CN104003702B - A kind of preparation method of calcium permanent ferrite material - Google Patents
A kind of preparation method of calcium permanent ferrite material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of calcium permanent ferrite material.The present invention utilizes fused salt as the medium of solid phase reaction, by adjustment fused salt kind and proportioning, the control of sintering process, to manufacture not containing the high magnetic characteristics calcium permanent ferrite material of cobalt, have the advantages that the cost of material is low, combination property is high, preparation method of the present invention has the advantage that reaction temperature is low, energy consumption is little.
Description
Technical field
The present invention relates to a kind of preparation method of permanent-magnet ferrite material, particularly a kind of preparation method of calcium permanent ferrite material.
Background technology
The composite oxides that ferrite is made up of iron family element and other one or more suitable metallic elements.The magneto plumbite type ferrite with hexaplanar is a class permanent-magnet ferrite, since nineteen fifty-two is developed out, because having superior cost performance, higher saturation magnetization and coercive force, high magnetocrystalline anisotropy and the feature such as Curie temperature, excellent chemical stability, make its range of application very extensive, can be used for various Denso motor, household electrical appliance motor, all kinds of automobile component motors such as motorcar electric lifting motor, wiper motor, the every field such as CD-ROM drive motor is established in medical treatment, office appliances motor.
The method now preparing Ferrite Material mainly contains following several:
(1) china-clay method is also known as oxidizing process, mainly by powdery starting material by preset ratio mixing, high temperature pre-burning, form bulk through high temperature solid state reaction and be prepared from through operations such as coarse crushing, secondary fine grinding, shaping, sintering again.This method is current industrialized preparing process, and main feature is: technical process is simply controlled, and production cost is lower.Shortcoming is: particle size distribution range is wider, granule-morphology is uneven, calcined temperature is higher.
(2) spray burning method, this method is developed by salt decomposition method and spray burning combine with technique, mainly metal salt solution is mixed with liquid fuel, at high temperature with spray pattern spray combustion, solution is decomposed by transient heating, obtain highly purified ultra-fine ferrite powder, main feature is: powder diameter is evenly distributed, stoichiometric proportion is accurate, sample sintering temperature is low, purity is higher.Shortcoming is: the gas of decomposition has corrosivity, environment is produced pollute, requirement for experiment condition is high.This method is difficult to realize suitability for industrialized production at present.
(3) coprecipitation, mainly presses the stoichiometric proportion Homogeneous phase mixing preset, with certain density alkaline solution (NaOH, NH by certain density metal salt solution
4oH etc.) as precipitation reagent, make precipitation by metallic ion, then after sediment filtration, washing being dried, high temperature sintering obtains product.The feature of this method is: epigranular, chemism are better, solid phase reaction temperature is low.Shortcoming is: when formula Design is rare earth ion doped, and the co-precipitation of ion is more difficult and uniformity is poor, and the particle of preparation is more easily reunited.
(4) hydro thermal method, this method is that strong basicity suspension-turbid liquid co-precipitation obtained is put into autoclave and is heated to below more than the boiling point of water and zero boundary's temperature, and making reacts between sediment obtains ferrite.The feature of this method is: react thus particle in aqueous and not easily reunite, the ferrite powder good dispersion of preparation, narrow diameter distribution, good crystallinity.Shortcoming is: material purity and equipment requirement high, hydro-thermal reaction is uncontrollable in addition, easily generates dephasign.
(5) sol-gal process is that metal salt solution is stoichiometrically hybridly prepared into solution, then adds organic acid and make part, and then regulate pH value, slow evaporation obtains gel presoma, obtains ferrite through high temperature sintering.The feature of this method is: easily realize ionic compartmentation, and particle diameter is little and be evenly distributed.Shortcoming is: cost is high, and sample easily ftractures.Be not suitable for suitability for industrialized production, be mainly used in laboratory research at present.
