CN110204326A - A kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure - Google Patents

A kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure Download PDF

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CN110204326A
CN110204326A CN201910410429.0A CN201910410429A CN110204326A CN 110204326 A CN110204326 A CN 110204326A CN 201910410429 A CN201910410429 A CN 201910410429A CN 110204326 A CN110204326 A CN 110204326A
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powder
preparation
slurry
shell
magnet materials
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CN110204326B (en
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李玉平
包大新
何震宇
李军华
吴云飞
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Abstract

The present invention relates to Ferrite Material field, disclose a kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure, the ferrite permanent-magnet materials mixed by nuclear composition and shell component after through plus magnetic, molding, sintering and obtain；Each element mass content is Sr in the nuclear composition1‑xLaxFe12‑yCoyO19, wherein x=0-0.08, y=0-0.05；Each element mass content is Sr in the shell component1‑w‑ vLawCavFe12‑zCozO19, wherein w=0.2-0.45, v=0.2-0.45, z=0.15-0.35；The crystal grain of gained ferrite permanent-magnet materials is in core-shell structure, and La element and content of the Co element in crystal grain are in that uneven gradient is incremented by from inside to outside.The present invention can make ferrite permanent-magnet materials in the case where reducing La-Co element usage amount, and higher magnetic property can still be maintained.

Description

A kind of ferrite permanent-magnet materials and preparation method thereof with core-shell structure
Technical field
The present invention relates to Ferrite Material field more particularly to a kind of ferrite permanent-magnet materials with core-shell structure and its Preparation method.
Background technique
Iron strontium oxide permanent magnetic material (SrFe12O19) due to good chemical stability, environment friendly, it is higher Magnetic property and lower price, have been widely used for motor and sensor field.In recent years, with magnetic device increasingly to Miniaturization, lightness development, more stringent requirements are proposed for magnetic property of the market to ferrite permanent-magnet materials.On the other hand, in order to Control magnetic device production cost, people wish again Ferrite Material price will not because of performance improvement and significantly increase It is long.
Ion substitution is usually used in the method that tradition improves ferrite permanent-magnet materials, for example uses La3+、Nd3+、Sm3+、 Pr3+、Ce3+Deng substitution Sr2+, using Al3+、Cu2+、Zn2+、Co2+Deng substitution Fe3+.Wherein, La3+-Co2+Joint substitution is proved to It is a kind of very effective method, the intrinsic magnetic properties energy of material can be increased substantially, therefore is widely used in high-performance iron oxygen The batch production of body permanent-magnet material.But this method needs a large amount of consumption La and Co.It is well known that La belongs to rare earth element, Earth reserves are limited；And cobalt is then a kind of strategic resource, main product in South America, Africa and Oceania, price is very expensive.Therefore Using La3+-Co2+The method of ion substitution can cause the significantly promotion of Ferrite Material price.Therefore, people are highly desirable A kind of magnetic property that material not only can be improved, but also the method that material cost will not be increased substantially are found, namely finds a kind of guarantor While holding magnetism of material energy, method that La, Co element usage amount can be reduced.
On the other hand, by optimizing Ferrite Material microstructure, it can also be improved the magnetic property of material.According to relevant Theory of magnetism makes its size be less than domain size by refining the crystal grain of ferrite permanent-magnet materials, can significantly coercive Power.Currently, common method is that Preburning material is carried out prolonged ball milling for the microstructure of refiner material, grain is prepared The tiny magnetic powder particle of diameter, is then sintered again.But prolonged ball milling would generally bring many impurity, reduce material The magnetic property of material.Moreover, magnetic powder particle is meticulous also to make material difficult forming in subsequent handling, product is easy to appear after sintering Crackle.
In addition, the grain growth by control material during the sintering process, makes the draw ratio of material grains be maintained at certain Range, the also magnetic property of adjustable material.For example some compounds containing Ca, Si ion are added in mechanical milling process, And by the ratio of control Ca/Si, make the remanent magnetism of magnet and coercivity that the relationship of trade-off a kind of be presented, that is, loses certain While one performance indicator, another performance indicator is improved.In general, the value of Ca/Si rises, and the remanent magnetism of material can improve, and rectifys Stupid power can decline, and on the contrary then coercivity rises, remanent magnetism decline.But only adjusted by Ca/Si, for changing for magnetism of material energy It is kind to be limited.Increase moreover, excessive addition will lead to material non-magnetic phase containing the compound of Ca, Si ion, drops instead Low magnetism of material energy.
