CN101372417B - High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof - Google Patents
High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof Download PDFInfo
- Publication number
- CN101372417B CN101372417B CN2008102316338A CN200810231633A CN101372417B CN 101372417 B CN101372417 B CN 101372417B CN 2008102316338 A CN2008102316338 A CN 2008102316338A CN 200810231633 A CN200810231633 A CN 200810231633A CN 101372417 B CN101372417 B CN 101372417B
- Authority
- CN
- China
- Prior art keywords
- saturation magnetization
- magnetic powder
- coercive force
- powder
- specific saturation
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The present invention provides a method for preparing a strontium ferrite magnetic powder with high specific saturation magnetization and high coercive force. Nitrates and chlorides of Sr, R Fe and M with limited amounts are dissolved, added with citric acid and ammonia gas to adjust the solution obtained to neutral or slightly alkaline so as to prepare sol; the sol is heated and evaporated to prepare gel, a precursor is prepared by self-propagating combustion, and the magnetic powder is obtained by calcining the precursor at a low temperature. In the composition, R is at least one of Y, La, Pr, Nd and Ce, and M is at least one of Co, Ni, Zn, Cu and Mn. In the method, the magnetic powder can be obtained by mixing, ball milling, calcining, fine grinding and annealing the precursor obtained by self-propagating combustion and at least one of the nano-grade SiO2, CaCO3, B2O3, SrSO4, Al2O3 and Cr2O3. The magnetic powder prepared by the technology has the specific saturation magnetization of 71-75emu/g and the coercive force of 5.5-6.5kOe. The magnetic powder is suitable for preparing bonded permanent magnets and automobile motor magnets requiring high magnetic property.
Description
Technical field
The invention belongs to the nano-functional material preparing technical field, relate to a kind of preparation method of strontium ferrite magnetic powder, relate in particular to a kind of method that adopts the strontium ferrite magnetic powder of sol-gel technology preparing high specific saturation magnetization, high-coercive force and high remanent magnetism.
Technical background
Sol-gel method is one of main method of preparation nano-powder.This technology forms metal complex by complexing agent and metal ion, then by being cross-linked to form high-molecular gel.In gel, the metal ion uniform distribution is removed by thermal treatment in the process of gelifying agent, and metal ion generation oxidizing reaction forms nanometer oxide material.The method of removing gelifying agent has two kinds of thermal decomposition method and combustion methods, and heat treated temperature and soaking time play a decisive role to the particle diameter and the performance of nano-powder.
During complex metal oxides, the sol-gel law technology is slightly different in preparation, not necessarily forms composite oxides because remove the powder of getting behind the gel, needs to adopt special processing method just can prepare required composite oxides.After these special processing methodes are included in and remove gelifying agent, under higher temperature or longer soaking time, calcine, perhaps calcine through after the granulation.Adopting the characteristics of Prepared by Sol Gel Method composite oxides is to reduce calcining temperature, the composite oxides that generate are dispersion state, do not need fragmentation or broken easily, particle diameter can reach nano level, particle size range is narrow and be normal distribution, has special physicals or traditional application performance is improved significantly.
M type hexagonal strontium ferrites is a kind of composite oxides of being made up of ferric oxide and strontium oxide, has the magnetoplumbite structure, and molecular formula can be expressed as SrFe12O19, is topmost permanent-magnet ferrite magneticsubstance.Its performance perameter comprises remanent magnetism (Br), and coercive force (HcJ) and magnetic energy product ((BH) max) obtain the target that high remanent magnetism and high-coercive force are the strontium ferrite material technical researches.
Chinese patent CN1139648 discloses a kind of preparation method who prepares ultra thin hexagonal crystal system ferrite.This method is a raw material with metal oxide, oxyhydroxide, organic acid salt or nitrate, is that gelifying agent descends the preparation gels at 80～150 ℃ with the stearic acid, passes through calcination again, prepares ultra thin hexagonal crystal system ferrite at 600～1300 ℃ of high temperature solid state reactions.The ferrite powder particle of this method preparation is 20～90nm, and this patent does not have the report of magnetic property yet.
