CN114195498A - Low-cost permanent magnet barium ferrite and preparation method thereof - Google Patents
Low-cost permanent magnet barium ferrite and preparation method thereof Download PDFInfo
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- CN114195498A CN114195498A CN202111522878.8A CN202111522878A CN114195498A CN 114195498 A CN114195498 A CN 114195498A CN 202111522878 A CN202111522878 A CN 202111522878A CN 114195498 A CN114195498 A CN 114195498A
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- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 35
- 238000000498 ball milling Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 39
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005381 magnetic domain Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical group 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
-
- 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
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- 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
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- 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
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- 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
- C04B2235/3215—Barium oxides or oxide-forming salts thereof
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
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- Hard Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
Abstract
A low-cost permanent-magnet barium ferrite with a chemical formula of Ba and a preparation method thereof1‑x‑yCaxSryFe2nO19Wherein x is more than or equal to 0.03 and less than or equal to 0.2, y is more than or equal to 0.03 and less than or equal to 0.2, and n is more than or equal to 5.6 and less than or equal to 6.0. The permanent magnet barium ferrite preparation raw material selects low-cost iron scale, the permanent magnet ferrite is prepared by pretreating the iron scale, and the total purity of the oxide after pretreatment is more than or equal to 99.2%. The permanent magnet barium ferrite prepared by the invention has low price of the selected raw materials, and the prepared permanent magnet barium ferrite still has better permanent magnetic property, and the preparation method has simple process and low production cost.
Description
Technical Field
The invention relates to a permanent magnetic ferrite and a preparation method thereof, in particular to a low-cost permanent magnetic barium ferrite and a preparation method thereof.
Background
Compared with other metal magnetic materials, the M-type permanent magnetic ferrite material has the advantages of low price, good chemical stability, low relative quality and higher performance-price ratio than other magnetic materials, plays an important role in the industries of household appliances, computers, automobiles, communication and the like, and is dominant in the market.
The iron oxide is a main raw material for producing the permanent magnet pre-sintering material, and the iron oxide used by the current permanent magnet pre-sintering material mainly comes from the following two aspects: 1. iron oxide is produced by adopting chemical methods such as dissolving iron raw materials by adding acid or pickling waste liquid 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 scale is also called as scale, and generally refers to scale-like substances peeled off from steel materials due to an iron oxide layer formed by oxidation of the surface of the steel materials in 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.
Along with the sharp rise of the price of ferrite raw materials, the production cost of the pre-sintering material also rises rapidly, and the profit of permanent magnetic ferrite manufacturers also drops greatly. The competition of the middle grade permanent magnetic ferrite is further increased, and the use of the raw material of steel rolling iron scale with wide source and low price is also gradually increased.
CN 109400139B discloses a preparation process of a low-cost permanent magnetic ferrite material: the high-performance permanent magnetic ferrite is manufactured by using iron scale, and the pretreatment steps comprise 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 SiO is2Less than or equal to 0.1 percent. The pretreatment steps are complicated, the purity of the obtained oxide is not high, the secondary ball milling time is long, more dispersing agents are required to be added, and the wet forming process efficiency is low, so that the production cost is still high in practice although the production cost is claimed to be low.
CN 102815933A discloses a permanent-magnet barium ferrite material and a preparation method thereof, wherein the permanent-magnet barium ferrite is prepared by using steel rolling iron scale and barium carbonate, and the structural formula of the product is BaO. nFe2 O 3Wherein n = 5~ 5.9. The ferrite does not contain expensive metal and belongs to low-cost ferrite. However, the iron scale in the method is not pretreated, contains Fe ions with different valence states, the formed crystal structure has deviation, and the magnetic property of the product is reduced.
CN102249658A discloses a rare earth permanent magnetic ferrite material and a preparation method thereof, wherein the chemical formula of the obtained ferrite material is D1-xRxO·nFe2-y-zLnzCoyO3And conventional permanent magnetic ferrite AB12019Compared with the method that the A bit and the B bit are partially substituted by lanthanide, the magnetoelectric property of the permanent magnetic ferrite prepared by the method is improved, but a large amount of expensive Nd is used2O3And Gd2O3The production cost is greatly increased, and the characteristic of high cost performance of the M-type permanent magnetic ferrite is lost.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide the low-cost permanent magnet barium ferrite with low production cost and high cost performance.
