CN109400139B - Preparation process of low-cost permanent magnetic ferrite material - Google Patents

Preparation process of low-cost permanent magnetic ferrite material Download PDF

Info

Publication number
CN109400139B
CN109400139B CN201811079980.3A CN201811079980A CN109400139B CN 109400139 B CN109400139 B CN 109400139B CN 201811079980 A CN201811079980 A CN 201811079980A CN 109400139 B CN109400139 B CN 109400139B
Authority
CN
China
Prior art keywords
powder
iron scale
iron
particle size
equal
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.)
Active
Application number
CN201811079980.3A
Other languages
Chinese (zh)
Other versions
CN109400139A (en
Inventor
丁伯明
胡良权
叶华
韦晓阳
吕舒宏
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 CN201811079980.3A priority Critical patent/CN109400139B/en
Publication of CN109400139A publication Critical patent/CN109400139A/en
Application granted granted Critical
Publication of CN109400139B publication Critical patent/CN109400139B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B35/2683—Other ferrites containing 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
    • C04B35/2608—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
    • C04B35/2666—Other ferrites containing nickel, copper or cobalt
    • 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
    • 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
    • H01F1/11—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 in the form of particles
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides 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
    • C04B2235/3217—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
    • 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
    • C04B2235/327—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
    • C04B2235/34—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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Landscapes

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

Abstract

The invention relates to a method for improving the purity and activity of iron scale by pretreating the iron scale and manufacturing a high-performance permanent magnetic ferrite by the iron scale; the pretreatment comprises impurity removal, crushing, oxidation, fine grinding and screening. The pretreated iron scale can meet the following index requirements: the total purity of the oxide is more than or equal to 98.9 percent, the average particle size is less than or equal to 5um, and SiO2 is less than or equal to 0.1 percent. After the invention is treated by a special process, part of high-performance permanent magnetic ferrite materials can be obtained; the production process is simple and reliable, the material consumption and the energy consumption are low, the production cost is low, and the production process has no secondary pollution; has no other impurity phase, has uniform particle size and the proportion of the particles is in accordance with SrFe12O19The composition range of ferrite.