CN1378996 has proposed a kind of microwave induction and low-temp burning synthesis of nano BaFe
12O
19The method of powder is by Ba
2+, Fe
3+Inorganic salt (nitrate or carbonate), citric acid, muriate with mol ratio 1:(8～13): (5～60): the mixed of (0.5～3), wherein muriate is Repone K or sodium-chlor or the combination of the two, the combination mol ratio is NaCl/KCl=1:(0.5～1.5), by the synthetic presoma that loosens that obtains of microwave induction and low-temp burning, presoma is heat-treated after washing, can make nanometer hexagonal crystal form B aFe
12O
19, size of microcrystal 50～300nm, crystal formation are the sheet sexangle of rule, and magnetic property is adjustable; Saturation magnetization is 55.79～66.79emu/g, and HCJ is 4.59～5.08kOe.
Chinese patent CN1458118 discloses a kind of preparation method of nanometer permanent-magnet ferrite powder, this preparation method is main raw material with nitrate, form colloidal sol, gel, be dried into technological processs such as former powder and calcining by its mixing solutions and polyoxyethylene glycol, can obtain the permanent-magnet ferrite powder.Its particle diameter is 20～120 nanometers.This kind preparation method is very low to the requirement of equipment, and technology is simple, and prepared product particle is even, narrow diameter distribution, product purity height.This patent both can be used to prepare the W type ferrite, also can be used to prepare the M type ferrite, but the report of magnetic magnetic property is not arranged.
CN1472166 discloses the method that a kind of citric acid complex prepares M-type ferrite nanoparticle.Be that carbonate, citric acid and/or ethylene glycol with iron nitrate, barium and strontium is raw material, earlier iron nitrate be precipitated as Fe (OH)
3, repetitive scrubbing is removed NO
3 -Ion, through sol-gel process, high-temperature roasting thermal treatment (thermal treatment temp is 700～1100 ℃, heat treatment time 1～10 hour) and getting.The magnetic property of the strontium ferrite magnetic powder of this technology preparation is 65.2～74emu/g, and coercive force reaches 5750～6028Oe, and the magnetic particle diameter is 100～130 nanometers.
CN1654144 has proposed a kind of method of auto-combustion method synthesizing barium ferrite micro mist.This method comprises the steps: 1) nitrate of baryta is made into the solution of 0.125M～0.25M, iron nitrate is made into the solution of 0.75～1.0M, is 12 ratio according to the Fe/Ba mol ratio, under agitation makes its mixing, obtains mixed solution A; 2) mol ratio by nitrate ion in the mixed solution A and citric acid is 1:1～3, takes by weighing citric acid, and citric acid is dissolved in mixed solution A, stir, obtain mixing solutions B, regulate pH value to 7.5～8.5 with acid or alkali, in 75～85 ℃ of heating evaporations, 8～12 hours formation gels; After treating the moisture evaporate to dryness, move to self-propagating combustion formation powder presoma can take place in 200 ℃ of constant temperature electric furnaces; 3) presoma is incubated 2～4 hours 600 ℃～700 ℃ calcinings, promptly obtains the barium ferrite micro mist.The ferrite micropowder particle diameter is 0.1～0.5 μ m, and saturation magnetization is 41～48emu/g, and coercive force is 3078～3707Oe.
Chinese patent CN1749208 discloses a kind of method for preparing M type barium ferrite magnetic powder with the carbohydrate hydrolysate as the complexing gelifying agent, this method is to desolvate as complexing agent with the low-carbon alcohol extrct with the carbohydrate hydrolysate, metal salt solution is mixed with saccharide solution, add the salts solution of wanting adulterated metal ion then on demand, heating evaporation moisture, generate a kind of hydrate of barium iron oxygen through liquid phase reaction, with this reacted solution cooling, regulate the pH value, the extrct branch that anhydrates, vacuum filtration and drying obtain presoma then, and the precursor thermal treatment with forming obtains magnetic ferrite powder.This method has overcome that citric acid method prepares the raw material type that ferrite magnetic material exists and the conditional request that forms gel is higher, and the citric acid consumption is big, raw materials cost height, deficiency such as dehydration and heat treatment time are long.But the magnetic property of the magnetic powder of this method preparation only is: saturation magnetization 38.46～64.48emu/g, and residual magnetization is 20.6～43.8emu/g, coercive force is 1624.9～1848.9Oe;
Utilize the gel-sol legal system to be equipped with ferrite magnetic material and can avoid in the coprecipitation method process existing distributing and separate out, thereby cause the ununiformity formed, have bigger superiority aspect the preparation high performance magnetic material.But in the prior art, sol-gel method prepares the technology of M type ferrite, basically only adopt and contain strontium or/and the compound of baric and iron containing compounds prepared in reaction strontium ferrites, the magnetic property of ferrite powder is all lower, can not embody the advantage of sol-gel technique aspect raising ferrite magnetic performance.
