CN104692786A - Low-radial shrinkage ratio permanent magnetic ferrite magnet and preparation method thereof - Google Patents
Low-radial shrinkage ratio permanent magnetic ferrite magnet and preparation method thereof Download PDFInfo
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- CN104692786A CN104692786A CN201510119902.1A CN201510119902A CN104692786A CN 104692786 A CN104692786 A CN 104692786A CN 201510119902 A CN201510119902 A CN 201510119902A CN 104692786 A CN104692786 A CN 104692786A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 124
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 186
- 239000000463 material Substances 0.000 claims description 85
- VAWSWDPVUFTPQO-UHFFFAOYSA-N calcium strontium Chemical class [Ca].[Sr] VAWSWDPVUFTPQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 27
- 239000011268 mixed slurry Substances 0.000 claims description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- -1 BaCO 3 Inorganic materials 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 6
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 229910052710 silicon Inorganic materials 0.000 abstract description 17
- 239000010703 silicon Substances 0.000 abstract description 17
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000696 magnetic material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 230000004907 flux Effects 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 235000012041 food component Nutrition 0.000 description 4
- 239000005417 food ingredient Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ROYOLNQPXVHWNE-UHFFFAOYSA-N [Co].[Ca].[La] Chemical compound [Co].[Ca].[La] ROYOLNQPXVHWNE-UHFFFAOYSA-N 0.000 description 2
- QBYHSJRFOXINMH-UHFFFAOYSA-N [Co].[Sr].[La] Chemical compound [Co].[Sr].[La] QBYHSJRFOXINMH-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a low-radial shrinkage ratio permanent magnetic ferrite magnet and a preparation method thereof and belongs to the field of permanent magnetic material. The magnet has hexagonal main phase and is composed of metal element expressed by SrxCayLa1-x-y FezCom, wherein x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.4, z is more than or equal to 9.0 and less than or equal to 11.0, m is more than or equal to 0.1 and less than or equal to 0.2, and y/m is more than or equal to 1.5 and less than or equal to 2.0; and meanwhile, through using with secondary additive, the Br thereof arrives at 4200 Gs to 4600 Gs, the Hcj arrives at 4000 Oe to 5600 Oe, and the rectangular degree Hk/HCJ is higher than 0.90. According to the low-radial shrinkage ratio permanent magnetic ferrite magnet and the preparation method thereof, through controlling the content of primary pre-sintering powder and the silicon of the secondary additive, the radial shrinkage ratio of the sintered magnet is 1.10 to 1.12, the production efficiency of the sintering process is improved, the production cost is lowered, and the large industrial production demand is satisfied.
Description
Technical field
The present invention relates to permanent magnet material field, more particularly, relate to a kind of low radial shrinkage than Permanent magnetic ferrite and preparation method thereof, this strontium calcium permanent ferrite magnet is widely used in the fields such as automobile, household electrical appliance or power tool.
Background technology
Hexagonal Magnetoplumbite permanent magnetic ferrite magnet is by divalent cation metal oxide compound (SrO and BaO) and ferric oxide (Fe
2o
3) general name of compound that forms, Permanent magnetic ferrite is widely applicable for the industries such as automobile, household electrical appliance and industrial automation.As permanent-magnet ferrite material, there is the strontium ferrites (SrFe of hexagonal magnetoplumbite type
12o
19) and barium ferrite (BaFe
12o
19) be widely used.The significant parameter affecting permanent-magnet ferrite material magnetic property has two, i.e. residual magnetic flux density (Br) and HCJ (Hcj).The residual magnetic flux density (Br) of magnet determined by the saturation magnetization (4 π Is) of density, orientation degree and crystalline structure.Therefore, Br is expressed as Br=4 π Is × orientation degree × density.On the other hand, HCJ (Hcj) is proportional to H
aХ fc, wherein H
a(H
a=2K
1/ Is) be anisotropy field, fc is the ratio of single domain particle, K
1anisotropy constant, K
1equally with Is also to be determined by crystalline structure.Recently, the particularly miniaturization of car motor rotor and lightweight, and the Ferrite method of frequency-changeable compressor magnet (transferring ferrite to by neodymium iron boron) all needs to use high performance Permanent magnetic ferrite.About the preparation of high-performance permanent-magnet ferrite magnet, in recent years, propose: at above-mentioned strontium ferrites (SrFe
12o
19) in, by the part of the rare earth element such as lanthanum (La) displacement strontium (Sr), replace a part for iron (Fe) with cobalt (Co) and generate strontium lanthanum cobalt (SrLaCo) ferrite, make strontium lanthanum cobalt (SrLaCo) ferritic residual magnetic flux density (Br) and HCJ (Hcj) raising thus.In addition, propose: with strontium ferrites (SrFe
12o
19) situation similarly, at calcium ferrite (CaFe
12o
19) middle lanthanum (La) replace calcium (Ca) a part, replace a part for iron (Fe) with cobalt (Co) and generate calcium lanthanum cobalt (CaLaCo) ferrite, due to calcium ferrite (CaFe
12o
19) lanthanum, cobalt replacement amount higher, therefore calcium lanthanum cobalt (CaLaCo) ferrite obtains higher residual magnetic flux density (Br) and HCJ (Hcj).