Several technical solutions in the prior art exemplified below:
1, the Chinese patent of Publication No. CN 1658340A is disclosed by adding La-Co element into material, can be significantly Improve the magnetic property of material.But the technology, using traditional ion adding method, La-Co constituent content is higher, substantially Degree improves the cost of material.
2, the Chinese patent of Publication No. CN 1767087A proposes that addition is few on the basis of traditional La-Co element substitution The Pr/Nd of amount can improve the magnetic property of material under the premise of not increasing Co element.But this method is for the magnetic of material Performance improvement is limited, and the usage amount of La-Co element can not be greatly lowered.
3, in Publication No. CN 104261811B, CN 104003707B, CN 101542646A, CN102471162A etc. State's patent proposes the technology of Ca-La-Co ionic association substitution, this method can be big on the basis of traditional La-Co element substitution The magnetic property of amplitude raising material.But this method is to improve La, Co element in ferrite crystalline substance by the addition of Ca ion Solid solution capacity in lattice, can to achieve the purpose that be promoted magnetism of material.So although the magnetic property of material promotes very big, essence Upper is also the cost also substantial increase by improving the additive amount of La, Co element come improving performance.
Summary of the invention
To overcome above-mentioned shortcoming and defect of the existing technology, the purpose of the present invention is to provide one kind to have nucleocapsid knot The ferrite permanent-magnet materials and its method of structure, the present invention can make ferrite permanent-magnet materials in the feelings for reducing La-Co element usage amount Under condition, higher magnetic property can still be maintained.
The specific technical proposal of the invention is: a kind of ferrite permanent-magnet materials with core-shell structure, the ferrite is forever Magnetic material by nuclear composition and shell component mixing after through plus magnetic, molding, sintering and obtain；Each element molar content is in the nuclear composition Sr1-xLaxFe12-yCoyO19, wherein x=0-0.08, y=0-0.05；Each element molar content is Sr in the shell component1-w- vLawCavFe12-zCozO19, wherein w=0.2-0.45, v=0.2-0.45, z=0.15-0.35.
The crystal grain of gained ferrite permanent-magnet materials is in core-shell structure, La element and content of the Co element in crystal grain from it is interior to It is incremented by outside in uneven gradient.
Team of the present invention is in order to prepare the high and inexpensive ferrite permanent-magnet materials of magnetic property, to the micro- of Ferrite Material The correlation seen between tissue-magnetic property is studied in detail, and discovery makes material by ingredient design and process innovation Crystal grain present core-shell structure, can while guaranteeing magnetism of material energy, reduction Co element usage amount.In the core-shell structure In, as shown in Figure 1, the stratum nucleare of crystal grain is the few Co or Sr without Co1-xLaxFe12-yCoyO19(x=0-0.08；Y=0-0.05) Ingredient, the shell (dash area) of crystal grain are then the Sr of richness Co1-w-vLawCavFe12-zCozO19(w=0.2-0.45；V=0.2- 0.45；Z=0.15-0.35) ingredient.Wherein, shell with a thickness of 0.2-0.5 μm.It should be noted that of the present invention In core-shell structure, the ingredient of crystal grain is not uniform from inside to outside, distribution gradient, with the increasing with a distance from core part Add, the concentration of La and Co element increases therewith.
As row technology known in the industry, adding La, Co element can be improved the coercivity of ferrite permanent-magnet materials, and And in certain composition range, the increase of coercivity La, Co constituent content of material and improve.Tool of the present invention There are core-shell structure ferrite permanent-magnet materials, although total La, Co content declines, but still there is good magnetic property, principle As follows: La, Co concentration of element of material grains core part are lower, and the magnetic moment at the position is caused to be easy overturning, still, crystal grain Shell La, Co concentration of element is very high, and magnetic moment is difficult to overturn.Under the action of counter magnetic field, although the magnetic moment of crystal grain core part holds It is easily flipped, but is difficult to expand to the shell of crystal grain, i.e., the rich Co shell on the outside of crystal grain, which plays, hinders material domain expansion Pinning effect, finally making Ferrite Material macroscopically has very high coercivity.