Summary of the invention
The present invention gets purpose and is to provide the preparation method of a kind of high specific saturation magnetization and high coercitive force strontium ferrite magnetic powder at the lower defective of the ferrite powder magnetic property of prior art for preparing.
Strontium ferrite magnetic powder of the present invention has the Magnetoplumbate-type crystalline structure, and it consists of:
Sr
1-xR
x(Fe
12-yM
y)
zO
19
Wherein: 0.01≤x≤0.4
0.01≤y≤0.4
0.7≤z≤1.4
0.9≤x/yz≤1.08
0.05≤(1-x)/(12-y)z≤0.11
R is at least a in yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd) and the cerium (Ce);
M is at least a in cobalt (Co), nickel (Ni), zinc (Zn), copper (Cu) and the manganese (Mn);
The preparation method of strontium ferrite magnetic powder of the present invention may further comprise the steps successively:
The compound that 1. will contain Sr, Fe, R and M is dissolved in the deionized water solution of citric acid, and Fe concentration is 0.5～1.5 mol in the solution, Fe
3+With the mol ratio of citric acid be 1:1～1:5; The mol ratio of Sr, Fe, R, M is 1:(11.5～12.5 in the solution): (0.03～0.3): (0.03～0.3); R is at least a in yttrium, lanthanum, praseodymium, neodymium, the cerium; The compound of the described Sr of containing, R, Fe, M is muriate, nitrate, oxyhydroxide, carbonate, organic acid salt or the alkoxide of Sr, R, Fe and M; M is at least a in cobalt, nickel, zinc, copper, the manganese;
2. feed ammonia, regulator solution pH value to 7.5～8.5 obtain colloidal sol;
3. with colloidal sol in 60～90 ℃ of following evaporating solvents, gel;
4. gel is placed retort furnace, under 200～500 ℃, ignite, obtain the powder precursor after self-propagating combustion is complete;
5. after the powder precursor being placed the mortar porphyrize, in the crucible of packing into,, obtain magnetic in 500～1000 ℃ of calcinings 1～5 hour.
The strontium ferrite magnetic powder of the present invention's preparation is a dispersion state, and particle diameter is between 30～150 nanometers, and its specific saturation magnetization is that coercive force is between 5.5～6.2kOe between 73～75emu/g.
The compound that contains Sr, R, Fe and M as raw material among the present invention can be muriate, nitrate, oxyhydroxide, carbonate, organic acid salt or alkoxide, these salt can generate the Citrate trianion of respective metal element with citric acid generation complex reaction, the Citrate trianion that is generated is the inner complex between metal ion and the citrate, and stability is very high.In the reaction that contains the above-claimed cpd of forming ferritic metallic element and citric acid logical ammonia regulate pH value for neutrality to weakly alkaline, its purpose is the acidic cpd that generates in the consumption reaction process, promotes that the carrying out of citric acid complex formation reaction of metal ion is complete.The present invention adopts logical ammonia to substitute to use ammoniacal liquor as acidity-basicity regulator, can reduce to bringing a large amount of moisture in the system into, the influence of concentration in the accurate control reaction process is had positive effect, and can shorten the time that forms gel.
In order to improve the coercive force of strontium ferrites powder, in strontium ferrite magnetic powder, also add the nano level additive.Its concrete adding technology is: in step 4. in the gained powder precursor, add the nano level additive of powder precursor quality 0.1～1% and the dispersion agent of powder precursor quality 0.1～10%, and add water and mix, the granule content in the control mixed slurry is 30～90wt%; Mixture after 80～150 ℃ of oven dry, is preheated 1～4 hour at 100～400 ℃, 600～1200 ℃ of calcinings 1～4 hour, obtain mixing grog then; To mix grog wet ball grinding to particle diameter again is 0.6～1.5 μ m, obtains magnetic; Maybe will mix grog 500～800 ℃ of annealing 1～5 hour, obtain magnetic.
