CN103030388A - High-performance permanent magnetic ferrite material and preparation method thereof - Google Patents
High-performance permanent magnetic ferrite material and preparation method thereof Download PDFInfo
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- CN103030388A CN103030388A CN2013100179924A CN201310017992A CN103030388A CN 103030388 A CN103030388 A CN 103030388A CN 2013100179924 A CN2013100179924 A CN 2013100179924A CN 201310017992 A CN201310017992 A CN 201310017992A CN 103030388 A CN103030388 A CN 103030388A
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Abstract
The invention provides a high-performance permanent magnetic ferrite material and a preparation method thereof. The corresponding high-performance permanent magnetic ferrite material contains hexagonal ferrite main phases of A, R, M and Fe, and has the structural formula with the characteristic as follows: [CaxRyA1-x-y] [Fe12-m-nMmCan] zO19. The preparation method comprises the following steps: weighing raw materials according to the structural formula, and grinding the weighed raw materials with a wet mixing process; after mixing, the average grain diameter of slurry is not larger than 0.8 mu m; after the slurry is dried, pre-burning in air or oxygen atmosphere to obtain a pre-burning material; smashing the pre-burning material to coarse powder, taking a certain amount of coarse powder, adding a secondary additive in proportion, and grinding for several hours with a wet method until achieving the needed grain size; centrifugally dewatering the slurry obtained through grinding, adjusting the concentration of the slurry to 65-80 percent, pressing under a magnetic field to obtain a preset shape of forming body, and causing the forming magnetic field not to be smaller than 8000 Gs; putting the forming body at 200-400 DEG C to remove water in a forming blank, and then sintering in the air or oxygen atmosphere to obtain a sintered magnet.
Description
Technical field
The present invention relates to a kind of high-performance permanent magnetic ferrite material and manufacture method, belong to the ferrite permanent-magnet materials technical field.
Background technology
All the time, ferrite permanent-magnet materials is widely used in the parts of automobile, OA/AV apparatus, household electrical appliances usefulness motor component, sensor and generator owing to having higher cost performance.In recent years, miniaturization, high performance along with electronic unit, require ferrimagnet both to keep high remanent magnetism Br, having again not can be owing to the high-coercive force Hcj that is slice-type and causes demagnetization, and squareness ratio (Hk/Hcj) also must improve simultaneously with these characteristics simultaneously.When squareness ratio is low, limit demagnetizing field intensity reduces, so can easily cause the demagnetization problem, especially in permanent magnet direct current motor, ferrimagnet is owing to being subject to the effect of winding demagnetizing field, expects especially both higher high performance ferrite magnets of coercivity H j and squareness ratio (Hk/Hcj).
The M type Sr(Ba with superior performance that is widely used at present) ferrite sintered magnet is by following operation manufacturing: at first, carbonate of ferric oxide and Sr or Ba etc. is mixed, carry out the Ferrite method reaction by pre-burning, obtain Preburning material, add SiO in order to control crystal growth and raising density
2, CaCO
3And Al
2O
3Or Cr
2O
3Deng, carry out the wet method Crushing of Ultrafine take water as medium to requiring particle diameter; The slip that obtains is orientated in magnetic field is pressed into blank, sintering post-treatment established practice setting shape manufactures ferrite sintered magnet.
In the preparation technology of magnet, when the median size of the slip that obtains through the wet grinding Crushing of Ultrafine is lower than 0.7 μ m, water discharge time phenomenal growth in the time of can causing the slip moulding.And formed body number (shaping efficiency) reduces in the unit time.This problem causes the tooling cost of ferrite sintered magnet to rise.If adopt median size greater than the slip moulding of 0.7 μ m, shaping efficiency can significantly improve.But the magnetic property of ferrite sintered magnet can significantly reduce along with the increase of granularity.In order to obtain higher magnetic property, require the density particle diameter high and crystal particles of ferrimagnet little, simultaneously good moldability.But prior art is difficult to satisfy these requirements.
