magnetic ferrite material according to claim 5, wherein the secondary additive in the step (3) comprises SiO in an amount of 0.05 to 2.0wt% based on the solid content20.4 to 2.0wt% of CaCO30 to 2.0wt% of Al2O30 to 1.5wt% of Cr2O30 to 0.6wt% of ZnO, 0.1 to 1.0wt% of SrCO3And 0 to 0.8wt% of H3BO3And the average particle size of the secondary additive is less than or equal to 5 mu m.
10. The method for preparing a hexagonal magnetoplumbite permanent magnetic ferrite material according to claim 5 or 9, wherein the additive in the step (3) comprises one or more of calcium gluconate, polyvinyl alcohol and sorbitol, and the addition amount is 0.2-1.2 wt% of the solid content.
CN201911234047.3A 2019-12-05 2019-12-05 Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof Pending CN111362686A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911234047.3A CN111362686A (en) 2019-12-05 2019-12-05 Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911234047.3A CN111362686A (en) 2019-12-05 2019-12-05 Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111362686A true CN111362686A (en) 2020-07-03

Family

ID=71202059

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911234047.3A Pending CN111362686A (en) 2019-12-05 2019-12-05 Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111362686A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679207A (en) * 2020-12-29 2021-04-20 横店集团东磁股份有限公司 Permanent magnetic ferrite material and preparation method thereof
CN113072369A (en) * 2021-03-25 2021-07-06 电子科技大学 U-shaped hexagonal ferrite material with high remanence ratio and preparation method thereof
CN114014644A (en) * 2021-10-15 2022-02-08 横店集团东磁股份有限公司 Calcium permanent magnetic ferrite material and preparation method thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552069A (en) * 2009-01-08 2009-10-07 横店集团东磁股份有限公司 Magnetoplumbite permanent magnetic ferrite and method of producing the same
CN102050619A (en) * 2010-08-02 2011-05-11 横店集团东磁股份有限公司 Method for preparing permanent magnet oxysome material
CN102964120A (en) * 2012-08-31 2013-03-13 横店集团东磁股份有限公司 Sintered permanent magnetic ferrite and its preparation method
CN104230322A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium permanent magnetic ferrite and preparation method thereof
CN104230323A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium-lanthanum-cobalt permanent magnetic ferrite and preparation method thereof
CN104230326A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 Preparation method of M-type calcium permanent magnetic ferrite
CN104230321A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium permanent magnetic ferrite and preparation method thereof
JP2015130493A (en) * 2013-12-04 2015-07-16 Tdk株式会社 Ferrite sintered magnet
CN106083025A (en) * 2016-06-21 2016-11-09 中钢集团安徽天源科技股份有限公司 A kind of preparation method of high-performance Strontium ferrite powder
CN106187144A (en) * 2016-07-07 2016-12-07 成都信息工程大学 A kind of high-performance low-temperature sintered hexagonal crystalline substance M-type strontium ferrite and preparation method thereof
CN109796200A (en) * 2019-02-21 2019-05-24 成都锦钛精工科技有限公司 Rear-earth-doped permanent-magnet ferrite and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552069A (en) * 2009-01-08 2009-10-07 横店集团东磁股份有限公司 Magnetoplumbite permanent magnetic ferrite and method of producing the same
CN102050619A (en) * 2010-08-02 2011-05-11 横店集团东磁股份有限公司 Method for preparing permanent magnet oxysome material
CN102964120A (en) * 2012-08-31 2013-03-13 横店集团东磁股份有限公司 Sintered permanent magnetic ferrite and its preparation method
CN104230322A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium permanent magnetic ferrite and preparation method thereof
CN104230323A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium-lanthanum-cobalt permanent magnetic ferrite and preparation method thereof
CN104230326A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 Preparation method of M-type calcium permanent magnetic ferrite
CN104230321A (en) * 2013-06-24 2014-12-24 广东江粉磁材股份有限公司 M-type calcium permanent magnetic ferrite and preparation method thereof
JP2015130493A (en) * 2013-12-04 2015-07-16 Tdk株式会社 Ferrite sintered magnet
CN106083025A (en) * 2016-06-21 2016-11-09 中钢集团安徽天源科技股份有限公司 A kind of preparation method of high-performance Strontium ferrite powder
CN106187144A (en) * 2016-07-07 2016-12-07 成都信息工程大学 A kind of high-performance low-temperature sintered hexagonal crystalline substance M-type strontium ferrite and preparation method thereof
CN109796200A (en) * 2019-02-21 2019-05-24 成都锦钛精工科技有限公司 Rear-earth-doped permanent-magnet ferrite and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679207A (en) * 2020-12-29 2021-04-20 横店集团东磁股份有限公司 Permanent magnetic ferrite material and preparation method thereof
CN112679207B (en) * 2020-12-29 2022-03-15 横店集团东磁股份有限公司 Permanent magnetic ferrite material and preparation method thereof
CN113072369A (en) * 2021-03-25 2021-07-06 电子科技大学 U-shaped hexagonal ferrite material with high remanence ratio and preparation method thereof
CN114014644A (en) * 2021-10-15 2022-02-08 横店集团东磁股份有限公司 Calcium permanent magnetic ferrite material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN112679207B (en) Permanent magnetic ferrite material and preparation method thereof
CN101552069A (en) Magnetoplumbite permanent magnetic ferrite and method of producing the same
CN102050619B (en) Method for preparing permanent magnet oxysome material
EP3473606B1 (en) Ferrite sintered magnet
CN102964120A (en) Sintered permanent magnetic ferrite and its preparation method
EP3364426A1 (en) Ferrite magnetic material and ferrite sintered magnet
CN103058641B (en) Method for preparing non-rare-earth high-magnetism permanent magnetic ferrite material
CN111362686A (en) Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof
CN102701721B (en) Low-cost sintered calcium permanent magnetic ferrite and preparation method thereof
EP4036071A1 (en) Permanent magnet material and preparation method therefor
CN101205137A (en) Method for manufacturing sintered permanent magnetic ferrite formed by dry pressing
CN103548101B (en) Magneto-plumbite type ferrite magnetic material and segment permanent magnet body therefrom
CN101209920B (en) Economic sintering permanent-magnet ferrite and preparing method thereof
CN104496444B (en) A kind of low cost sintered permanent magnet materials and preparation method thereof
CN111362687A (en) Permanent magnetic ferrite and preparation method thereof
CN105418062B (en) A kind of permanent-magnet ferrite and its manufacture method
WO2001035424A1 (en) Ferrite magnet powder and magnet using the magnet powder, and method for preparing them
KR102430475B1 (en) Method for preparing ferrite sintered magnet and ferrite sintered magnet
KR102407046B1 (en) Ferrite magnetic material and ferrite sintered magnet
KR102258552B1 (en) Ferrite magnetic material and sintered ferrite magnet
CN111196720A (en) Improved high-performance strontium ferrite for magnetic ring and preparation method thereof
JPH11307331A (en) Ferrite magnet
KR102664651B1 (en) Method for preparing ferrite sintered magnet
JP2001068320A (en) Ferrite magnet
KR102588230B1 (en) Ferrite magnetic material and ferrite sintered magnet

Legal Events

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

Application publication date: 20200703