Adopt nanometer additive be utilize add nano particle advantages such as high reaction activity, high-specific surface area the iron strontium oxide magnetic micro mist of Prepared by Sol Gel Method is carried out cutting pattern, can adapt to of the requirement of different application intended application to the strontium ferrite magnetic powder magnetic property.The nano level additive can adopt SiO
2, CaCO
3, B
2O
3, SrSO
4, Al
2O
3, Cr
2O
3Deng.
The present invention has the nano level particle diameter by the iron strontium oxide magnetic micro mist of Prepared by Sol Gel Method, and the additive that adds also is a nano particle, so in the process of adding additive, only use hybrid technology, and do not adopt ball milling method, can reduce mechanical milling process and introduce excessive detrimental impurity element, the control accuracy that strontium ferrites is formed is favourable.Use the wet-mixed technology to reach uniform mixing easily, but because the trend of the tangible one-tenth coacervate of nanoparticle, it is necessary adding suitable dispersion agent.The dispersion that is added should be removed by solution in follow-up calcination process.The present invention studies and confirms to have the organic compound of hydroxyl or carboxyl, or have hydroxyl or carboxyl organic compound neutral salt or have hydroxyl or the lactone of the organic compound of carboxyl is proper dispersion agent.As glyconic acid (C
6H
12O
7), lactobionic acid (C
12H
22O
12), glucoheptonic acid gamma lactone (C
7H
12O
7), sorbose (C
6H
14O
6), or have can dissociate into acid the organic compound xitix (C with enol form hydroxyl
6H
8O
6).
The calcination of chamotte that adds the nanometer additive preparation is the dispersed particles shape, be easier to obtain the magnetic that particle diameter is 0.6～1.5 μ m through wet ball grinding, magnetic property can reach the specific saturation magnetization of 71～74emu/g and the coercive force of 5.9～6.5kOe, is suitable for preparing the ferrite sintered body magnet of high remanent magnetism (Br) and high-coercive force (HcJ); Magnetic after annealing is suitable for making the high-performance bonded permanent ferrite.
This shows that the adding of nanometer additive the coercive force of improveing the strontium magneticsubstance is had more significantly effect, and specific saturation magnetization only has very little reduction.
The present invention adopts sol-gel method to prepare the method for strontium ferrite permanent magnet powder, utilizes rare earth element to replace Sr element in the part strontium ferrites, with can form+transition metal of divalent metal ion replaces the Fe in the strontium ferrites
3+Electric charge with the balance strontium ferrites; Pass through to adopt the coercive force of nano level additive on the other hand, thereby realize utilizing sol-gel method to prepare the strontium ferrite magnetic powder of high specific saturation magnetization and high-coercive force with raising strontium ferrites powder.
Embodiment
Embodiment 1
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 1.0991g, and cobalt chloride (CoCl
36H
2O) 0.6257g.
The above-mentioned raw material that takes by weighing is placed beaker, add the 500ml deionized water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again; In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of evaporating solvents; Gel D moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; With precursor powder E porphyrize in mortar, in the corundum crucible of packing into, calcining insulation 4h under 700 ℃ constant temperature, the strontium ferrites micro mist that obtains.
Consisting of of gained strontium ferrites micro mist: Sr
0.8La
0.2(Fe
11.8Co
0.2) O
19Particle diameter is 30～80nm; Saturation magnetization is 74.5emu/g, and coercive force is 5800Oe (adopting vibrating sample magnetometer (VSM) to measure the magnetic property of magnetic).
Embodiment 2
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 1.0991g, and cobalt chloride (CoCl
36H
2O) 0.6257g.
The above-mentioned raw material that takes by weighing is placed beaker, add 500ml secondary water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again; In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of following evaporating solvents; Gel D moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; Take by weighing precursor powder E30g, the nanometer SiO of particle diameter 20～80nm
20.15g particle diameter is less than the nanometer CaCO of 100nm
30.20g calcium gluconate 0.35g places beaker, adds water 45ml, mixes 30 minutes, obtains mixture of viscous form F; With mixture F 90 ℃ of oven dry, in mortar levigate after, place muffle furnace to preheat 3 hours at 280 ℃, obtained mixing grog G in 1.5 hours 1200 ℃ of calcinings then; To mix grog G wet ball grinding to particulate D90 less than 1 μ m (adopting MS-2000 type laser particle analyzer to measure granularity), oven dry, 600 ℃ down annealing obtained magnetic in 3 hours.