Preferably, in the crystal grain shell with a thickness of 0.2-0.5 μm.
The thickness of shell can control by adjusting nuclear composition and the ratio of shell component.
A kind of preparation method of ferrite permanent-magnet materials, comprising the following steps:
1) each initial feed of nuclear composition is weighed according to the ratio, and is uniformly mixed by way of wet ball-milling；
2) by the pre-burning at 1200-1300 DEG C of step 1) resulting materials, Preburning material is obtained；
3) by Preburning material coarse crushing, and wet ball-milling to powder diameter is 0.6-1 μm, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree becomes 900-1100 DEG C, and it is 0.05-0.1 μm that powder diameter is milled to after pre-burning；
5) slurry M1 is mixed with M2, CaCO is added by the 0.8-1.2% and 0.5-0.7% of total powder quality in slurry respectively3 And SiO2, continue ball milling；
6) compression moulding under magnetic field；
7) it is sintered.
Core-shell structure why can be formed by above-mentioned technique, principle can be explained as follows: due to calcined temperature and ball There is very big difference in the partial size of the difference of time consuming, M1 and two kinds of slurries of M2；After two kinds of slurry mixing, show many tiny M2 granular absorption is the M1 particle the case where；When sintering, M1 particle and the element of M2 particle are diffused into one another, due to the difference of partial size, M2 particle is easy by M1 granular absorption and swallows, and forms the layer structure of M1 particle, and many a M2 particles are swallowed, then can be formed Shelly-shaped layer structure.Moreover, because two kinds of materials diffusing into one another during the sintering process, can make in the crystal grain newly formed La, Co element are in non-uniform gradient distribution.
The ferrite sintered body prepared through the invention, since crystal grain has core-shell structure, so even reducing La, Co Usage amount, it is also possible to obtain very high coercivity.
Preferably, the initial feed is Fe2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder, CaCO3Powder End.
Preferably, ball milling solvent is deionized water or tap water, Ball-milling Time 4-6h in step 1).
Preferably, in step 2), burn-in time 1.5-2.5h.
Preferably, ball milling 15-25h, ball milling 50-100h after pre-burning when preparing slurry M2 after pre-burning when preparing slurry M1.
Under above-mentioned different Ball-milling Time, the slurry M1 and M2 of available different-grain diameter.
Preferably, the mass ratio of slurry M1 and M2 are 1: 1-5: 1, Ball-milling Time 0.5-1.5h in step 5).
The thickness of shell can control by adjusting nuclear composition and the ratio of shell component.
Preferably, in step 6), magnetic field strength 1.3-1.7T.
Preferably, being sintered 50-70min at 1100-1300 DEG C in step 7).
Under above-mentioned magnetic field strength and sintering process, the Ferrite Material of better performances can be made.
It is compared with the prior art, the beneficial effects of the present invention are: the crystal grain of ferrite permanent-magnet materials of the invention is in nucleocapsid Structure, La, Co concentration of element of crystal grain core part are lower in the material, and the magnetic moment at the position is caused to be easy overturning, still, brilliant Grain shell La, Co concentration of element is very high, and magnetic moment is difficult to overturn.Under the action of counter magnetic field, although the magnetic moment of crystal grain core part It is easy to happen overturning, but is difficult to expand to the shell of crystal grain, i.e., the rich Co shell on the outside of crystal grain, which plays, hinders material magnetic domain to expand The pinning effect opened, finally making Ferrite Material macroscopically has very high coercivity.Therefore, although ferrite of the invention Total La, Co content decline of permanent-magnet material, but still there is good magnetic property, cost can be greatly reduced.
Detailed description of the invention
The core-shell structure schematic diagram of Fig. 1 ferrite crystal grains；
Ferrite crystal grains and its ectonexine constituent analysis in Fig. 2 present invention.
Appended drawing reference are as follows: stratum nucleare A, shell B.
Specific embodiment
The present invention will be further described with reference to the examples below.
Total embodiment
A kind of ferrite permanent-magnet materials with core-shell structure, after the ferrite permanent-magnet materials are mixed by nuclear composition and shell component Added magnetic, molding, sintering and obtain；Each element molar content is Sr in the nuclear composition1-xLaxFe12-yCoyO19, wherein x=0- 0.08, y=0-0.05；Each element molar content is Sr in the shell component1-w-vLawCavFe12-zCozO19, wherein w=0.2- 0.45, v=0.2-0.45, z=0.15-0.35.