The structural formula of magnetoplumbite M type ferrite is expressed as A all the time
1Fe
12O
19, A is Ba
2+Or Sr
2+The time can form the M type ferrite.When A is than Ba
2+Or Sr
2+The Ca that radius is little
2+The time, can not form the M type ferrite; Ca
2+By a part of La
3+Displacement can obtain the ferritic crystalline structure of six sides, simultaneously Fe
3+A part by Co
2+During displacement, ferrite sintered magnet shows preferably magnetic property.
Patent CN101542646A has proposed to require Ca to replace the part of Sr or Ba in specialized range, can more put into La or Co in its crystalline structure.The general formula that consists of the metallic element of its principal phase is expressed as R
xCa
mA
1-x-m(Fe
12-yM
y)
zThink La in the Magnetoplumbite permanent magnetic ferrite that patent CN101552069A proposes and the manufacture method
3+And Ca
2+The common Sr that replaces
2+, improved Co
2+The amount of displacement iron ion, thus fine magnetic property obtained.The ferrite sintered magnet that patent CN1849675A proposes has following characteristics: have M type ferrite structure, take the A element that consisted of by Sr or Sr and Ba, as at least a of the rare earth element that contains Y and R element, Ca, Fe and the Co that must contain La as necessary element.The essentially consist of described oxidate magnetic material is expressed as R
yCa
xA
1-x-yFe
2n-zM
zO
19z, show that from this general formula Ca has replaced Sr or Ba.In the above-mentioned patent, Ca and Sr, La etc. occupy the A position.
But the granularity of the technological forming slip that patent CN101552069A provides is controlled at below the 0.65 μ m, and the moulding difficulty is large, has therefore adopted the way that reduces water content.The overall dimension of the crystal particles c-axis direction of the ferrite sintered magnet among the patent CN101542646A is 0.95 μ m or lower, consider in the sintering circuit about 2 times of grain growings, the granularity of moulding slip is 0.5 μ m or lower, easily cause production efficiency to reduce, cause high-performance and high productivity to be difficult to balance.The sintered permanent ferrite magnet that patent CN101844914A provides, sintering under air conditions, Br with 430～470mT, the Hcj of 400～464KA/m and 80% squareness ratio, but squareness ratio is still lower, Hk is defined as squareness ratio divided by the value (Hk/Hcj) of the Hcj gained of demagnetizing curve, and Parameter H k is in the second quadrant of 4 π I--H curves, and 4 π I values equal H axial coordinate value corresponding to position of 0.95Br.
Summary of the invention
The problem that moulding difficulty large, production efficiency lower, squareness ratio lower of the present invention for existing in the existing ferrite permanent-magnet materials technology of solution, and then a kind of high-performance permanent magnetic ferrite material and manufacture method are provided.For this reason, the invention provides following technical scheme:
A kind of high-performance permanent magnetic ferrite material contains the Hxagonal ferrite principal phase of A, R, M and Fe, has the structural formula of following characteristics: [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19
Wherein, A represents one or both elements among Sr, the Ba; R represents at least a element among rare earth element and the Bi, and must contain La; M represents at least a element among Co, Mn, Zn, the Ni and contains at least Co; 0.10≤x+n≤0.70; 0.10≤y≤0.70; 0.10≤m≤0.60; 0.80≤z≤1.10.
A kind of manufacture method of high-performance permanent magnetic ferrite material comprises:
According to described structural formula [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19Raw materials weighing is ground the raw material of weighing by material by wet type mixing technique, the median size of slip is not more than 0.8 μ m after mixing;
After the slip drying, pre-burning in air or in the oxygen atmosphere obtains Preburning material;
Described Preburning material is broken into meal, takes by weighing a certain amount of meal, add in proportion secondary additive, by wet grinding a few hours, until reach desired particle size;
To grind the gained slip and carry out centrifuge dehydration, and adjust pulp density to 65～80%, again by pressing under magnetic field and obtain the formed body of predetermined shape, forming magnetic field is not less than 8000Gs;
Described formed body is removed moisture in the molded blank under 200 ℃～400 ℃, then sintering under air atmosphere or oxygen atmosphere obtains sintered magnet.