The invention further aims to solve the technical problem of providing a preparation method of the low-cost permanent magnet barium ferrite by taking low-price iron scale as a raw material and having a simple process.
The invention adopts the technical scheme that the low-cost permanent magnet barium ferrite has a chemical formula of Ba1-x-yCaxSryFe2nO19Wherein x is more than or equal to 0.03 and less than or equal to 0.2, y is more than or equal to 0.03 and less than or equal to 0.2, and n is more than or equal to 5.6 and less than or equal to 6.0. In ferrite, Ba2+In combination with a small amount of Sr2+、Ca2+The distortion of the M-shaped hexagonal lattice is effectively reduced.
The invention further solves the technical problem by adopting the technical scheme that the preparation method of the low-cost permanent magnet barium ferrite comprises the following steps:
(1) pretreating raw material iron scale: ball-milling and crushing the scale, calcining and oxidizing, ball-milling again, and sieving to obtain scale powder;
(2) material preparation and ball milling: mixing the scaly iron powder obtained in the step (1) with BaCO3、SrCO3And CaCO3Mixing the powder in a ball mill, adding water and ball milling to obtain mixed slurry;
(3) drying and pre-sintering: drying the mixed slurry obtained in the step (2), and pre-burning to obtain a pre-burnt material;
(4) vibration grinding: performing vibration grinding on the pre-sintering material obtained in the step (3) to obtain coarse powder;
(5) secondary ball milling: adding an additive and water into the coarse powder obtained in the step (4), and performing ball milling to obtain fine slurry;
(6) pressing and molding and sintering: pressing and molding the fine slurry obtained in the step (5) under the condition of a magnetic field to obtain a molded body; and sintering the obtained formed body to obtain the low-cost permanent magnet barium ferrite.
Further, in the step (1), the average particle size of the iron scale powder is 5-8 μm, and the total purity of the oxide is more than or equal to 99.2%.
Further, in the step (1), the calcining temperature is 550-900 ℃; the calcining time is 1-3 h.
Further, in the step (1), the ball milling time is 2-5 h.
Further, in the step (1), the crushing is carried out until the grain size of the iron scale is 15-20 μm.
Further, in the step (2), the raw materials in the ingredients comprise: iron scale powder (Fe)2O3) 9.9 to 11.3 portions of SrCO30.1 to 0.4 part of BaCO30.05 to 0.2 portion of CaCO30.3 to 0.6 portion.
Further, in the step (3), the drying time is 6-10 h; the drying temperature is 100-130 ℃.
Further, in the step (3), the pre-sintering is performed for 2-4 hours at 1100-1250 ℃ in air or oxygen atmosphere. After pre-sintering in the temperature range, an obvious M-shaped hexagonal crystal structure is formed, certain chemical activity is reserved, and a ferrite structure with a complete crystal form can be obtained after secondary sintering.
Further, in the step (4), the duration of the vibromilling is 90-120 s.
Further, in the step (4), the average particle size of the coarse powder is 2-5 μm.
Further, in the step (5), the additive is used in an amount of 0.5 to 2wt% of the coarse powder.
Further, in the step (5), the additive is CaCO3、SiO2And boric acid.
The additive can produce low-melting-point products in the sintering process, reduce the sintering temperature, promote solid-phase reaction, improve residual magnetism, refine crystal grains and improve coercivity. The addition of the additive in the secondary ball milling can improve the activity of the pre-sintered material, so that the crystal structure of the obtained ferrite is complete.
Further, in the step (5), the mass of the water is 1.8-2.4 times of the mass of the coarse powder.
Further, in the step (5), the ball milling time is 10-12 h.
Further, in the step (5), the water content of the fine slurry is 65-72 wt%.
Further, in the step (5), the average particle size of solid material particles in the fine slurry is 0.6-0.8 μm, and the particle size range can effectively improve the molding efficiency of the annular magnet.
Further, in the step (6), the pressure of the compression molding is 6-12 MPa, and the strength of the molding magnetic field is more than or equal to 9000 Gs.