As shown in Figure 1, the crystal grain of gained ferrite permanent-magnet materials be in core-shell structure, stratum nucleare A be lack Co or without Co at Point, shell B (dash area) is then richness Co ingredient, and La element and content of the Co element in crystal grain are in uneven ladder from inside to outside Degree is incremented by.
Preferably, in the crystal grain shell with a thickness of 0.2-0.5 μm.
A kind of preparation method of ferrite permanent-magnet materials, comprising the following steps:
1) each initial feed (Fe of nuclear composition is weighed according to the ratio2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder and CaCO3Powder), and be uniformly mixed by way of wet ball-milling；Wherein ball milling solvent is deionized water or tap water, when ball milling Between be 4-6h；
2) by step 1) resulting materials at 1200-1300 DEG C pre-burning 1.5-2.5h, obtain Preburning material；
3) by Preburning material coarse crushing, and wet ball-milling 15-25h is 0.6-1 μm to powder diameter, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree become 900-1100 DEG C, after pre-burning ball milling 50-100h to powder diameter be 0.05-0.1 μm；
5) in mass ratio 1: 1-5: 1 slurry M1 is mixed with M2, respectively by the 0.8-1.2% and 0.5- of total powder quality in slurry 0.7% is added CaCO3And SiO2, continue ball milling 0.5-1.5h；
6) compression moulding under the magnetic field 1.3-1.7T；
7) 50-70min is sintered at 1100-1300 DEG C.
Embodiment 1
1) prepare original material below: Fe2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder, CaCO3Powder.
2) it is weighed, according to Sr1-xLaxFe12-yCoyO19(x=0.02；Y=0-0.02) ingredient composition, and pass through wet type The mode of ball milling is uniformly mixed, and solvent is deionized water when ball milling, and Ball-milling Time is 5 hours.
3) by the material of mixing at 1250 DEG C pre-burning 2 hours, obtain Preburning material.
4) Preburning material is subjected to coarse crushing, and wet ball-milling 20 hours, obtains powder D50The slurry that partial size is 0.6 μm or so M1。
5) step 2) -4 is repeated), slurry M2 is obtained, the difference is that the component of material becomes Sr in step 2)1-w- vLawCavFe12-zCozO19(w=0.45；V=0.45；Z=0.25), calcined temperature becomes 1000 DEG C in step 2, ball in step 3 Time consuming becomes 100 hours, while powder diameter D50Become 0.05 μm or so.
6, slurry M1 is mixed with M2 in mass ratio 1: 1, is added respectively by 1% and 0.6% of total powder quality in slurry CaCO3And SiO2, continue ball milling 1h.
7, the compression moulding under the magnetic field of 1.5T.
8, it is sintered 1 hour at 1200 DEG C.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4455Gs, Coercivity Hcj=4420Oe, maximum magnetic energy product (BH)max=4.75MGOe.
Embodiment 2
The present embodiment difference from example 1 is that: x=0；Y=0.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4407Gs, Coercivity Hcj=4328Oe, maximum magnetic energy product (BH)max=4.63MGOe.
Embodiment 3
The present embodiment difference from example 1 is that: x=0.08；Y=0.05.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4475Gs, Coercivity Hcj=4528Oe, maximum magnetic energy product (BH)max=4.87MGOe.
Embodiment 4
The present embodiment difference from example 1 is that: w=0.2；V=0.2；Z=0.15.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4275Gs, Coercivity Hcj=4028Oe, maximum magnetic energy product (BH)max=4.12MGOe.
Embodiment 5
The present embodiment difference from example 1 is that: in step 5), Ball-milling Time becomes 50 hours, M2 powder diameter become It is 0.1 μm or so.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4412Gs, Coercivity Hcj=4431Oe, maximum magnetic energy product (BH)max=4.69MGOe.
Embodiment 6
The present embodiment difference from example 1 is that: in step 5), Ball-milling Time becomes 75 hours, M2 powder diameter become It is 0.08 μm or so.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.3-0.5 μm, remanent magnetism Br=4432Gs, Coercivity Hcj=4531Oe, maximum magnetic energy product (BH)max=4.76MGOe.