The invention provides a kind of and existing ferrite sintered magnet compares, can realize remanent magnetism 〉=440mT, HCJ 〉=400KA/m, the rectangular degree of magnet reaches high performance sintered permanent-magnet ferrite material and the manufacture method thereof more than 90% simultaneously, can fully satisfy the expectation that in recent years magnetic property is improved; Dewatering efficiency is good when adopting Wet-pressing molding simultaneously, can avoid occuring the be full of cracks of formed body.
Description of drawings
Fig. 1 is the embodiment of the invention 1 obtained permanent ferrite prefiring ball stereoscan photograph;
Fig. 2 is the embodiment of the invention 1 obtained permanent-magnet ferrite sintering magnetic patch parallel magnetic field direction profile scanning electromicroscopic photograph;
Fig. 3 is the embodiment of the invention 1 obtained permanent-magnet ferrite sintering magnetic patch parallel magnetic field direction profile scanning electromicroscopic photograph;
Fig. 4 is Comparative Examples 1 obtained permanent ferrite prefiring ball stereoscan photograph of the present invention.
Embodiment
Below in conjunction with the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making all other embodiment that obtain under the creative work prerequisite.
The specific embodiment of the present invention provides a kind of high-performance permanent magnetic ferrite material, contains the Hxagonal ferrite principal phase of A, R, M and Fe, has the structural formula of following characteristics: [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19
Wherein, A represents one or both elements among Sr, the Ba; R represents at least a element among rare earth element and the Bi, and must contain La; M represents at least a element among Co, Mn, Zn, the Ni and contains at least Co; 0.10≤x+n≤0.70; 0.10≤y≤0.70; 0.10≤m≤0.60; 0.80≤z≤1.10.
Generally, the permanent-magnet ferrite chemical structural formula is expressed as A
1B
12O
19, the A position is occupied by Ba or Sr, and the B position is occupied by Fe.Ba
2+Or Sr
2+Ionic radius large, can't occupy Fe
3+The position; Same Fe
3+Ionic radius little, also can't occupy Ba
2+Or Sr
2+The position.La, Co replace normally La
3+Replace Sr
2+The position, Co
2+Replace Fe
3+The position, its structural formula can be expressed as: Sr(Ba)
1-xLa
xFe
12-yCo
yO
19
Ferrite sintered magnet in this embodiment is a kind of M phase ferrite with hexagonal structure, by Sr or Sr and Ba consists of the A element, R represents at least a element among rare earth element and the Bi, and must contain La, Ca, Fe and Co element, its chemical structural formula is expressed as [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19
The principal element that affects the ionic replacement amount comprises: a. charge balance is relevant with the ion combination valency; B. lattice distortion is determined by ionic radius; For existing ferrite permanent-magnet materials, because the ionic radius of lanthanum when lanthanum replacing section strontium, can cause that lattice parameter c reduces less than the ionic radius of Sr; Along with the increase of replacement amount, it is large that lattice distortion becomes, and makes La can not replace more Sr, easily produces simultaneously Spinel and orthoferrites and equate impurity.This embodiment is utilized Ca
2+Radius is
Between Fe
3+ 
Radius and Sr
2+ 
Between the radius.Ca
2+Can the while replacement of fe
3+And Sr
2+In order to reduce lattice distortion, the present invention makes Ca
2+Part replacing section Fe
3+, stop c-axis to diminish.This structure is more stable.In order to realize charge balance, should satisfy following relation: La between La, Co, the Ca
3++ Co
2+=Sr
2++ Fe
3+, La
3++ Ca
2+=Sr
2++ Fe
3+The high-performance permanent magnetic ferrite material that this embodiment provides can reach remanent magnetism Br 〉=440mT, HCJ Hcj 〉=400KA/m, and the rectangular degree of magnet reaches the high-performance magnet more than 90% simultaneously.