Further, in the step (6), the sintering is performed by firstly preserving heat for 1-3 hours at 400-600 ℃, and then raising the temperature to 1200-1280 ℃ and preserving heat for 1.5-3 hours.
The principle of the invention is as follows: due to Ba in barium ferrite2+Large ionic radius and Ba contained in crystal lattice and grain boundary2+The crystal lattice distortion is larger, the grain boundary stress is increased, the invention improves the crystal structure of barium ferrite, and combines a small amount of Sr on the basis of reducing the raw material cost by preprocessing steel rolling iron scale2+、Ca2+Effective reduction of M-shaped hexagonal latticeDistortion, small amount of Sr in grain boundary2+、Ca2+The addition of the magnetic domain improves the effective arrangement of magnetic moments, the structure of the magnetic domain is more stable, and the magnetic performance of the ferrite is better.
Compared with the prior art, the invention has the beneficial effects that: in the ferrite of the present invention, Ba2+In combination with a small amount of Sr2+、Ca2+The addition of the permanent magnetic barium ferrite effectively reduces the distortion of the M-shaped hexagonal lattice, so that the permanent magnetic barium ferrite still has better permanent magnetic performance (the remanence reaches 4100 Gs); the iron scale which is used as the main raw material and has lower price is further oxidized by calcination, so that the purity of the iron oxide is effectively improved; BaCO used3The price is relatively low, high-cost additives such as La, Co and the like do not need to be added, the obtained permanent magnet barium ferrite still has good permanent magnetic property, the cost is well controlled, the process is simple, the industrial production is easy, the production cost of the permanent magnet ferrite is reduced, and the obtained permanent magnet barium ferrite has high cost performance.
Detailed Description
The present invention will be further described with reference to the following examples. These examples are not intended to be construed as limiting the scope of the invention.
The starting materials used in the embodiments of the present invention are all available from conventional commercial sources.
Example 1
The chemical formula of the permanent magnetic ferrite in this embodiment is Ba0.9Ca0.05Sr0.05Fe11.7O19。
The preparation method of the permanent magnetic ferrite in the embodiment comprises the following steps:
(1) iron scale pretreatment: firstly, placing the iron scale material in an oven to dry for 20 minutes; crushing the dried iron scale materials to 20 microns by vibration ball milling, calcining for 2 hours at 850 ℃, then performing vibration ball milling, and screening by a 200-mesh screen to obtain iron scale powder with the average particle size of 5-8 microns and the total oxide purity of 99.2%;
(2) material preparation and ball milling: 1329g of the iron scale powder obtained in the step (1) and 253g of BaCO are weighed3、10gSrCO3And 7g of CaCO3Mixing the powder, placing the mixture in a roller ball mill, adding 2000ml of deionized water, and ball-milling4h, obtaining mixed slurry;
(3) drying and pre-sintering: drying the mixed slurry obtained in the step (1) for 8 hours at 120 ℃ to obtain powder; then presintering the powder for 2h at 1220 ℃ in an air atmosphere to obtain a presintering material;
(4) vibration grinding: putting the pre-sintered material obtained in the step (3) into a vibration mill to obtain coarse powder with the average particle size of 3 mu m;
(5) secondary ball milling: weighing 600g of coarse powder obtained in the step (4), and adding 2.4g of CaCO3、1.2gSiO2Placing 1g of boric acid and 1400mL of deionized water in a ball mill for ball milling for 12.5h to ensure that the average particle size is 0.75 mu m; then, precipitating the slurry to obtain fine slurry with the water content of 65 wt%;
(6) pressing and molding and sintering: pressing the fine slurry obtained in the step (5) under the conditions that the forming magnetic field intensity is 9500Gs and the forming pressure is 10MPa to obtain a forming body; then sintering the formed body for 2h at 600 ℃ in air atmosphere, then heating to 1190 ℃ and sintering for 2h to obtain the Ba as the main phase0.9Ca0.05Sr0.05Fe11.7O19Permanent magnetic ferrite.