Embodiment 7
A kind of ferrite permanent-magnet materials with core-shell structure, crystal grain be in core-shell structure, stratum nucleare be lack Co or without Co at Divide Sr1-xLaxFe12-yCoyO19(x=0, y=0), shell B are then rich Co ingredient Sr1-w-vLawCavFe12-zCozO19(w=0.2, v =0.2, z=0.15), La element and content of the Co element in crystal grain are in that uneven gradient is incremented by from inside to outside.
Preparation method are as follows:
1) each initial feed (Fe of nuclear composition is weighed according to the ratio2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder and CaCO3Powder), and be uniformly mixed by way of wet ball-milling；Wherein ball milling solvent is deionized water, Ball-milling Time 4h；
2) by step 1) resulting materials at 1200 DEG C pre-burning 2.5h, obtain Preburning material；
3) by Preburning material coarse crushing, and wet ball-milling is to powder diameter D50It is 0.6 μm, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree becomes 900 DEG C, and powder diameter D is milled to after pre-burning50It is 0.05 μm；
5) in mass ratio 2: 1 slurry M1 is mixed with M2, is added respectively by 0.8% and 0.5% of total powder quality in slurry CaCO3And SiO2, continue ball milling 0.5h；
6) compression moulding under the magnetic field 1.3T；
7) 70min is sintered at 1100 DEG C.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.15-0.3 μm, remanent magnetism Br=4321Gs, Coercivity Hcj=4131Oe, maximum magnetic energy product (BH)max=4.46MGOe.
Embodiment 8
A kind of ferrite permanent-magnet materials with core-shell structure, crystal grain be in core-shell structure, stratum nucleare be lack Co or without Co at Divide Sr1-xLaxFe12-yCoyO19(x=0.04, y=0.025), shell B are then rich Co ingredient Sr1-w-vLawCavFe12-zCozO19| (w=0.325, v=0.325, z=0.25), La element and content of the Co element in crystal grain are in uneven gradient from inside to outside It is incremented by.
Preparation method are as follows:
1) each initial feed (Fe of nuclear composition is weighed according to the ratio2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder and CaCO3Powder), and be uniformly mixed by way of wet ball-milling；Wherein ball milling solvent is deionized water, Ball-milling Time 5h；
2) by step 1) resulting materials at 1250 DEG C pre-burning 2h, obtain Preburning material；
3) by Preburning material coarse crushing, and wet ball-milling is to powder diameter D50It is 0.8 μm, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree becomes 1000 DEG C, ball-milled powder partial size D after pre-burning50It is 0.08 μm；
5) in mass ratio 3: 1 slurry M1 is mixed with M2, CaCO is added by 1% and 0.6% of total powder quality in slurry respectively3 And SiO2, continue ball milling 1h；
6) compression moulding under the magnetic field 1.5T；
7) 60min is sintered at 1200 DEG C.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.15-0.2 μm, remanent magnetism Br=4281Gs, Coercivity Hcj=4061Oe, maximum magnetic energy product (BH)max=4.40MGOe.
Embodiment 9
A kind of ferrite permanent-magnet materials with core-shell structure, crystal grain be in core-shell structure, stratum nucleare be lack Co or without Co at Divide Sr1-xLaxFe12-yCoyO19(x=0.08, y=0.05), shell B are then rich Co ingredient Sr1-w-vLawCavFe12-zCozO19|(w =0.45, v=0.45, z=0.35), La element and content of the Co element in crystal grain are in that uneven gradient is incremented by from inside to outside.
Preparation method are as follows:
1) each initial feed (Fe of nuclear composition is weighed according to the ratio2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder and CaCO3Powder), and be uniformly mixed by way of wet ball-milling；Wherein ball milling solvent is tap water, Ball-milling Time 6h；
2) by step 1) resulting materials at 1300 DEG C pre-burning 1.5h, obtain Preburning material；
3) by Preburning material coarse crushing, and wet ball-milling is to powder diameter D50It is 1 μm, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree becomes 1100 DEG C, ball-milled powder partial size D after pre-burning50It is 0.1 μm；
5) in mass ratio 5: 1 slurry M1 is mixed with M2, is added respectively by 1.2% and 0.7% of total powder quality in slurry CaCO3And SiO2, continue ball milling 1.5h；
6) compression moulding under the magnetic field 1.7T；
7) 50min is sintered at 1300 DEG C.