This embodiment also provides a kind of manufacture method of high-performance permanent magnetic ferrite material, comprising:
According to described structural formula [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19Raw materials weighing is ground the raw material of weighing by material by wet type mixing technique, the median size of slip is not more than 0.8 μ m after mixing;
After the slip drying, pre-burning in air or in the oxygen atmosphere obtains Preburning material;
Described Preburning material is broken into meal, takes by weighing a certain amount of meal, add in proportion secondary additive, by wet grinding a few hours, until reach desired particle size;
To grind the gained slip and carry out centrifuge dehydration, and adjust pulp density to 65～80%, again by pressing under magnetic field and obtain the formed body of predetermined shape, forming magnetic field is not less than 8000Gs;
Described formed body is removed moisture in the molded blank under 200 ℃～400 ℃, then sintering under air atmosphere or oxygen atmosphere obtains sintered magnet.
Therefore the ferrite sintered body magnet that this embodiment provides contains Ca as the main component of principal phase ferrite phase, in the situation that contain calcium as minor element, the amount of analyzing Ca from sintered compact is the total amount of principal phase and submember.Structural formula [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19In the atomic ratio x+n of Ca only be the value of Ca in the principal phase ferrite, do not comprise the value of submember.Wherein, be subject to the impact of valence mumber of ratio of components, each element of each metallic element, the composition of increase and decrease oxygen is to keep intracrystalline electric neutrality.Fe exists with 3 valencys in the M type ferrite usually, but also has the possibility of appraising at the current rate; Also there is the possibility of appraising at the current rate in Co; For R, also there is the possibility of 3 valencys valence mumber in addition, mainly determined by pre-burning and sintering atmosphere.In this external follow-up sintering circuit, if sintering atmosphere is reducing atmosphere, then there is the possibility that the oxygen room occurs.The ratio of oxygen and atoms metal also may change thereupon, and the oxygen atomicity in the explanation is 19, but the actual quantity of Sauerstoffatom may the nonstoichiometry number.
Below by specific embodiment technical scheme of the present invention is described further, but the technical characterictic of the present invention protection is not limited to these embodiment.
Embodiment 1
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 84.69wt%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 5.86wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.38wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.27wt%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 1.79wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain Preburning material.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, with known crumbling method, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours is until the mean particle size of particle is 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering in air or under the oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Comparative Examples 1
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 84.69wt%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 5.86wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.38wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.27wt%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 1.79wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
(x+n)La
ySr
1-x-y] [(Fe
12-m-nCo
m] O
19
Preburning material is broken into meal, with known crumbling method, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours is until the mean particle size of particle is 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Embodiment 2
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 85.08wt%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 4.44wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 4.44wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.02wt%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 2.02wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, with known crumbling method, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% La
2O
3, 0.8wt% Co
2O
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours, to the mean particle size of particle be 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 81.04%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.01%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 2.01%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 9.83%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.11%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, with known crumbling method, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% La
2O
3, 0.8wt% Co
2O
3, 0.3wt% Al
2O
3, 1.5wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours, to the mean particle size of particle be 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Embodiment 4
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 80.80wt%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 5.16wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 2.29wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 9.40wt%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 2.35wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 0.2wt% H
3BO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours, to the mean particle size of particle be 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1220 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Embodiment 5
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 83.27wt%;
BaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 7.49wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.31wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.18wt%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 1.75wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, BaCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
yBa
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours, to the mean particle size of particle be 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1200 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Embodiment 6
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 84.92wt%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 5.85wt%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.37wt%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.27wt%;
The CoO powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 1.59wt%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3With the CoO powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, fine grinding 10 hours, to the mean particle size of particle be 0.80 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Embodiment 7
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 81.04%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.01%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 2.01%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 9.83%;
Co
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.11%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3And Co
2O
3Powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
xLa
ySr
1-x-y] [(Fe
12-m-nCo
mCa
n] O
19
Preburning material is broken into meal, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, by adjusting the fine grinding time, obtain the slip that particle diameter is respectively 1.00 μ m, 0.90 μ m, 0.80 μ m, 0.75 μ m, 0.70 μ m, 0.65 μ m, 0.60 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.Grind top and bottom to sintered compact, measures its magnetic property as shown in the table.