Description

Preparation process of low-cost permanent magnetic ferrite material
Technical Field
The invention relates to a preparation technology of a permanent magnetic ferrite material, in particular to a preparation technology for preparing a high-performance M-type sintered permanent magnetic ferrite by using iron scale as a raw material, belonging to the field of permanent magnetic ferrite materials.
Background
The iron oxide is a main raw material for producing the permanent magnet pre-sintering material, the performance and the price ratio of the iron oxide directly influence the development of the permanent magnet industry, and the iron oxide for the permanent magnet pre-sintering material mainly comes from the following two aspects: 1. iron oxide is produced by adopting a chemical method of dissolving an iron raw material by adding acid or pickling waste liquor in the steel industry and the like; 2. the ultra-pure iron ore concentrate and the steel rolling iron scale have the defects of complex process and high cost, and the product performance of the ultra-pure iron ore concentrate and the steel rolling iron scale is poor although the price of the ultra-pure iron ore concentrate is low.
The M-type permanent magnetic ferrite material does not contain high-price metal elements such as Ni, Co, rare earth and the like, and has lower price compared with other magnetic materials; meanwhile, the remanence is moderate, the chemical stability is good, the relative quality is low, and the cost performance is higher than that of other magnetic materials; therefore, the permanent magnetic ferrite plays an important role in the industries of household appliances, computers, automobiles, communication and the like, and is dominant in the market.
The M-type hexagonal ferrite is represented by: MO 6Fe2O3Wherein M is Ba, Sr, Pb, etc., wherein, Fe2O3The main sources of the iron oxide are acid-washed iron oxide red and hot-rolled iron scale.
Along with the technological progress, the performance requirements of electronic products on permanent magnetic ferrite are higher and higher, the magnetic performance of the ferrite is improved by adding rare earth elements such as LaCo and the like in the current market, and the permanent magnetic ferrite material added with the rare earth elements has relatively higher cost due to higher price and larger fluctuation of the rare earth elements.
When the conventional trace element additive is adopted to replace the rare earth element additive to prepare the permanent magnetic ferrite material at present, the magnetic property can not reach the residual magnetic induction strength Br of more than or equal to 415mT, the coercive force Hcb of more than or equal to 290kA/m and the intrinsic coercive force Hcj of more than or equal to 305 kA/m.
The scale is also called as scale, and generally refers to scale-like substances peeled off from the surface of steel products by the oxidation of the surface of the steel products during the heating and rolling processes.
The iron scale is one of the main raw materials for producing the permanent magnetic ferrite, and is influenced by steel variety, smelting process control and other factors, so that the iron scale is extremely unstable in components and has great influence on the performance and quality of products.
If the ferrite is not pretreated, the magnetic property of the ferrite is difficult to ensure, and in order to fully utilize the raw material of iron scale, which has wide sources and low price, to produce the middle-high end permanent magnetic ferrite material, the deep processing is required to be carried out on the permanent magnetic ferrite material.
The patent technology of 'a preparation method of permanent magnetic ferrite' (CN101996722A) adopts SrCO3、Fe2O3、La2O3、Co3O4、CaCO3Wet mixing raw materials, drying, granulating, presintering, coarse crushing, fine crushing, precipitating, filtering, wet pressing and molding, and sintering. The technology has complex operation and does not produce Fe as the synthesized main raw material2O3Analysis of the composition of (1), Fe2O3Too much or too complicated impurity content of (b) may result in poor magnetic properties of the ferrite.
"a method for preparing permanent magnetic ferrite with high fracture toughness" (CN200910010068.7) patent technique, adopting nano SrCO3And Fe2O3Proportioning according to a certain proportion, adopting ball milling to fully mix and refine the raw material powder again, if the method is put into production, a large amount of nano SrCO is needed3And Fe2O3And is difficult to be industrially produced due to its high price.
A preparation method of nano strontium ferrite (CN101913854A) is characterized in that strontium carbonate and ferric nitrate crystals are weighed according to the molar ratio of Sr to Fe of 1: 12 and are dissolved by nitric acid and deionized water, tartaric acid and polyethylene glycol are added after the strontium carbonate and the ferric nitrate crystals are uniformly mixed, the PH value is adjusted to 7 by ammonia water, the obtained mixed solution is heated to form sol-gel and dried, and the sol-gel is calcined to form the nano permanent magnetic ferrite by sections at 860-1100 ℃. The method adds tartaric acid, glycol and ammonia water into the solution, so that impurities are easily introduced, and the magnetic property of the ferrite is reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to improve the purity and activity of the iron scale by pretreating the iron scale and to prepare the high-performance permanent magnetic ferrite by the iron scale.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation process of a low-cost permanent magnetic ferrite material adopts iron scale as a raw material, and comprises the following steps:
1) firstly, carrying out magnetic separation on iron scale, and removing magnetic metal impurities in oil materials by using magnetic force; crushing the iron scale subjected to magnetic separation to below 10 microns in a dry manner by using a ball mill; keeping the temperature at 350-850 ℃ for 1-3 hours to oxidize into ferric oxide; carrying out wet ball milling on the oxidized iron scale again, grinding the iron scale into fine powder with the average particle size of about 3 microns, sieving the fine powder and the coarse powder with large particles, and preferably removing the fine iron powder and the coarse powder with large particles to obtain pretreated iron scale powder;
2) mixing the scaly iron powder pretreated in the step 1) with SrCO3Carrying out wet ball milling on boric acid, and then drying;
3) pre-pressing the powder obtained in the step 2) and then pre-burning to obtain a pre-burnt material;
4) adding SiO into the pre-sintering material obtained in the step 3)2、CaCO3Carrying out secondary fine grinding on alumina, boric acid and deionized water to obtain slurry;
5) centrifugally dewatering the slurry obtained in the step 4), adjusting the concentration of the slurry to 66%, then forming, and applying a 10000Oe forming magnetic field in the pressing direction while pressing to obtain a formed body;
6) heat-treating the molded body obtained in step 5) at a temperature of 100 to 600 ℃, then sintering in air at a temperature rise rate of 150 ℃/h, and keeping the temperature at 1210 ℃ for 90 minutes to obtain a sintered body.
Preferably, the sintered body is a hexagonal M-type magnetoplumbite ferrite containing Sr, La, Co, and Fe as main phases, and has a molecular formula characterized by: sr1-xLaxFe3+ 2n-yCoyO19，0.01≤x≤0.1；0.05≤y≤0.15；5.6≤n≤6.1。
Preferably, one or more of the following compounds are added before the secondary fine grinding in step 4), and the addition amount of each element compound in the total amount of the weighed mixture is as follows: CaCO3：0.4～1.3wt％、Al2O3：0.1～1.0wt％、Cr2O3: 0.1 to 1.0wt%, boric acid: 0.05-0.3 wt%, calcium gluconate: 0.4 to 1.3wt%, lanthanum oxide: 0.8-2.6wt% and SiO2：0.3～0.8wt％。
Preferably, the adding amount of the boric acid in the step 2) is 0.05-0.3% of the mass of the scaly iron powder.
Preferably, the pretreated iron scale meets the following index requirements: the total purity of the oxide is more than or equal to 98.9 percent, the average particle size is less than or equal to 5 mu m, and the SiO2 is less than or equal to 0.1 percent.
Preferably, the molded article is a cylinder having a diameter of 43.2mm and a height of 13mm, and the molding pressure is 5 MPa.
Preferably, lanthanum oxide and cobalt oxide are added during wet ball milling in the step 2), and the addition amount of the lanthanum oxide and the cobalt oxide is 0.05-0.3% of the mass of the iron scale powder.
Preferably, the powder dried in the step 3) is pre-pressed under the pressure of 10MPa, and then is pre-sintered in the air at 1260 ℃.
The invention has the beneficial effects that:
after the invention is treated by a special process, part of high-performance permanent magnetic ferrite materials can be obtained; the production process is simple and reliable, the material consumption and the energy consumption are low, the production cost is low, and the production process has no secondary pollution; no other impurity phase, uniform particle size, and the proportion of SrFe12O19The composition range of ferrite. The coercive force of the powder is 232kA/m, the residual magnetization is 410mT, and the saturation magnetization is 68 emu/g.
Detailed Description
The invention is further described below in conjunction with specific embodiments, the following examples are intended to illustrate the invention but not to limit it further, and the invention may be practiced in any of the ways described in this summary.
In order to avoid repetition, the raw materials, the dispersing agent and the related process parameters related to the present embodiment are uniformly described in the following embodiments, which are not repeated.
Example 1:
1. firstly, carrying out magnetic separation on iron scale, removing magnetic metal impurities in oil materials by using magnetic force, and carrying out dry crushing on the iron scale subjected to magnetic separation to below 10 mu m by using a ball mill; keeping the temperature at 350-850 ℃ for 1-3 hours to oxidize into ferric oxide; performing wet ball milling on the oxidized iron scale again, grinding into fine powder with average particle size of about 3 μm, sieving to remove fine iron powder and large iron powder, and preparing a powder containing SrFe11.9O19Pre-sintering material of ferrite main phase. Weighing oxidized scale powder (purity is more than or equal to 98.6 wt%, and original average particle size of particles is less than or equal to 3 μm) and SrCO according to proportion3(the purity is more than or equal to 97 wt%, the original average particle size of the particles is less than or equal to 1.5 mu m), 0.2 wt% of boric acid and other raw materials are added for carrying out wet primary ball milling for 5 hours, the average particle size of the mixed particles is 0.75 mu m, and then the slurry is dried in an oven.