The magnetic property for the magnet that the present embodiment obtains is as follows: shell with a thickness of 0.05-0.15 μm, remanent magnetism Br= 4269Gs, coercivity Hcj=3852Oe, maximum magnetic energy product (BH)max=4.35MGOe.
Comparative example 1
1) prepare original material: Fe2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder, CaCO3Powder.
2) it is weighed, according to Sr1-xLaxFe12-yCoyO19(x=0.02；Y=0-0.02) ingredient composition, and pass through wet type The mode of ball milling is uniformly mixed, and solvent is deionized water when ball milling, and Ball-milling Time is 5 hours.
3) by the material of mixing at 1250 DEG C pre-burning 2 hours, obtain Preburning material.
4) Preburning material is subjected to coarse crushing, and wet ball-milling 20 hours, obtains powder diameter D50For 0.6 μm of slurry M1。
5) compression moulding under the magnetic field of 1.5T.
6) it is sintered 1 hour at 1200 DEG C.
The magnetic property for the magnet that this comparative example obtains is as follows: remanent magnetism Br=4355Gs, coercivity Hcj=3220Oe, maximum magnetic flux Energy product (BH)max=4.1MGOe.
Comparative example 2
This comparative example and comparative example 1 the difference is that: in step 2), by Sr1-w-vLawCavFe12-zCozO19(w=0.45； V=0.45；Z=0.25) ingredient.
The magnetic property for the magnet that this comparative example obtains is as follows: remanent magnetism Br=4461Gs, coercivity Hcj=4420Oe, maximum magnetic flux Energy product (BH)max=4.67MGOe.
As shown in Fig. 2, its constituent analysis for the ferritic crystal grain of 1 gained of the embodiment of the present invention and its each point of ectonexine Figure.By data in figure it is found that La element with content of the Co element in crystal grain is in that uneven gradient is incremented by from inside to outside.
The data of embodiment 1-9 and comparative example 1-2 are compared, as a result as shown in the table:
By being compared to the data in upper table, it is known that, in comparative example 1, although La, Co content are few, it is integrated Magnetic property is far weaker than the Ferrite Material of embodiment 1-9.And in comparative example 2, although its comprehensive magnetic can be with embodiment 1-9 phase When, but its La, Co additive amount increased significantly, increased costs.
To sum up, ferrite permanent-magnet materials of the invention can make ferrite permanent-magnet materials reduce La-Co element usage amount In the case of, higher magnetic property can still be maintained.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side The protection scope of case.

Claims (10)

1. a kind of ferrite permanent-magnet materials with core-shell structure, it is characterised in that: the ferrite permanent-magnet materials are by nuclear composition With shell component mixing after through plus magnetic, molding, sintering and obtain；Each element molar content is Sr in the nuclear composition1-xLaxFe12- yCoyO19, wherein x=0-0.08, y=0-0.05；Each element molar content is Sr in the shell component1-w-vLawCavFe12- zCozO19, wherein w=0.2-0.45, v=0.2-0.45, z=0.15-0.35；
The crystal grain of gained ferrite permanent-magnet materials is in core-shell structure, and La element and content of the Co element in crystal grain are from inside to outside It is incremented by uneven gradient.
2. a kind of ferrite permanent-magnet materials with core-shell structure as described in claim 1, which is characterized in that in the crystal grain Shell with a thickness of 0.05-0.5 μm.
3. a kind of preparation method of ferrite permanent-magnet materials as claimed in claim 1 or 2, it is characterised in that the following steps are included:
1) each initial feed of nuclear composition is weighed according to the ratio, and is uniformly mixed by way of wet ball-milling；
2) by the pre-burning at 1200-1300 DEG C of step 1) resulting materials, Preburning material is obtained；
3) by Preburning material coarse crushing, and wet ball-milling to powder diameter is 0.6-1 μm, obtains slurry M1；
4) slurry M2 is obtained according to step 1) to method 3), difference is to carry out ingredient, and pre-burning temperature by the proportion of shell component Degree becomes 900-1100 DEG C, and it is 0.05-0.1 μm that powder diameter is milled to after pre-burning；
5) slurry M1 is mixed with M2, CaCO is added by the 0.8-1.2% and 0.5-0.7% of total powder quality in slurry respectively3And SiO2, continue ball milling；
6) compression moulding under magnetic field；
7) it is sintered.