Comparative Examples 2
Adopt following raw material:
Fe
2O
3Powder: (the original mean particle size of purity 〉=99.2wt%, particle: 1.0 μ m), 81.04%;
SrCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 3.01%;
CaCO
3Powder: (the original mean particle size of purity 〉=98.0wt%, particle: 2.0 μ m), 2.01%;
La
2O
3Powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 9.83%;
The CoO powder: (the original mean particle size of purity 〉=99.0wt%, particle: 0.8 μ m), 4.11%.
Weighing CaCO
3Powder, La
2O
3Powder, Fe
2O
3Powder, SrCO
3With the CoO powder.With the raw material powder wet mixing of gained 4 hours, carry out drying.Then, in air, 1250 ℃ of pre-burnings 3 hours, obtain the pre-burning ball.Make it have structural formula to be: [Ca
(x+n)La
ySr
1-x-y] [(Fe
12-m-nCo
m] O
19
Preburning material is broken into meal, takes by weighing the meal 300g of aforesaid way preparation, add the SiO of 0.65wt%
2, 1.2wt% CaCO
3, 1.0wt% calglucon; Add the 600mL deionized water as ball-milling medium, by adjusting the fine grinding time, obtain the slip that particle diameter is respectively 0.80 μ m, 0.75 μ m, 0.70 μ m; The slip of gained is carried out centrifuge dehydration, adjust pulp density to 65～80%, then pressing under magnetic field, forming magnetic field is not less than 8000Gs; The diameter of gained formed body is 34.2mm, highly is the right cylinder of 13mm, and forming pressure is 10MPa.Formed body 200 ℃～400 ℃ lower insulations 3 hours, is removed the moisture in the molded blank, sintering under air atmosphere or oxygen atmosphere then, 1210 ℃ of sintering temperatures be incubateds 3 hours, the acquisition sintered magnet.The top and bottom of sintered compact are ground, measure shown in its magnetic property as above shows.As can be seen from Table 7, when Slurry Granularity was 0.60～1.0 μ m, the magnet for preparing according to embodiment 7 had high Br, Hcj and rectangular degree.In addition, the ferrite slurry granularity of embodiment 7 preparations still has high magnetic property more than 0.70 μ m, can take into account performance and production efficiency.
The specific embodiment of the present invention provides a kind of and existing ferrite sintered magnet to compare, can realize remanent magnetism 〉=440mT, HCJ 〉=400KA/m, the rectangular degree of magnet reaches high performance sintered permanent-magnet ferrite material and the manufacture method thereof more than 90% simultaneously, can fully satisfy the expectation that in recent years magnetic property is improved; Dewatering efficiency is good when adopting Wet-pressing molding simultaneously, can avoid occuring the be full of cracks of formed body.
The above; only be the better embodiment of the present invention; but protection scope of the present invention is not limited to this; anyly be familiar with those skilled in the art in the technical scope that the embodiment of the invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (9)
1. high-performance permanent magnetic ferrite material contains the Hxagonal ferrite principal phase of A, R, M and Fe, it is characterized in that having the structural formula of following characteristics: [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19
Wherein, A represents one or both elements among Sr, the Ba; R represents at least a element among rare earth element and the Bi, and must contain La; M represents at least a element among Co, Mn, Zn, the Ni and contains at least Co; 0.10≤x+n≤0.70; 0.10≤y≤0.70; 0.10≤m≤0.60; 0.80≤z≤1.10.
2. high-performance permanent magnetic ferrite material according to claim 1 is characterized in that, the squareness ratio Hk/Hcj of described high-performance permanent magnetic ferrite material 〉=90%.
3. high-performance permanent magnetic ferrite material according to claim 1 is characterized in that, the coercivity H j of described high-performance permanent magnetic ferrite material 〉=400KA/m.
4. high-performance permanent magnetic ferrite material according to claim 1 is characterized in that, the remanent magnetism Br 〉=440mT of described high-performance permanent magnetic ferrite material.