Adopt vibrating sample magnetometer (VSM) to measure the magnetic property of magnetic, the saturation magnetization that obtains magnetic is 72.5emu/g, and coercive force is 6300Oe.
Embodiment 3
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 0.5496g, ceric ammonium nitrate ((NH
4)
2Ce (NO
3)
4) 0.3477g, Yttrium trinitrate (Y (NO
3)
36H
2O) 0.2510g and cobalt chloride (CoCl
36H
2O) 0.6257g.
The above-mentioned raw material that takes by weighing is placed beaker, add the 500ml deionized water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again; In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of evaporating solvents; Gel D moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; With precursor powder E porphyrize in mortar, in the corundum crucible of packing into, calcine insulation 4h, the strontium ferrites micro mist that obtains down at 700 ℃.
Consisting of of the strontium ferrites micro mist that obtains: Sr
0.8La
0.1Y
0.05Ce
0.05(Fe
11.8Co
0.2) O
19Particle diameter is 40～100nm.Saturation magnetization is 74.0emu/g, and coercive force is 6100Oe.
Embodiment 4
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 1.0991g, ceric ammonium nitrate ((NH
4)
2Ce (NO
3)
4) 0.3477g, Yttrium trinitrate (Y (NO
3)
36H
2O) 0.2510g and cobalt chloride (CoCl
36H
2O) 0.6257g.
The above-mentioned raw material that takes by weighing is placed beaker, add 500ml secondary water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again;
In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of following evaporating solvents; Gel D moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; Take by weighing precursor powder E30g, the nanometer SiO of particle diameter 20～80nm
20.15g particle diameter is less than the nanometer CaCO of 100nm
30.20g calcium gluconate 0.35g places beaker, adds water 45ml, mixes 30 minutes, obtains mixture of viscous form F; Mixture F is 90 ℃ of oven dry, levigate in mortar, place muffle furnace to preheat 3 hours at 280 ℃, obtained mixing grog G in 1.5 hours 1200 ℃ of calcinings then; To mix grog G wet ball grinding to particulate D90 less than 1 μ m (adopting MS-2000 type laser particle analyzer to measure granularity), oven dry, 600 ℃ down annealing obtained magnetic in 3 hours.
Adopt vibrating sample magnetometer (VSM) to measure the magnetic property of magnetic, the saturation magnetization that obtains magnetic is 73.3emu/g, and coercive force is 6500Oe.
Embodiment 5
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 1.0991g, cobalt chloride (CoCl
36H
2O) 0.3128g, nickelous chloride (NiCl
26H
2O) 0.1553g, and zinc chloride (ZnCl
2) 0.0893g.
The above-mentioned raw material that takes by weighing is placed beaker, add 500ml secondary water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again; In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of following evaporating solvents; Gel D moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; With precursor powder E porphyrize in mortar, calcine insulation 4h, the strontium ferrites micro mist that obtains down at 700 ℃ in the corundum crucible of packing into.
Consisting of of the strontium ferrites micro mist that obtains: Sr
0.8La
0.2(Fe
11.8Co
0.1Ni
0.05Zn
0.05) O
19Particle diameter is 30～110nm; Saturation magnetization is 73.8emu/g; Coercive force is 6000Oe.
Embodiment 6
Take by weighing iron nitrate (Fe (NO
3)
36H
2O) 60.6243g, strontium nitrate (Sr (NO
3)
2) 2.55354g, lanthanum nitrate (La (NO
3)
36H
2O) 1.0991g, cobalt chloride (CoCl
36H
2O) 0.6257g, nickelous chloride (NiCl
26H
2O) 0.1553g, and zinc chloride (ZnCl
2) 0.0893g.