Example 2
The chemical formula of the permanent magnetic ferrite in the embodiment is: ba0.85Ca0.1Sr0.05Fe11.7O19。
The preparation method comprises the following steps: in the step (2) of this example, 1335g of iron scale powder and 240g of BaCO were weighed3、10g SrCO3And 14g of CaCO3The powder is used as raw material, other operation steps are the same as example 1, and the main phase is Ba0.85Ca0.1Sr0.05Fe11.7O19Permanent magnetic ferrite.
Example 3
The chemical formula of the permanent magnetic ferrite in the embodiment is: ba0.85Ca0.05Sr0.1Fe11.7O19。
The preparation method comprises the following steps: in the step (2) of this example, 1332g of iron scale powder and 239g of BaCO were weighed3、21g SrCO3And 7g of CaCO3The powder is used as raw material, other operation steps are the same as example 1, and the main phase is Ba0.85Ca0.05Sr0.1Fe11.7O19Permanent magnetic ferrite.
Example 4
The chemical formula of the permanent magnetic ferrite in the embodiment is: ba0.8Ca0.1Sr0.1Fe11.7O19。
The preparation method comprises the following steps: in the step (2) of this example, 1338g of iron scale powder and 226g of BaCO were weighed3、21g SrCO3And 14g of CaCO3The powder is used as raw material, other operation steps are the same as example 1, and the main phase is Ba0.8Ca0.1Sr0.1Fe11.7O19Permanent magnetic ferrite.
Comparative example 1
The difference compared with example 1 is that the main phase of Ba obtained in step (2) is directly carried out with untreated mill scale0.9Ca0.05Sr0.05Fe11.7O19Permanent magnetic ferrite.
Comparative example 2
(1) Material preparation and ball milling: 1374g of iron scale and 145g of BaCO are weighed3、21gSrCO3And 59g of CaCO3Mixing the powder materials, adding 2000ml of deionized water, placing the mixture in a roller ball mill, and carrying out ball milling for 3 hours to obtain mixed slurry;
(2) drying and pre-sintering: drying the mixed slurry obtained in the step (1) at 100 ℃ for 9 hours to obtain powder, and then pre-burning the powder for 4 hours at 1220 ℃ in an air atmosphere to obtain a pre-burnt material;
(3) vibration grinding: putting the pre-sintered material obtained in the step (2) into a vibration mill, and performing vibration milling for 120s to obtain coarse powder with the average particle size of 3 microns;
(4) secondary ball milling: weighing 600g of coarse powder obtained in the step (3), adding 1400mL of deionized water, placing in a ball mill, adding 2.4g of CaCO3、1.2gSiO21g of boric acid and 1400mL of deionized water, and performing ball milling for 12.5h to ensure that the average particle size is 0.8 mu m; then, precipitating the slurry to obtain fine slurry with the water content of 65 wt%;
(5) pressing and molding and sintering: pressing the fine slurry obtained in the step (4) under the conditions that the forming magnetic field intensity is 8500Gs and the forming pressure is 10MPa to obtain a forming body, and then placing the forming body in a moldSintering at 600 deg.C for 2h, heating to 1190 deg.C, and sintering for 2h to obtain Ba as main phase0.5Ca0.4Sr0.1Fe11.7O19Permanent magnetic ferrite.
Comparative example 3
Compared with comparative example 2, the difference is that the iron scale is pretreated by the same method as in example 1 before the batching, and the subsequent ferrite is prepared by the same method as in comparative example 2, so that the main phase of Ba is obtained0.5Ca0.4Sr0.1Fe11.7O19Permanent magnetic ferrite.
The results of the magnetic property test of the permanent magnetic ferrites obtained in examples 1 to 4 of the present invention and comparative examples 1 to 3 are shown in table 1.
TABLE 1 magnetic property test results of the permanent magnetic ferrites obtained in examples 1 to 4 and comparative examples 1 to 3
| Numbering | Br（Gs） | Hcb（Oe） | Hcj（Oe） | （BH）max |
| Example 1 | 4050 | 2822 | 2913 | 3.95 |
| Example 2 | 4031 | 2774 | 2875 | 3.90 |
| Example 3 | 4104 | 2638 | 2746 | 3.98 |
| Example 4 | 4134 | 2648 | 2759 | 4.03 |
| Comparative example 1 | 3442 | 2576 | 2710 | 2.69 |
| Comparative example 2 | 3815 | 2520 | 2564 | 3.4 |
| Comparative example 3 | 3896 | 2630 | 2665 | 3.68 |
As can be seen from the properties of the samples of the examples and the comparative examples in Table 1, the remanence of the permanent magnetic ferrites in examples 1 to 4 of the invention is higher than 4030Gs, 600Gs higher than the comparative example 1 without processed iron scale, and 200-300Gs higher than the comparative examples 2 and 3 with other Sr-Ba-Ca atomic ratios, the invention effectively maintains better magnetic property on the basis of reducing cost.