Existing the most widely used permanent-magnet ferrite is the Sr ferrite (SrFe with M type hexaplanar structure
12o
19) and Ba ferrite (BaFe
12o
19), along with all kinds of motor requires miniaturization, lightweight, precise treatment in recent years, this just requires that M type permanent-magnet ferrite needs to have higher magnetic property.The raising M type permanent-magnet ferrite magnetic property of current report has following several mode: 1) by ionic compartmentation Sr
2+, Ba
2+, Fe
3+obtain than Sr ferrite and the more excellent ferrite of Ba ferrite performance.If number of patent application is 200610169039 Ferrite Materials disclosing a kind of La, Co replacement Sr, Ba, after coarse crushing operation, twice Crushing of Ultrafine operation is added described in patent, average grain diameter is milled to 0.08-0.8 μm by Crushing of Ultrafine for the first time, be more preferably 0.1-0.2 μm, then through Overheating Treatment by the Ultramicro-powder less than 0.1 μm and comparatively meal reaction.Powder after heat treatment is broken to less than 0.8 μm by second time Crushing of Ultrafine, be more preferably 0.1-0.2 μm, so thin powder is very difficult in pressing under magnetic field process, shaping efficiency reduces greatly, be the performance of acquisition Br4510Gs and Hcj 5585 Oe in addition in this patent Example, the alternative amount of Co reaches 0.4, and production cost is higher.For another example number of patent application is 201110153849 permanent-magnet ferrite materials disclosing the replacement of a kind of rare earth, and its chemical formula is D
1-xr
xonFe
2-y-zln
zco
yo3, described permanent-magnet ferrite material and traditional permanent-magnet ferrite AB
120
19compare, A position and B position all part are replaced by lanthanide series, wherein: D is one in Ca, Ba and Sr element, two or three, A position can not comprise La, and B position can not comprise Co.In embodiment, D position replaces that to employ mol ratio be that to employ mol ratio be the Gd of the 0.38 and Co of 0.26 for the Nd of 0.41 and the La of 0.23, Ln in 3, magnetic property Br=0.47T, Hcj=430kA/m, maximum magnetic energy product (BH) max=43.3 kJ/m
3performance, but employ expensive Nd in a large number
2o
3and Gd
2o
3, significantly add production cost, lose the characteristic of M type permanent-magnet ferrite high performance-price ratio.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of calcium permanent ferrite material, utilize fused salt as the medium of solid phase reaction, to manufacture not containing the high magnetic characteristics calcium permanent ferrite material of cobalt, have the advantages that the cost of material is low, combination property is high, preparation method of the present invention has the advantage that reaction temperature is low, energy consumption is little.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for calcium permanent ferrite material, comprises the following steps:
(1) batching and batch mixing
Principal component is by (1-x-y) CaOxAO
r
2o
3nFe
2-zal
zo
3composition formula, A is one or both in Sr, Ba, and R is La, wherein 0.2≤x≤0. 5,0.005≤
≤ 0.15, and 0.3≤1-x-y≤0.7,0.01≤z≤0.15,5.5≤n≤6.2;
The fused salt accurately taking each raw material of principal component and each raw material total weight 10%-20% of principal component carries out wet ball-milling and obtains compound;
Average grain diameter through wet ball-milling compound is preferably 0.6-1 μm.Grain diameter is little, and surface area is large, and particle and fused salt contact area are conducive to molten salt react ion more greatly, improves diffusion rate, reduces reaction time and temperature.
(2) pre-burning
The compound of step (1) is first at 400-600 DEG C of scope inside holding 1-3h under standard atmosphere condition, then be warming up to 900-1050 DEG C of insulation 1-5 hour, after cooling, dry-type pulverizing obtains Preburning material;
(3) material and fine grinding is washed
Put into sedimentation basin after being weighed by the Preburning material of step (2) to add water agitator treating, after washing precipitation, slip is proceeded to sand mill, adding Preburning material weight 0.2-1% grinding aid and 1-1.5% dispersant, to be milled to average grain diameter be 0.5-1.5 μm, proceed in centrifugal ball mill again, and add accessory ingredient ball milling 2.5-4h;
This fine grinding technology coordinates molten salt growth method can better control fine grinding particle diameter, improves fine grinding efficiency, and particle size is even, and crystal formation is complete, in normal distribution.Well known in the art, fine grinding particle diameter is meticulous, and during average grain diameter less than 0.5 μm, water discharge time increases, and shaping efficiency significantly reduces, and affects production efficiency.Particle diameter is excessively thick, then remanent magnetism and coercive force can decline.