2. And pre-pressing the dried powder under the pressure of 10MPa, pre-sintering the powder in air at 1260 ℃, and preserving the heat for 3 hours to obtain the massive pre-sintered material. And (3) carrying out dry coarse grinding treatment on the pre-sintered material, wherein the average particle size of the powder after coarse grinding is 3.5 mu m.
3. Weighing 500g of the pre-sintered material;
comparative example 1: preparation of a steel sheet having SrFe directly from untreated mill scale11.9O19500g of a pre-sintered ferrite main phase.
Example 1 and comparative example 1 were added with 2.0gSiO2、3.0gCaCO3The mixture of 3g of alumina and 1g of boric acid was put into a ball mill, and 720ml of deionized water was added as a ball milling medium to conduct milling for 20 hours.
5) After the wet grinding, the molding slurry was subjected to centrifugal dehydration to adjust the slurry concentration to 66%, and then molded, and a molding magnetic field of 10000Oe was applied in the pressing direction at the same time as the pressing. The resulting molded article was a cylinder having a diameter of 43.2mm and a height of 13mm, and the molding pressure was 5 MPa.
6) And heat-treating the molded body at a temperature of 100 to 600 ℃, then sintering the molded body in air at a temperature rise rate of 150 ℃/h, and keeping the temperature at 1210 ℃ for 90 minutes to obtain a sintered body. The upper and lower surfaces of the sintered body were polished, and the residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), and maximum magnetic energy product (BH) max were measured.
Figure BDA0001802201320000041
Example 2
1) Firstly, carrying out magnetic separation on the iron scale, removing magnetic metal impurities in the oil material by using magnetic force, and carrying out dry crushing on the iron scale subjected to magnetic separation to below 10 mu m by using a ball mill; keeping the temperature at 350 ℃ for 1 hour to oxidize into ferric oxide; performing wet ball milling on the oxidized iron scale again, grinding into fine powder with average particle size of about 3 μm, sieving, removing fine iron powder and large iron powder, and preparing a Sr0.75Ca0.05La0.1Fe11.2Co0.05O19Pre-sintering material of ferrite main phase, weighing treated iron powder (purity not less than 98.8 wt%, Cl-not more than 0.2 wt%, original level of particles)Average particle size less than or equal to 1.5 mu m), La2O3(purity is more than or equal to 99.3 wt%, and original average particle size of particles is less than or equal to 5 mu m), C02O3(Co content is more than or equal to 72 wt%, original average particle size of particles is less than or equal to 3 mu m), SrCO3(the purity is more than or equal to 97 wt%, the original average particle size of the particles is less than or equal to 1.5 mu m) and other raw materials are subjected to wet primary ball milling for 5 hours, the average particle size of the mixed particles is 0.72 mu m, then the slurry is dried in an oven, pre-pressed under the pressure of 10MPa, pre-sintered at 1210 ℃ in the air, and the heat preservation time is 1 hour, so that the blocky pre-sintered material is obtained. And (3) carrying out dry coarse grinding treatment on the pre-sintered material, wherein the average particle size of the powder after coarse grinding is 3.5 mu m.
2) 500g of the pre-sintered powder was weighed and 2.0g of SiO was added thereto2、5gCaCO3And 3.0g of calcium gluconate are put into a ball mill, 720ml of deionized water is added as a ball milling medium for milling, the milling time is 24 hours, and the average particle size of the slurry after ball milling is 0.68 mu m.
3) After the wet grinding, the molding slurry was subjected to centrifugal dehydration to adjust the slurry concentration to 69%, and then molded, and a molding magnetic field of 13000Oe was applied in the pressing direction at the same time as the pressing. The resulting molded article was a cylinder having a diameter of 43.2mm and a height of 13mm, and the molding pressure was 5 MPa.
4) And carrying out heat treatment on the formed body at the temperature of 100 ℃ to completely remove the organic dispersing agent, then sintering in the air at the temperature rise speed of 150 ℃/h, and carrying out heat preservation at 1205 ℃ for 60 minutes to obtain a sintered body. The upper and lower surfaces of the sintered body were polished, and the residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), and maximum magnetic energy product (BH) max were measured.
Numbering Br(Gs) Hcb(Oe) Hcj(Oe) (BH)max
1-1 4210 3750 3950 4.21
1-2 4198 3794 3900 4.19
Example 3