Claims (10)
1. A low-cost permanent-magnet barium ferrite is characterized in that the chemical formula is Ba1-x-yCaxSryFe2nO19In the formula, x is more than or equal to 0.03 and less than or equal to 0.2, y is more than or equal to 0.03 and less than or equal to 0.2, and n is more than or equal to 5.6 and less than or equal to 6.0.
2. A method for preparing the low-cost permanent magnetic barium ferrite of claim 1, comprising the steps of:
(1) iron scale pretreatment: ball-milling and crushing the scale, calcining and oxidizing, ball-milling again, and sieving to obtain scale powder;
(2) material preparation and ball milling: mixing the scaly iron powder obtained in the step (1) with BaCO3、SrCO3And CaCO3Mixing the powder in a ball mill, adding water and ball milling to obtain mixed slurry;
(3) drying and pre-sintering: drying the mixed slurry obtained in the step (2), and then pre-burning to obtain a pre-burnt material;
(4) vibration grinding: performing vibration grinding on the pre-sintering material obtained in the step (3) to obtain coarse powder;
(5) secondary ball milling: adding an additive and water into the coarse powder obtained in the step (4), and performing ball milling to obtain fine slurry;
(6) pressing and molding and sintering: pressing and molding the fine slurry obtained in the step (5) under the condition of a magnetic field to obtain a molded body; and sintering the obtained formed body to obtain the low-cost permanent magnet barium ferrite.
3. The preparation method of the low-cost permanent magnet barium ferrite according to claim 2, wherein in the step (1), the calcining temperature is 550-900 ℃; the calcining time is 1-3 h.
4. The low cost permanent magnet according to claim 2 or 3The preparation method of the magnetic barium ferrite is characterized in that in the step (2), the ingredients comprise the following raw materials in parts by weight: 9.9-11.3 parts of iron scale powder and SrCO30.1 to 0.4 part of BaCO30.05 to 0.20 portion of CaCO30.3 to 0.6 portion.
5. The preparation method of the low-cost permanent magnetic barium ferrite according to any one of claims 2 to 4, wherein in the step (3), the drying time is 6 to 10 hours; the drying temperature is 100-130 ℃; the pre-sintering is performed for 2-4 hours at 1100-1250 ℃ in air or oxygen atmosphere.
6. The preparation method of the low-cost permanent magnet barium ferrite according to any one of claims 2 to 5, wherein in the step (4), the duration of the vibromilling is 90 to 120 s; the average particle size of the coarse powder is 2-5 μm.
7. The method for preparing a low-cost permanent magnet barium ferrite according to any one of claims 2 to 6, wherein in the step (5), the amount of the additive is 0.5 to 2wt% of the coarse powder; the additive is CaCO3、SiO2And boric acid.
8. The preparation method of low-cost permanent magnetic barium ferrite according to any one of claims 2 to 7, wherein in the step (5), the mass of the water is 1.8 to 2.4 times of the mass of the coarse powder; the ball milling time is 10-15 h; the water content of the fine slurry is 65-72 wt%; the average particle size of solid material particles in the fine slurry is 0.6-0.8 mu m.
9. The preparation method of low-cost permanent magnet barium ferrite according to any one of claims 2 to 8, wherein in the step (6), the pressure of the compression molding is 6 to 12MPa, and the molding magnetic field strength is not less than 9000 Gs.
10. The preparation method of the low-cost permanent magnet barium ferrite according to any one of claims 2 to 9, wherein in the step (6), the sintering is performed by firstly preserving heat at 400-600 ℃ for 1-3 h, and then raising the temperature to 1200-1280 ℃ for 1.5-3 h.
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