(4) shaping
Slip precipitation after step (3) has been processed, reaching moisture content is 25-40%, at 10000-14000Gs magnetic field compacted under;
(5) sinter
The formed body that step (4) obtains is incubated 1-3 hour at 100 DEG C-400 DEG C, then is warming up to 800-850 DEG C, be then warming up to 1050 DEG C-1200 DEG C, insulation 1-3 hour.
The barium permanent-magnet ferrite material that the present invention obtains is M type hexagonal ferrite.
Fused salt is as the medium of high temperature solid state reaction, and itself does not participate in the middle of solid phase reaction.When reaching uniform temperature, fused salt can present molten condition, each reactive component mobility in the liquid phase is obviously increased, reactant is not limited to the direct contact interface of adjacent material, also have the Free Surface along reactant particle to carry out simultaneously, diffusion rate is significantly improved, and this significantly can reduce time and the temperature of reaction.Well known in the art, the sintering temperature of Ferrite Material is up to 1200-1300 DEG C, and the great many of experiments through inventor shows, adopt fused salt as reaction media, sintering temperature can be made to be reduced to about 900-1050 DEG C, reduce energy resource consumption, this is fairly obvious to the energy-saving effect in production process.On the other hand, dissolve after fused salt melting and parcel component particles material, alleviate the mutual bonding between particle, the Preburning material powder granule therefore obtained is reunited less, only has slightly weakly agglomerated.
The patent report of current high-performance M type ferrite focuses mostly on to improve saturation magnetization and magnetocrystalline anisotropy at ion doping and add additive and improves in magnet density, the degree of orientation etc. and improve magnetic property.
Experiment and sem analysis show, there is the crystalline form of hexangle type sheet, the ratio more than 20% that in Preburning material magnet, the radius-thickness ratio ratio of thickness (crystal particle diameter with) of crystal is 2.5-4.5, preferably more than 50%, average crystal grain diameter about 3 μm, the crystal radius-thickness ratio in sintered magnet is the ratio more than 20% of 1.5-3.5, be preferably more than 50%, the ratio more than 20% of about crystal particle diameter 1-1.2 μm, is preferably more than 50%, can obtains high Br, Hcj.If radius-thickness ratio is excessive, crystal is along C direction of principal axis undue growth, and hexangle type flat crystal is long excessively thin, increases according to formula Hcj=0.48 (Ha-NMs) demagnetizing factor, and demagnetizing field increases, and causes Hcj to reduce.If radius-thickness ratio is too small, along the growth of C direction of principal axis not exclusively, hexagonal plate crystal is thickening to shorten crystal, causes Br to decline.
Experiment shows to utilize fused salt can well control pattern and the size of crystal, this with the surface energy between fused salt and reactant, interface energy is relevant.The reaction starting stage, saturated solution is formed in reactants dissolved and fuse salt, after reaction generates ferrite, because ferrite is insoluble to fuse salt, through slow cooling, ferrite is separated out gradually from fuse salt, forms hexagonal plate M type ferrite crystal, ferrite hexangle type flat crystal production rate prepared by molten salt growth method is high, the complete requirement meeting high performance ferrite of crystal formation.
As preferably, described grinding aid is selected from the one in sodium hexametaphosphate, calgon, sodium metasilicate, polyacrylate, ethylene glycol.
As preferably, described dispersant is selected from the one in calcium gluconae, D-sorbite.
As preferably, described accessory ingredient comprises CaCO
3and SiO
2, according to each raw material total weight CaCO of principal component
3addition is 0.5-1.5%, SiO
2addition is 0.1-1%.CaCO
3and SiO
2, can CaSiO be formed
3although the fusing point of itself reaches 1540 DEG C, after combining with ferrite, significantly can reduce and reach about 1150 DEG C, can reduce sintering temperature on the one hand, energy acceleration of sintering, increases magnet density on the other hand, improve remanent magnetism, excessively growing up of crystal grain can also be suppressed, thus improve magnetic property.