4. preparation method as claimed in claim 3, which is characterized in that in step 1), ball milling solvent is for deionized water or originally Water, Ball-milling Time 4-6h.
5. preparation method as claimed in claim 3, which is characterized in that in step 2, burn-in time 1.5-2.5h.
6. preparation method as claimed in claim 3, which is characterized in that ball milling 15-25h after pre-burning when preparing slurry M1, preparation Ball milling 50-100h after pre-burning when slurry M2.
7. preparation method as claimed in claim 3, which is characterized in that in step 5), the mass ratio of slurry M1 and M2 are 1:1- 5:1, Ball-milling Time 0.5-1.5h.
8. preparation method as claimed in claim 3, which is characterized in that in step 6), magnetic field strength 1.3-1.7T.
9. preparation method as claimed in claim 3, which is characterized in that in step 7), be sintered 50- at 1100-1300 DEG C 70min。
10. preparation method as claimed in claim 3, which is characterized in that the initial feed is Fe2O3Powder, SrCO3Powder, La2O3Powder, Co2O3Powder, CaCO3Powder.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113724953A (en) * 2021-09-12 2021-11-30 杨杭福 Method for preparing high-performance permanent magnet composite material by using high-pressure ultrasonic thermal decomposition method
CN114133233A (en) * 2022-01-30 2022-03-04 天通控股股份有限公司 High-frequency high-Bs composite ferrite material and preparation method thereof
CN115043651A (en) * 2021-03-08 2022-09-13 Tdk株式会社 Ferrite sintered magnet and method for producing ferrite sintered magnet

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221765A2 (en) * 1985-10-29 1987-05-13 Atsushi Ogura Ferrite-ceramic composite powder and method of manufacturing the same
US4764429A (en) * 1986-09-30 1988-08-16 Basf Aktiengesellschaft Finely, divided, spherical, two-layer solid particles
US4876022A (en) * 1985-11-08 1989-10-24 Fuji Photo Film Co., Ltd. Method for preparing ferromagnetic iron oxide particles
US4988648A (en) * 1985-11-29 1991-01-29 Okura Techno-Research Kabushiki Kaisha Homogeneous solid solution material and method of manufacturing the same
JPH0328160A (en) * 1989-06-26 1991-02-06 Tokin Corp Ferrite sintered product and its preparation
US5366761A (en) * 1993-06-04 1994-11-22 National Science Council Method for preparing barium-ferrite-coated γFE2 O3 magnetic power
CN1641970A (en) * 2004-12-24 2005-07-20 横店集团东磁有限公司 Crystallite-cladded sintered magnet, and its manufacturing method, motor and binding magnet
KR100550194B1 (en) * 2002-04-17 2006-02-08 인터내셔널 비지네스 머신즈 코포레이션 Synthesis of Magnetite Nanoparticles and the Process of Forming Fe-Based Nanomaterials
CN1919783A (en) * 2006-09-20 2007-02-28 浙江大学 Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic
CN102093045A (en) * 2010-12-01 2011-06-15 北京航空航天大学 Barium titanate and barium ferrite composite powder with nucleus shell structure and preparation method thereof
CN103265295A (en) * 2013-05-24 2013-08-28 中国计量学院 Preparation method of barium ferrite magnetic material with high coercivity
CN104003703A (en) * 2014-02-27 2014-08-27 横店集团东磁股份有限公司 Preparing method for high-performance permanent-magnetic ferrite materials
CN104261811A (en) * 2014-04-15 2015-01-07 横店集团东磁股份有限公司 High-performance permanent magnetic ferrite and manufacturing method thereof
CN104496444A (en) * 2014-09-15 2015-04-08 横店集团东磁股份有限公司 Low-cost sintered permanent magnet ferrite material and preparation method thereof
CN104556996A (en) * 2015-01-14 2015-04-29 陕西科技大学 BaFe12O19/CoFe2O4 permanent-magnet composite ceramic material and preparation method thereof
CN106145917A (en) * 2016-06-23 2016-11-23 南京航空航天大学 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method