1) Firstly, carrying out magnetic separation on the iron scale, removing magnetic metal impurities in the oil material by using magnetic force, and carrying out dry crushing on the iron scale subjected to magnetic separation to below 10 mu m by using a ball mill; keeping the temperature at 850 ℃ for 3 hours to oxidize into ferric oxide; performing wet ball milling on the oxidized iron scale again, grinding into fine powder with average particle size of about 3 μm, sieving, removing fine iron powder and large iron powder, and preparing a Sr0.75Ca0.05La0.1Fe11.2Co0.05O19Pre-sintering material of ferrite main phase, weighing processed iron powder (purity not less than 98.8 wt%, Cl-not more than 0.2 wt%, original average particle size not more than 1.5 μm), La2O3(purity is more than or equal to 99.3 wt%, and original average particle size of particles is less than or equal to 5 mu m), Co2O3(Co content is more than or equal to 72 wt%, original average particle size of the particles is less than or equal to 3 μm), SrCO3 (purity is more than or equal to 97 wt%, original average particle size of the particles is less than or equal to 1.5 μm), and the like are subjected to wet primary ball milling for 5 hours, the average particle size of the mixed particles is 0.72 μm, and thenAnd drying the slurry in an oven, pre-pressing under the pressure of 10MPa, pre-sintering at 1210 ℃ in air, and preserving heat for 1 hour to obtain the blocky pre-sintered material. And (3) carrying out dry coarse grinding treatment on the pre-sintered material, wherein the average particle size of the powder after coarse grinding is 3.5 mu m. When wet ball milling is carried out, boric acid, lanthanum oxide and cobalt oxide are added, wherein the addition amount of the boric acid is 0.05 percent of the mass of the scaly iron powder, and the addition amount of the lanthanum oxide and the cobalt oxide (the mass ratio is 1: 1) is 0.3 percent of the mass of the scaly iron powder.
2) 500g of the pre-sintered powder was weighed and 2.0g of SiO was added thereto2、5gCaCO3And 3.0g of calcium gluconate are put into a ball mill, 720ml of deionized water is added as a ball milling medium for milling, the milling time is 24 hours, and the average particle size of the slurry after ball milling is 0.68 mu m.
3) After the wet grinding, the molding slurry was subjected to centrifugal dehydration to adjust the slurry concentration to 69%, and then molded, and a molding magnetic field of 13000Oe was applied in the pressing direction at the same time as the pressing. The resulting molded article was a cylinder having a diameter of 43.2mm and a height of 13mm, and the molding pressure was 5 MPa.
4) And carrying out heat treatment on the formed body at the temperature of 600 ℃ to completely remove the organic dispersing agent, then sintering in the air at the temperature rise speed of 150 ℃/h, and carrying out heat preservation at 1205 ℃ for 60 minutes to obtain a sintered body.
Example 4
1) Firstly, carrying out magnetic separation on the iron scale, removing magnetic metal impurities in the oil material by using magnetic force, and carrying out dry crushing on the iron scale subjected to magnetic separation to below 10 mu m by using a ball mill; keeping the temperature at 550 ℃ for 2 hours to oxidize into ferric oxide; performing wet ball milling on the oxidized iron scale again, grinding into fine powder with average particle size of about 3 μm, sieving, removing fine iron powder and large iron powder, and preparing a Sr0.75Ca0.05La0.1Fe11.2Co0.05O19Pre-sintering material of ferrite main phase, weighing processed iron powder (purity not less than 98.8 wt%, Cl-not more than 0.2 wt%, original average particle size not more than 1.5 μm), La2O3(purity is more than or equal to 99.3 wt%, and original average particle size of particles is less than or equal to 5 mu m), Co2O3Carrying out wet primary ball milling on raw materials (the Co content is more than or equal to 72 wt%, the original average particle size of the particles is less than or equal to 3 mu m), SrCO3 (the purity is more than or equal to 97 wt%, the original average particle size of the particles is less than or equal to 1.5 mu m), and the like, wherein the ball milling time is 5 hours, the average particle size of the mixed particles is 0.72 mu m, then drying the slurry in an oven, carrying out pre-pressing treatment under the pressure of 10MPa, then presintering in the air at 1210 ℃, and keeping the temperature for 1 hour to obtain the blocky presintering material. And (3) carrying out dry coarse grinding treatment on the pre-sintered material, wherein the average particle size of the powder after coarse grinding is 3.5 mu m. When wet ball milling is carried out, boric acid, lanthanum oxide and cobalt oxide are added, wherein the addition amount of the boric acid is 0.3 percent of the mass of the scaly iron powder, and the addition amount of the lanthanum oxide and the cobalt oxide (the mass ratio is 1: 1) is 0.05 percent of the mass of the scaly iron powder.
2) 500g of the pre-sintered powder was weighed and 2.0g of SiO was added thereto2、5gCaCO3And 3.0g of calcium gluconate are put into a ball mill, 720ml of deionized water is added as a ball milling medium for milling, the milling time is 24 hours, and the average particle size of the slurry after ball milling is 0.68 mu m.
3) After the wet grinding, the molding slurry was subjected to centrifugal dehydration to adjust the slurry concentration to 69%, and then molded, and a molding magnetic field of 13000Oe was applied in the pressing direction at the same time as the pressing. The resulting molded article was a cylinder having a diameter of 43.2mm and a height of 13mm, and the molding pressure was 5 MPa.
4) And carrying out heat treatment on the formed body at the temperature of 400 ℃ to completely remove the organic dispersing agent, then sintering in the air at the temperature rise speed of 150 ℃/h, and carrying out heat preservation at 1205 ℃ for 60 minutes to obtain a sintered body.