As preferably, described fused salt is selected from the one in following combination: Na
2sO
4+ K
2cO
3+ Li
2cO
3(respective molar percentage: 31.5%, 43.5%, 25%), K
2b
4o
7+ Na
2b
4o
7the respective molar percentage of+NaCl(: 10%, 18.5%, 71.5%), NaBr+KBr+NaBO
2(respective molar percentage: 26%, 40%, 34%), NaBr+KBr+K
2sO
4(respective molar percentage: 25%, 35%, 40%).A large amount of explorative experiment through the present inventor show, different fused salts is very remarkable on the impact of ferrite crystal, and choosing suitable fused salt, to meet high performance ferrite crystal to generation very important.Because combination fused salt can combine the advantage utilizing variety classes fused salt, therefore combine the easier proportioning of the more single fused salt of fused salt to use, the fused salt with eutectic can be preferably selected in combination fused salt, eutectic fused salt has lower fusing point and higher boiling point, contributes to convenient collocation fused salt and wider temperature regulated space.In addition, the fused salt selected should have lower vapour pressure, low viscosity, high capillary physical property.Therefore the present invention has selected above-mentioned specific fused salt combination.
As preferably, in step (5), the formed body that step (4) obtains is incubated 1-3 hour at 100 DEG C-400 DEG C, be warming up to 800-850 DEG C with the heating rate of 0.8-1.5 DEG C/min again, be then warming up to 1050 DEG C-1200 DEG C with the heating rate of 1.4-2.5 DEG C/min, insulation 1-3 hour.The crystal grain radius-thickness ratio obtained under this sintering process is the ratio more than 50% of 1.5-3.5, and the ratio of about crystal particle diameter 1-1.2 μm can reach more than 50%, and crystal boundary is clear, and crystal formation is complete in hexagonal plate, meets high magnetic characteristics feature.
The invention has the beneficial effects as follows:
The M type ferrite adopting process of the present invention to coordinate the major-minor composition of specific proportioning to prepare, can obtain the Br of about 4300-4400GS, about Hcj4900-5200Oe, (BH) about max4.4MGOe.
Compared with prior art, the present invention has advantage and the innovation of following uniqueness: be different from conventional method and rely on ionic compartmentation and introduce the methods such as additive to improve magnetic property, and focus on that utilizing the unique advantage of fused salt and the control of adjusting process method to ferrite microcosmic crystal morphology, grain size to prepare meets high-performance permanent magnetic ferrite material.Use fused salt Process, compared with the method such as hydro thermal method, collosol and gel, there are process conditions controlled, without the need to increasing extras, strong with conventional solid-state method associativity, be beneficial to suitability for industrialized production, reaction temperature is low, low power consumption and other advantages, by adjustment fused salt kind and proportioning, the control of sintering curre, obtains high performance permanent-magnet ferrite.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1: by principal component raw material by (1-x-y) CaOxAO
r
2o
3nFe
2-zal
zo
3composition formula, A is Sr and Ba, R is La.Wherein x=0.25(Sr:Ba=2:3), y=0.15, z=0.1, n=6.1 take weight (principal component raw material are specially: Fe
2o
3, La
2o
3, Al
2o
3, BaCO
3, Sr CO
3, CaCO
3), then take fused salt: Na
2sO
4+ K
2cO
3+ Li
2cO
3(respective molar percentage: 31.5%, 43.5%, 25%), fused salt weight is by each raw material total weight 10% of principal component, put into ball mill wet ball-milling together, Ball-milling Time 8 hours (average grain diameter 0.6-1 μm), by 500 DEG C of insulations 2 hours in atmospheric conditions after the compound drying that obtains, 900 DEG C are warming up to again with 3 DEG C/minute, be incubated 3 hours, by powdered for Preburning material oscillatory type crusher in crushing after cooling, recording particle diameter D50 is 2.6 μm, proceed in sedimentation basin by after Preburning material powder weighing again, with after water repeatedly washing precipitation, slip is proceeded to sand mill, add sodium hexametaphosphate and 1.4% D-sorbite of Preburning material weight 0.55%, sand milling 3 hours, detecting slip D50 is 1.1 μm, proceed to again in centrifugal ball mill, and add SiO
2the each raw material total weight of 0.7%(principal component), CaCO
3the each raw material total weight of 1.2%(principal component), rotating speed controls at 800 revs/min, fine grinding 3 hours, and it is 0.31 μm that slip detects D10, D50 is 0.74 μm, D90 is 1.36 μm and slip is proceeded to sedimentation basin precipitation, makes its water content be about 35%, shaping by forming machine wet type, forming magnetic field 10000Gs-14000 Gs, briquetting pressure 5MPa, gained molded blank diameter 43.2mm, height 13 mm.Molded blank is incubated 1 hour at 350 DEG C, to remove water in formed body and dispersant, be warming up to about 800 DEG C again, heating rate controls at 1.2 DEG C/min, after 800 DEG C, heating rate controls at 2 DEG C/min, then at 1205 DEG C, be incubated 1 hour, measure magnetic property (see table 1) by after the sample extraction surface grinding after sintering.