CN107311637A (en) * 2017-07-04 2017-11-03 浙江大学 A kind of method that low-power consumption manganese-zinc ferrite is prepared based on core shell structure crystal grain
CN107352991A (en) * 2017-07-04 2017-11-17 浙江大学 A kind of core shell structure MnZn/nickel zinc complex ferrite and preparation method thereof
CN110323026A (en) * 2018-03-28 2019-10-11 Tdk株式会社 Ferrite sintered magnet

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0221765A2 (en) * 1985-10-29 1987-05-13 Atsushi Ogura Ferrite-ceramic composite powder and method of manufacturing the same
US4876022A (en) * 1985-11-08 1989-10-24 Fuji Photo Film Co., Ltd. Method for preparing ferromagnetic iron oxide particles
US4988648A (en) * 1985-11-29 1991-01-29 Okura Techno-Research Kabushiki Kaisha Homogeneous solid solution material and method of manufacturing the same
US5110774A (en) * 1985-11-29 1992-05-05 Atsushi Ogura Homogeneous solid solution material and method of manufacturing the same
US4764429A (en) * 1986-09-30 1988-08-16 Basf Aktiengesellschaft Finely, divided, spherical, two-layer solid particles
JPH0328160A (en) * 1989-06-26 1991-02-06 Tokin Corp Ferrite sintered product and its preparation
US5366761A (en) * 1993-06-04 1994-11-22 National Science Council Method for preparing barium-ferrite-coated γFE2 O3 magnetic power
KR100550194B1 (en) * 2002-04-17 2006-02-08 인터내셔널 비지네스 머신즈 코포레이션 Synthesis of Magnetite Nanoparticles and the Process of Forming Fe-Based Nanomaterials
CN1641970A (en) * 2004-12-24 2005-07-20 横店集团东磁有限公司 Crystallite-cladded sintered magnet, and its manufacturing method, motor and binding magnet
CN1919783A (en) * 2006-09-20 2007-02-28 浙江大学 Preparation method of ferro-electricity/ferro-magnetism multiple phase ceramic
CN102093045A (en) * 2010-12-01 2011-06-15 北京航空航天大学 Barium titanate and barium ferrite composite powder with nucleus shell structure and preparation method thereof
CN103265295A (en) * 2013-05-24 2013-08-28 中国计量学院 Preparation method of barium ferrite magnetic material with high coercivity
CN104003703A (en) * 2014-02-27 2014-08-27 横店集团东磁股份有限公司 Preparing method for high-performance permanent-magnetic ferrite materials
CN104261811A (en) * 2014-04-15 2015-01-07 横店集团东磁股份有限公司 High-performance permanent magnetic ferrite and manufacturing method thereof
CN104496444A (en) * 2014-09-15 2015-04-08 横店集团东磁股份有限公司 Low-cost sintered permanent magnet ferrite material and preparation method thereof
CN104556996A (en) * 2015-01-14 2015-04-29 陕西科技大学 BaFe12O19/CoFe2O4 permanent-magnet composite ceramic material and preparation method thereof
CN106145917A (en) * 2016-06-23 2016-11-23 南京航空航天大学 A kind of coercitive secondary of permanently magnetic strontium ferrite that improves is combined adding method
CN107311637A (en) * 2017-07-04 2017-11-03 浙江大学 A kind of method that low-power consumption manganese-zinc ferrite is prepared based on core shell structure crystal grain
CN107352991A (en) * 2017-07-04 2017-11-17 浙江大学 A kind of core shell structure MnZn/nickel zinc complex ferrite and preparation method thereof
CN110323026A (en) * 2018-03-28 2019-10-11 Tdk株式会社 Ferrite sintered magnet

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115043651A (en) * 2021-03-08 2022-09-13 Tdk株式会社 Ferrite sintered magnet and method for producing ferrite sintered magnet
CN115043651B (en) * 2021-03-08 2023-10-13 Tdk株式会社 Ferrite sintered magnet and method for producing ferrite sintered magnet
CN113724953A (en) * 2021-09-12 2021-11-30 杨杭福 Method for preparing high-performance permanent magnet composite material by using high-pressure ultrasonic thermal decomposition method
CN114133233A (en) * 2022-01-30 2022-03-04 天通控股股份有限公司 High-frequency high-Bs composite ferrite material and preparation method thereof

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