The above-mentioned raw material that takes by weighing is placed beaker, add 500ml secondary water, stir fully dissolving, obtain mixed solution A; The 149g citric acid is joined in the mixed solution A, stirring and dissolving obtains solution B again; In solution B, feed ammonia and regulate pH value to 7.5, obtain deep green colloidal sol C; Colloidal sol C formed gel D in 6 hours at 80 ℃ of following evaporating solvents; The gel D that forms moved in 500 ℃ the retort furnace, gel expands rapidly, smolders, and burning, obtains the black powder precursor E of bulk multi-hole; Take by weighing precursor powder E 30g, the nanometer SiO of particle diameter 20～80nm
20.15g particle diameter is less than the nanometer CaCO of 100nm
30.20g, calcium gluconate 0.35g, place beaker, add water 45ml, mixed 30 minutes, obtain mixture of viscous form F; Mixture F is 90 ℃ of oven dry, levigate in mortar, in muffle furnace, preheat 3 hours at 280 ℃, obtained mixing grog G in 1.5 hours 1200 ℃ of calcinings then; To mix grog G wet ball grinding and (adopt MS-2000 type laser particle analyzer to measure granularity) less than 1 μ m particle greater than 90% to particle diameter, oven dry, 600 ℃ down annealing obtained magnetic in 3 hours.
Adopt vibrating sample magnetometer (VSM) to measure the magnetic property of magnetic, the saturation magnetization that obtains magnetic is 73emu/g, and coercive force is 6400Oe.
Claims (5)
1. the strontium ferrite magnetic powder of high specific saturation magnetization and high-coercive force, its composition can be expressed as:
Sr
1-xR
x(Fe
12-yM
y)
zO
19
0.01≤x≤0.4
0.01≤y≤0.4
0.7≤z≤1.4
0.9≤x/yz≤1.08
0.05≤(1-x)/(12-y)z≤0.11
R is at least a in yttrium, lanthanum, praseodymium, neodymium, the cerium;
M is at least a in cobalt, nickel, zinc, copper, the manganese;
Specific saturation magnetization is 73～75emu/g; High-coercive force is 5.5～6.2kOe;
Its preparation method may further comprise the steps successively:
1. will contain the compound of Sr, Fe, R and M, be dissolved in the deionized water solution of citric acid, make that Fe concentration is 0.5～1.5 mol in the solution, Fe
3+With the mol ratio of citric acid be 1: 1～1: 5; The mol ratio of Sr, Fe, R, M is 1 in the solution: (11.5～12.5): (0.03～0.3): (0.03～0.3); R is at least a in yttrium, lanthanum, praseodymium, neodymium, the cerium; M is at least a in cobalt, nickel, zinc, copper, the manganese;
2. feed ammonia, regulator solution pH value to 7.5～8.5 obtain colloidal sol;
3. with colloidal sol in 60～90 ℃ of following evaporating solvents, gel;
4. gel is placed retort furnace, under 200～500 ℃, ignite, obtain the powder precursor after self-propagating combustion is complete;
5. after the powder precursor being placed the mortar porphyrize, in the crucible of packing into,, obtain magnetic in 500～1000 ℃ of calcinings 1～5 hour.
2. the strontium ferrite magnetic powder of high specific saturation magnetization and high-coercive force according to claim 1, it is characterized in that: the compound of the described Sr of containing, R, Fe, M is muriate, nitrate, oxyhydroxide, carbonate, organic acid salt or the alkoxide of Sr, R, Fe and M.
3. the strontium ferrite magnetic powder of high specific saturation magnetization and high-coercive force as claimed in claim 1 or 2, it is characterized in that: in step 4. in the gained powder precursor, add the nano level additive of powder precursor quality 0.1～1% and the dispersion agent of powder precursor quality 0.1～10%, and add water and mix, the granule content in the control mixed slurry is 30～90wt%; Mixture after 80～150 ℃ of oven dry, is preheated 1～4 hour at 100～400 ℃, 600～1200 ℃ of calcinings 1～4 hour, obtain mixing grog then; To mix grog wet ball grinding to particle diameter again is 0.6～1.5 μ m, obtains magnetic; Maybe will mix grog 500～800 ℃ of annealing 1～5 hour, obtain magnetic.
4. as the strontium ferrite magnetic powder of high specific saturation magnetization as described in the claim 3 and high-coercive force, it is characterized in that: described additive is SiO
2, CaCO
3, B
2O
3, SrSO
4, Al
2O
3, Cr
2O
3In at least a.