Embodiment 2 fused salt consumption is each raw material total weight 15% of principal component, and all the other are with embodiment 1.
Embodiment 3 fused salt consumption is each raw material total weight 20% of principal component, and all the other are with embodiment 1.
Embodiment 4 fused salt consists of: K
2b
4o
7+ Na
2b
4o
7the respective molar percentage of+NaCl(: 10%, 18.5%, 71.5%), fused salt consumption is each raw material total weight 10% of principal component, and be warming up to 970 DEG C with 2 DEG C/minute during pre-burning, all the other are with embodiment 1.
Embodiment 5 fused salt consumption is each raw material total weight 15% of principal component, and all the other are with embodiment 4.
Embodiment 6 fused salt consumption is each raw material total weight 20% of principal component, and all the other are with embodiment 4.
Principal component raw material are pressed (1-x-y) CaOxAO by embodiment 7
r
2o
3nFe
2-zal
zo
3composition formula, A is Sr and Ba, R is La.Wherein x=0.2(Sr:Ba=3:7), y=0.2, z=0.14, n=6.1 take weight, and all the other are with embodiment 1.
Embodiment 8 fused salt consumption is each raw material total weight 15% of principal component, and all the other are with embodiment 7.
Embodiment 9 fused salt consumption is each raw material total weight 20% of principal component, and all the other are with embodiment 7.
Principal component raw material are pressed (1-x-y) CaOxAO by embodiment 10
r
2o
3nFe
2-zal
zo
3composition formula, A is Sr and Ba, R is La.Wherein x=0.2(Sr:Ba=3:7), y=0.2, z=0.14, n=6.1 take weight, and all the other are with embodiment 4.
Embodiment 11 fused salt consumption is each raw material total weight 15% of principal component, and all the other are with embodiment 10.
Embodiment 12 fused salt consumption is each raw material total weight 20% of principal component, and all the other are with embodiment 10.
Comparative example 1: by principal component raw material by (1-x-y) CaOxAO
r
2o
3nFe
2-zal
zo
3composition formula, A is Sr and Ba, R is La.Wherein x=0.25(Sr:Ba=2:3), y=0.15, z=0.1, n=6.1 takes weight, puts into ball mill wet ball-milling, Ball-milling Time 5 hours, 3 hours are incubated respectively by being warming up to 1250 DEG C with 4 DEG C/minute more in atmospheric conditions after the raw mixture drying obtained, by powdered for Preburning material oscillatory type crusher in crushing after cooling, recording particle diameter D50 is 2.8 μm, then by Preburning material powder and SiO
20.7%(principal component raw material total weight), CaCO
31.2%(principal component raw material total weight), calcium gluconae 1.3%(Preburning material weighing scale) to add in ball mill ball milling 21 hours, slip detection D10 is 0.15 μm, D50 is 0.85 μm, D90 is 3.5 μm, slip is proceeded to sedimentation basin precipitation, its water content is made to be about 35%, shaping by forming machine wet type, forming magnetic field 10000Gs-14000 Gs, briquetting pressure 5MPa, gained molded blank diameter 43.2mm, height 13mm.Molded blank is incubated 1 hour at 350 DEG C, and to remove water in formed body and dispersant, then be warming up to about 1210 DEG C, heating rate controls at 3 DEG C/min, is incubated 1 hour, measures magnetic property (see table 1) by after the sample extraction surface grinding after sintering.
Comparative example 2: by principal component raw material by (1-x-y) CaOxAO
r
2o
3nFe
2-zal
zo
3composition formula, A is Sr and Ba, R is La.Wherein x=0.2(Sr:Ba=3:7), y=0.2, z=0.14, n=6.1 take weight.Other is with comparative example 1.