Claims (3)

1. A preparation process of a low-cost permanent magnetic ferrite material is characterized in that iron scale is adopted as a raw material, and the preparation process comprises the following steps:
1) firstly, carrying out magnetic separation on iron scale, and removing magnetic metal impurities in oil materials by using magnetic force; crushing the iron scale subjected to magnetic separation to below 10 microns in a dry manner by using a ball mill; keeping the temperature at 350-850 ℃ for 1-3 hours to oxidize into ferric oxide; carrying out wet ball milling on the oxidized iron scale again, grinding into fine powder with the average particle size of 3 mu m,sieving and optimizing to remove fine iron powder and large-particle coarse powder to obtain pretreated iron scale powder; the pretreated iron scale meets the following index requirements: the total purity of the oxide is more than or equal to 98.9 percent, the average particle size is less than or equal to 5 mu m, and SiO is2≤0.1%；
2) Mixing the scaly iron powder pretreated in the step 1) with SrCO3Carrying out wet ball milling on boric acid, and then drying; the adding amount of the boric acid is 0.05-0.3% of the weight of the scaly iron powder; adding lanthanum oxide and cobalt oxide during wet ball milling, wherein the addition amount of the lanthanum oxide and the cobalt oxide is 0.05-0.3% of the mass of the iron scale powder;
3) pre-pressing the powder obtained in the step 2) and then pre-burning to obtain a pre-burnt material;
4) adding a compound SiO into the pre-sintering material obtained in the step 3)2、CaCO3Alumina, boric acid, Cr2O3One or more of calcium gluconate and lanthanum oxide, and deionized water for secondary fine grinding to obtain slurry;
the percentage of the addition amount of each compound in the total amount of the weighed mixture is respectively as follows: CaCO3：0.4～1.3wt%、Al2O3：0.1～1.0wt%、Cr2O3: 0.1 to 1.0wt%, boric acid: 0.05-0.3 wt%, calcium gluconate: 0.4 to 1.3wt%, lanthanum oxide: 0.8-2.6wt% and SiO2：0.3～0.8wt%；
5) Centrifugally dewatering the slurry obtained in the step 4), adjusting the concentration of the slurry to 66%, then forming, and applying a 10000Oe forming magnetic field in the pressing direction while pressing to obtain a formed body;
6) carrying out heat treatment on the formed body obtained in the step 5) at the temperature of 100-600 ℃, then sintering in the air, wherein the temperature rise speed is 150 ℃/h, and keeping the temperature at 1210 ℃ for 90 minutes to obtain a sintered body;
the sintered body is a hexagonal M-type magnetoplumbite ferrite containing Sr, La, Co and Fe as main phases and has the following characteristic molecular formula: sr1-xLaxFe3+ 2n-yCoyO19，0.01≤x≤0.1；0.05≤y≤0.15；5.6≤n≤6.1。
2. The process of claim 1, wherein the forming body is a cylinder with a diameter of 43.2mm and a height of 13mm, and the forming pressure is 5 MPa.
3. The process for preparing a low-cost permanent magnetic ferrite material according to claim 1, wherein the powder material dried in step 3) is pre-pressed under a pressure of 10MPa, and then pre-sintered at 1260 ℃ in air.
CN201811079980.3A 2018-09-17 2018-09-17 Preparation process of low-cost permanent magnetic ferrite material Active CN109400139B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811079980.3A CN109400139B (en) 2018-09-17 2018-09-17 Preparation process of low-cost permanent magnetic ferrite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811079980.3A CN109400139B (en) 2018-09-17 2018-09-17 Preparation process of low-cost permanent magnetic ferrite material