5. as the strontium ferrite magnetic powder of high specific saturation magnetization as described in the claim 3 and high-coercive force, it is characterized in that: described dispersion agent is the organic compound with hydroxyl or carboxyl; Or neutral salt, or be lactone with organic compound of hydroxyl or carboxyl with organic compound of hydroxyl or carboxyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102316338A CN101372417B (en) | 2008-09-25 | 2008-09-25 | High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102316338A CN101372417B (en) | 2008-09-25 | 2008-09-25 | High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101372417A CN101372417A (en) | 2009-02-25 |
| CN101372417B true CN101372417B (en) | 2011-08-10 |
Family
ID=40446825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102316338A Expired - Fee Related CN101372417B (en) | 2008-09-25 | 2008-09-25 | High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101372417B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295453A (en) * | 2010-06-22 | 2011-12-28 | 山东轻工业学院 | Method for preparing strontium ferrite magnetic material by aqueous solution method |
| CN101920999B (en) * | 2010-07-26 | 2012-09-05 | 暨南大学 | Method for preparing nano strontium ferrite |
| CN102030521A (en) * | 2010-10-29 | 2011-04-27 | 吉林大学 | Method for preparing M-shaped iron strontium oxide with high coercive force |
| CN102992744A (en) * | 2011-09-13 | 2013-03-27 | 张连墩 | M-type strontium ferrite powder for injection molding bonded permanent magnet and preparation process of M-type strontium ferrite powder |
| CN103601483B (en) * | 2013-12-03 | 2015-10-21 | 沈阳工业大学 | The synthetic method of lanthanum additive Mn iron strontium oxide magnetic powder |
| CN103936079B (en) * | 2014-03-28 | 2015-09-02 | 华南理工大学 | For the production of the high stable material and preparation method thereof of forming gas |
| CN106083021B (en) * | 2016-05-27 | 2018-08-17 | 慈溪市华夏电器实业有限公司 | A kind of ferrite magnetic material and preparation method thereof |
| CN108083794B (en) * | 2016-11-22 | 2021-02-23 | 比亚迪股份有限公司 | Ferrite material and application thereof |
| CN106882962A (en) * | 2017-03-08 | 2017-06-23 | 安徽省东方磁磁铁制造有限公司 | A kind of high magnetic energy M types barium ferrite permanent-magnet material and preparation method thereof |
| CN107311635A (en) * | 2017-06-29 | 2017-11-03 | 中国医科大学附属第医院 | A kind of synthetic method of lanthanum zinc doping iron strontium oxide magnetic powder |
| CN107324406B (en) * | 2017-07-31 | 2019-09-24 | 电子科技大学 | A kind of composite modified strontium ferrite raw powder's production technology |
| CN109574083B (en) * | 2018-12-04 | 2021-06-25 | 浙江安特磁材股份有限公司 | Rubber-plastic ferrite magnetic powder and preparation method thereof, magnetic product and application |
| CN111439995B (en) * | 2019-01-17 | 2022-04-26 | 四川京都龙泰科技有限公司 | High-performance Co-free hexagonal permanent magnetic ferrite material and preparation method thereof |
| CN112939590B (en) * | 2021-03-12 | 2022-10-14 | 电子科技大学 | Hexahexaferrite material for X-band quasi-planar device and preparation method thereof |
| CN115925407A (en) * | 2022-05-25 | 2023-04-07 | 中国科学院赣江创新研究院 | Rare earth element doped Z-type ferrite material and preparation method thereof |
| CN115784732B (en) * | 2022-11-25 | 2023-09-05 | 中国科学院宁波材料技术与工程研究所 | Ce-Mn doped strontium ferrite and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183988B1 (en) * | 1984-11-30 | 1989-12-13 | Kabushiki Kaisha Toshiba | Magnetic powders for magnetic recording media and magnetic recording media employing said magnetic powder therein |
| EP0377821A1 (en) * | 1988-12-14 | 1990-07-18 | Bayer Ag | Method for the preparation of particulate magnetic hexagonal ferrites by spray-drying barium salts and iron oxides, and their use |
| CN101117285A (en) * | 2007-07-26 | 2008-02-06 | 同济大学 | Ba(1-x)SrxTiO3-BaX6Ti6O19(X=Mg, Zn) diphasic composite micro-wave ceramic material and preparation method thereof |