In existing high-performance permanent-magnet ferrite magnet technology of preparing, principal concern is the residual magnetic flux density (Br) and the HCJ (Hcj) that improve Permanent magnetic ferrite further, but less open for the production efficiency and reduction production cost aspect how improving Permanent magnetic ferrite sintering process further.Published Patents file, mostly be from changing the food ingredient of Permanent magnetic ferrite to reduce production cost, as China Patent No. ZL2007100709427, authorized announcement date is on January 12nd, 2011, invention and created name is: a kind of economic sintering permanent-magnet ferrite and preparation method thereof, this application case relates to a kind of economic sintering permanent-magnet ferrite and preparation method thereof, this sintered permanent ferrite comprises the Hxagonal ferrite principal phase containing A, R, FE and AL, and has the molecular formula of following characteristics: A
1-Xr
x(FE
12-YaL
y)
zo
19, wherein A represents one or more elements in SR, BA, CA, but must contain SR; R represents one or more elements be selected from rare earth element and BI; X, Y, Z represent mol ratio, and X is 0.01 ~ 0.1; Y is 0.05 ~ 0.3; Z is 0.8 ~ 1.2.The economic sintering permanent-magnet ferrite of this application case adopts many AL that cost is relatively low
2o
3instead of expensive C
ooxide compound, and each element arrangements is reasonable, and considerably reduce the addition of rare earth element, cost is lower.But this kind reduces the method for production cost from the food ingredient changing Permanent magnetic ferrite, one be cannot ensure change Permanent magnetic ferrite food ingredient after still there is the good physical behavior before not changing food ingredient, two is synchronously to enhance productivity.How to improve Permanent magnetic ferrite sintering process production efficiency further and to reduce production cost, be Permanent magnetic ferrite manufacturing insoluble technical problem for many years always.
Summary of the invention
1. invent the technical problem that will solve
The present invention is directed to the deficiency that current Permanent magnetic ferrite cannot enhance productivity and reduce production cost further in sintering process, provide a kind of low radial shrinkage than Permanent magnetic ferrite and preparation method thereof, further increase the production efficiency of Permanent magnetic ferrite sintering process, reduce production cost, meet the needs of the large suitability for industrialized production of Permanent magnetic ferrite.
2. technical scheme
Radial shrinkage after Permanent magnetic ferrite sintering is than being judge that (radial direction is defined as the length and width direction perpendicular to alignment magnetic field for an important indicator of Permanent magnetic ferrite sintering process production efficiency, contraction ratio=green compact size/ripe base size), reduce the radial shrinkage ratio after Permanent magnetic ferrite sintering, the each shaping more number of packages of the moulding press of identical tonnage can be made, the sintering output of kiln improves on year-on-year basis simultaneously, reaches the dual function enhancing productivity and reduce production cost.But, in prior art, but rarely have the report about how reducing radial shrinkage ratio.