Publications (2)

Publication Number Publication Date
CN109400139A CN109400139A (en) 2019-03-01
CN109400139B true CN109400139B (en) 2021-05-18

Family

ID=65464794

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811079980.3A Active CN109400139B (en) 2018-09-17 2018-09-17 Preparation process of low-cost permanent magnetic ferrite material

Country Status (1)

Country Link
CN (1) CN109400139B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776088B (en) * 2019-04-01 2021-11-12 中钢集团南京新材料研究院有限公司 Preparation method of strontium ferrite pre-sintering material
CN110372362A (en) * 2019-07-15 2019-10-25 横店集团东磁股份有限公司 A kind of preparation method and permanent-magnet ferrite material of permanent-magnet ferrite material
JP7182016B2 (en) * 2020-07-14 2022-12-01 Ｊｆｅケミカル株式会社 MnCoZn ferrite
CN112209707B (en) * 2020-09-24 2022-03-25 横店集团东磁股份有限公司 Preparation method of high-performance permanent magnetic ferrite
CN112349508B (en) * 2020-12-08 2022-05-03 安徽泰龙锌业有限责任公司 Method for preparing magnetic material by using zinc-containing waste material
CN115724655A (en) * 2021-08-25 2023-03-03 横店集团东磁股份有限公司 Method for preparing high-performance permanent magnetic ferrite material from low-purity iron oxide red
CN115784733B (en) * 2022-12-22 2023-12-01 矿冶科技集团有限公司 High-performance calcium lanthanum cobalt ferrite material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1101164A (en) * 1993-09-28 1995-04-05 住友特殊金属株式会社 Process of producing calcined materials for ferrite magnet
CN1442388A (en) * 2002-03-06 2003-09-17 华能诸暨磁性材料厂 Method of manufacturing high performance ferrite strontium primary sintered material powder using iron scale

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0562817A (en) * 1991-08-30 1993-03-12 Tdk Corp Method of manufacturing iron oxide for ferrite

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1101164A (en) * 1993-09-28 1995-04-05 住友特殊金属株式会社 Process of producing calcined materials for ferrite magnet
CN1442388A (en) * 2002-03-06 2003-09-17 华能诸暨磁性材料厂 Method of manufacturing high performance ferrite strontium primary sintered material powder using iron scale

Also Published As

Publication number Publication date
CN109400139A (en) 2019-03-01

Similar Documents

Publication Publication Date Title
CN109400139B (en) Preparation process of low-cost permanent magnetic ferrite material
CN101844914B (en) Magnetoplumbate-type permanent magnetic ferrite and manufacturing method thereof
CN102050619B (en) Method for preparing permanent magnet oxysome material
CN112679207B (en) Permanent magnetic ferrite material and preparation method thereof
CN112876231A (en) Preparation method of permanent magnetic ferrite and permanent magnetic ferrite
CN111362687A (en) Permanent magnetic ferrite and preparation method thereof
CN115340373B (en) Preparation method of hexagonal ferrite material based on low-purity iron concentrate raw material system
CN110818402B (en) Preparation method of superfine ferrite powder
CN106747390B (en) Strontium ferrite pre-sintering material and preparation method thereof
CN109836147A (en) A kind of permanent-magnet ferrite and preparation method thereof
CN114014644A (en) Calcium permanent magnetic ferrite material and preparation method thereof
CN109102977A (en) A kind of high density dry-pressing opposite sex ferrimagnet and its manufacturing method
CN110937888B (en) High-performance permanent magnetic ferrite material with secondary pre-sintering of powder and preparation method thereof
CN112321294A (en) Ferrite permanent magnetic material and preparation method thereof
CN107473724A (en) A kind of preparation method and product of high-performance M types calcium strontium ferrite
CN112201428A (en) Method for preparing high-performance magnetic steel by using neodymium iron boron reclaimed materials
CN105481358A (en) High-coercivity permanent magnetic ferrite and preparation method thereof
CN114907130B (en) Additive for preparing permanent magnetic strontium ferrite material and application thereof
KR100707366B1 (en) Method for producing ferrite sintered compact
KR20200062262A (en) Ferrite plastic body, ferrite sintered magnet and method for manufacturing the same
CN113801632B (en) Dispersing agent for permanent magnetic ferrite material and preparation method and application thereof
KR102430475B1 (en) Method for preparing ferrite sintered magnet and ferrite sintered magnet
CN116120049B (en) Preparation method of calcium lanthanum cobalt ferrite magnet, calcium lanthanum cobalt ferrite magnet and application
KR102587856B1 (en) Ferrite calcined body and method for manufacturing sintered ferrite magnet
CN113896522B (en) Permanent magnetic ferrite and preparation method thereof

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
GR01 Patent grant
GR01 Patent grant