5. the manufacture method of a high-performance permanent magnetic ferrite material as claimed in claim 1 is characterized in that, comprising:
According to described structural formula [Ca
xR
yA
1-x-y] [(Fe
12-m-nM
mCa
n]
zO
19Raw materials weighing is ground the raw material of weighing by material by wet type mixing technique, the median size of slip is not more than 0.8 μ m after mixing;
After the slip drying, pre-burning in air or in the oxygen atmosphere obtains Preburning material;
Described Preburning material is broken into meal, takes by weighing a certain amount of meal, add in proportion secondary additive, by wet grinding a few hours, until reach desired particle size;
To grind the gained slip and carry out centrifuge dehydration, and adjust pulp density to 65～80%, again by pressing under magnetic field and obtain the formed body of predetermined shape, forming magnetic field is not less than 8000Gs;
Described formed body is removed moisture in the molded blank under 200 ℃～400 ℃, then sintering under air atmosphere or oxygen atmosphere obtains sintered magnet.
6. the manufacture method of high-performance permanent magnetic ferrite material according to claim 5 is characterized in that, in described process of lapping, described secondary additive comprises SiO
2, CaCO
3, Al
2O
3, Cr
2O
3, ZnO, SrCO
3, H
3BO
3, La
2O
3, Co
2O
3, V
2O
5Deng, wherein the mean particle size of each secondary additive is no more than 2 μ m; The weight percentage ranges that described secondary additive accounts for principal phase is SiO
2: 0.05～2.0wt%, CaCO
3: 0.4～2.0wt%, Al
2O
3: 0.05～1.2wt%, Cr
2O
3: 0.05～1.2wt%, ZnO:0.05～0.6wt%, SrCO
3: 0.05～1.0wt%, H
3BO
3: 0.05～0.8wt%, La
2O
3: 0.1～3.0wt%, Co
2O
3: 0.1～2.0wt%, V
2O
5: 0.05～0.5wt%.
7. the preparation method of high-performance permanent magnetic ferrite material according to claim 5, it is characterized in that, in described process of lapping, also comprise the adding dispersion agent, described dispersion agent is one or more in calglucon, polyvinyl alcohol or the Sorbitol Powder, and addition is 0.05～1.5wt% of Preburning material amount.
8. the manufacture method of high-performance permanent magnetic ferrite material according to claim 5 is characterized in that, described calcined temperature is 1150 ℃～1280 ℃, soaking time 1～3 hour.
9. the manufacture method of high-performance permanent magnetic ferrite material according to claim 5 is characterized in that, described sintering temperature is 1150 ℃～1280 ℃, soaking time 1～3 hour.
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| CN103288435A (en) * | 2013-06-13 | 2013-09-11 | 浙江凯文磁钢有限公司 | Method for changing shrinkage coefficient of permanent ferrite material |
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| CN1655295A (en) * | 2005-01-11 | 2005-08-17 | 横店集团东磁有限公司 | Process for preparing magnetic powder and sintered magnet and product produced thereby |
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| CN1655295A (en) * | 2005-01-11 | 2005-08-17 | 横店集团东磁有限公司 | Process for preparing magnetic powder and sintered magnet and product produced thereby |
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| CN103288435B (en) * | 2013-06-13 | 2015-07-22 | 浙江凯文磁钢有限公司 | Method for changing shrinkage coefficient of permanent ferrite material |
| CN104692785A (en) * | 2015-03-18 | 2015-06-10 | 马鞍山市鑫洋永磁有限责任公司 | High performance strontium-calcium permanent magnetic ferrite magnet and preparation method thereof |
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| CN106977191A (en) * | 2016-01-15 | 2017-07-25 | Tdk株式会社 | Ferrite sintered magnet |
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| CN113929445A (en) * | 2021-09-24 | 2022-01-14 | 横店集团东磁股份有限公司 | Preparation method of permanent magnetic ferrite pre-sintered material |
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Application publication date: 20130410 |