| CN101269953A (en) * | 2008-05-01 | 2008-09-24 | 浙江师范大学 | Soft magnetic ferrite with highly saturated magnetization strength and preparation method thereof |
-
2008
- 2008-09-25 CN CN2008102316338A patent/CN101372417B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0183988B1 (en) * | 1984-11-30 | 1989-12-13 | Kabushiki Kaisha Toshiba | Magnetic powders for magnetic recording media and magnetic recording media employing said magnetic powder therein |
| EP0377821A1 (en) * | 1988-12-14 | 1990-07-18 | Bayer Ag | Method for the preparation of particulate magnetic hexagonal ferrites by spray-drying barium salts and iron oxides, and their use |
| CN101117285A (en) * | 2007-07-26 | 2008-02-06 | 同济大学 | Ba(1-x)SrxTiO3-BaX6Ti6O19(X=Mg, Zn) diphasic composite micro-wave ceramic material and preparation method thereof |
| CN101269953A (en) * | 2008-05-01 | 2008-09-24 | 浙江师范大学 | Soft magnetic ferrite with highly saturated magnetization strength and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101372417A (en) | 2009-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101372417B (en) | High specific saturation magnetization and high coercitive force strontium ferrite magnetic powder and preparation thereof | |
| CN102260072A (en) | Method for synthesizing high-performance barium ferrite by using molten salt as flux and reaction medium | |
| CN100403461C (en) | Permanent magnet and method for preparation thereof | |
| EP2598443B1 (en) | Process for obtaining functionalized nanoparticulate magnetic ferrites for easy dispersion | |
| CN101481241A (en) | Preparation of complex phase nanocrystalline permanent ferrite material | |
| Godara et al. | Effect of calcium solubility on structural, microstructure and magnetic properties of SrFe12O19 | |
| JP6070454B2 (en) | Ferrite compound | |
| JP4194013B2 (en) | Ferrite magnet manufacturing method | |
| CN104003701B (en) | A kind of not containing the preparation method of rare earth permanent ferrite material | |
| CN104003707B (en) | Preparing method of barium permanent-magnetic ferrite materials | |
| CN103159469A (en) | Preparation method of Mn-Zn ferrite powder with high permeability | |
| Jeong et al. | Study on magnetic properties of the U-type ferrite according to substituted elements | |
| CN105600827A (en) | High induction grain-oriented la-doped strontium ferrite and preparation method thereof | |
| RU2768724C1 (en) | Method of producing nanostructured powder of lithium-zinc-manganese ferrite | |
| KR100554500B1 (en) | Manufacturing method thereof barium strontium ferrite particles | |
| WO2014084059A1 (en) | Ferrite compound | |
| JP2008187184A (en) | Production process of ferrite magnet | |
| TWI768299B (en) | SUBSTITUTION TYPE ε IRON OXIDE MAGNETIC PARTICLE POWDER, METHOD FOR MANUFACTURING SUBSTITUTION TYPE ε IRON OXIDE MAGNETIC PARTICLE POWDER, GREEN COMPACT, METHOD FOR MANUFACTURING GREEN COMPACT AND ELECTROMAGNETIC WAVE ABSORBER | |
| CN104003704B (en) | A kind of preparation method without lanthanum cobalt permanent-magnet ferrite | |
| CN104003702B (en) | A kind of preparation method of calcium permanent ferrite material | |
| Vedmid’ et al. | Structural and magnetic characteristics of gadolinium manganite modified with barium Gd0. 9Ba0. 1MnO3 | |
| JP2003048772A (en) | Method for producing ferritic sintered magnet | |
| Arjunwadkar et al. | Effect of sintering temperature on the structural, electrical and magnetic properties of Li0. 5Al1. 0Fe2O4 ferrite prepared by combustion method | |
| CN108298597B (en) | Preparation method of ferrous spinel of divalent metal | |
| CN101693622A (en) | Method for preparing barium ferrite at low temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110810 Termination date: 20140925 |
|
| EXPY | Termination of patent right or utility model |