Show from table 1 data analysis, in same recipe situation, the magnetic property of the permanent-magnet ferrite material adopting present invention process to obtain all is better than traditional handicraft, and present invention process reaction temperature is low, and energy consumption is low.
Protection range required by the claims in the present invention all can be implemented; the parameter of other each temperature, time, consumption all can adjust within the scope of the claims; the performance of gained permanent-magnet ferrite material is similar to the aforementioned embodiment, and therefore not to repeat here in the present invention.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (3)
1. a preparation method for calcium permanent ferrite material, is characterized in that, comprises the following steps:
(1) batching and batch mixing
Principal component is by (1-x-y) CaOxAO
r
2o
3nFe
2-zal
zo
3composition formula, A is one or both in Sr, Ba, and R is La, wherein 0.2≤x≤0. 5,0.005≤
≤ 0.15, and 0.3≤1-x-y≤0.7,0.01≤z≤0.15,5.5≤n≤6.2;
The fused salt accurately taking each raw material of principal component and each raw material total weight 10%-20% of principal component carries out wet ball-milling and obtains compound;
(2) pre-burning
The compound of step (1) is first at 400-600 DEG C of scope inside holding 1-3h under standard atmosphere condition, then be warming up to 900-1050 DEG C of insulation 1-5 hour, after cooling, dry-type pulverizing obtains Preburning material;
(3) material and fine grinding is washed
Put into sedimentation basin after being weighed by the Preburning material of step (2) to add water agitator treating, after washing precipitation, slip is proceeded to sand mill, adding Preburning material weight 0.2-1% grinding aid and 1-1.5% dispersant, to be milled to average grain diameter be 0.5-1.5 μm, proceed in centrifugal ball mill again, and add accessory ingredient ball milling 2.5-4h;
(4) shaping
Slip precipitation after step (3) has been processed, reaching moisture content is 25-40%, at 10000-14000Gs magnetic field compacted under;
(5) sinter
The formed body that step (4) obtains is incubated 1-3 hour at 100 DEG C-400 DEG C, then is warming up to 800-850 DEG C, be then warming up to 1050 DEG C-1200 DEG C, insulation 1-3 hour;
Described accessory ingredient comprises CaCO
3and SiO
2, according to each raw material total weight CaCO of principal component
3addition is 0.5-1.5%, SiO
2addition is 0.1-1%; Described fused salt is selected from the one in following combination: Na
2sO
4+ K
2cO
3+ Li
2cO
3, K
2b
4o
7+ Na
2b
4o
7+ NaCl, NaBr+KBr+NaBO
2, NaBr+KBr+K
2sO
4; In step (5), the formed body that step (4) obtains is incubated 1-3 hour at 100 DEG C-400 DEG C, 800-850 DEG C is warming up to again with the heating rate of 0.8-1.5 DEG C/min, then 1050 DEG C-1200 DEG C are being warming up to the heating rate of 1.4-2.5 DEG C/min, insulation 1-3 hour.
2. preparation method according to claim 1, is characterized in that: described grinding aid is selected from the one in sodium hexametaphosphate, calgon, sodium metasilicate, polyacrylate, triethanolamine, ethylene glycol.
3. preparation method according to claim 1, is characterized in that: described dispersant is selected from the one in calcium gluconae, D-sorbite.
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| CN101209920A (en) * | 2007-08-21 | 2008-07-02 | 横店集团东磁股份有限公司 | Economic sintering permanent-magnet ferrite and preparing method thereof |
| CN102010188A (en) * | 2010-10-12 | 2011-04-13 | 陕西科技大学 | Preparation method of nickel-zinc ferrite powder |
| CN102260072A (en) * | 2011-06-13 | 2011-11-30 | 中国地质大学（武汉） | Method for synthesizing high-performance barium ferrite by using molten salt as flux and reaction medium |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209920A (en) * | 2007-08-21 | 2008-07-02 | 横店集团东磁股份有限公司 | Economic sintering permanent-magnet ferrite and preparing method thereof |
| CN102010188A (en) * | 2010-10-12 | 2011-04-13 | 陕西科技大学 | Preparation method of nickel-zinc ferrite powder |
| CN102260072A (en) * | 2011-06-13 | 2011-11-30 | 中国地质大学（武汉） | Method for synthesizing high-performance barium ferrite by using molten salt as flux and reaction medium |
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