The present inventor sums up through great many of experiments and finds, the oxide compound of silicon and silicate affect very big on hexangle type Permanent magnetic ferrite anisotropic radial shrinkage ratio.In the preparation process of Permanent magnetic ferrite, contriver creatively proposes the mixing generating mode of strontium calcium ferrite and the proportioning of optimization, and change existing in Primary batching system, add silicon oxide compound or silicate produce ferritic traditional mode as ferrite sintering aid, employing is not added any non-master and is generated additive (i.e. silicon and compound thereof) mutually, secondary adds micro-silicon and compound makes the radial shrinkage of strontium calcium permanent ferrite magnet than reducing about 5%, coordinate the use of secondary additive in the present invention simultaneously, make the residual magnetic flux density of the strontium calcium permanent ferrite magnet prepared, HCJ and rectangular degree are all significantly improved.
For achieving the above object, technical scheme provided by the invention is:
The low radial shrinkage of one of the present invention is than Permanent magnetic ferrite, and the composition of a Preblend raw material of this strontium calcium permanent ferrite magnet is Sr by atomic ratio
xca
yla
1-x-yfe
zco
m, wherein: 0.2≤x≤0.8,0.1≤y≤0.4,9.0≤z≤11.0,0.1≤m≤0.2 and 1.5≤y/m≤2.0, the secondary additive of this strontium calcium permanent ferrite magnet comprises CaCO
3, SrCO
3, TiO
2, BaCO
3, SiO
2, Al
2o
3, Cr
2o
3, MnCO
3, ZnO, Nd
2o
3, V
2o
5, CuO, H
3bO
3, La
2o
3, Co
3o
4, HCOOH, C
6h
14o
6and Bi
2o
3, each additive adds all in powder form, and each additive is with a Preburning material grain weight gauge, and adding proportion is: CaCO
30.2 ~ 1.0wt%, SrCO
30.2 ~ 10.6wt%, TiO
20.01 ~ 0.15wt%, BaCO
30.01 ~ 0.15wt%, SiO
20.01 ~ 0.15wt%, Al
2o
30.01 ~ 1.2wt%, Cr
2o
30.01 ~ 1.2wt%, MnCO
30.01 ~ 0.15wt%, ZnO0.01 ~ 0.15wt%, Nd
2o
30.01 ~ 0.15wt%, V
2o
50.01 ~ 0.15wt%, CuO 0.01 ~ 0.15wt%, H
3bO
30.1 ~ 0.2wt%, La
2o
30.3 ~ 0.9wt%, Co
3o
40.2 ~ 0.6wt%, HCOOH 0.2 ~ 0.5wt%, C
6h
14o
60.1 ~ 0.6wt%, Bi
2o
30.01 ~ 0.3wt%.
As a further improvement on the present invention, this strontium calcium permanent ferrite magnet has the principal phase of structure of hexagonal crystal, and has Br:4200 Gs ~ 4600 Gs, Hcj:4000 Oe ~ 5600 Oe, rectangular degree Hk/Hcj higher than 0.90 high magnetic characteristics.
A kind of low radial shrinkage of the present invention is than the preparation method of Permanent magnetic ferrite, and concrete steps are as follows,
(1) Primary batching system: by atomic ratio Sr
xca
yla
1-x-yfe
zco
mcalculate the calcium carbonate powders, strontium carbonate powder, lanthanum oxide powder, cobalt oxide powder and the croci that weigh containing required element, obtain a Preblend raw material, wherein: 0.2≤x≤0.8,0.1≤y≤0.4,9.0≤z≤11.0,0.1≤m≤0.2 and 1.5≤y/m≤2.0;
(2) mix: an above-mentioned Preblend raw material is mixed by wet ball-milling technique, form the mixed slurry that mean particle size is 0.9 ~ 1.1 μm, then mixed slurry is dewatered;
(3) pre-burning: the mixed slurry after above-mentioned dehydration is carried out pre-burning, calcined temperature is 1250 ~ 1350 DEG C, and burn-in time is 5 ~ 7 hours, obtains a Preburning material particle after pre-burning;
(4) coarse reduction: become by an above-mentioned Preburning material particulate abrasive mean particle size to be the powder of 2.0 ~ 6.0 μm, obtain a Preburning material powder;
(5) second batch: take an above-mentioned Preburning material powder, and add secondary additive in weight proportion mode, forms second batch mixture;
(6) secondary ball milling: above-mentioned second batch mixture is adopted the mixing of wet ball-milling technique, mixed second batch mixture forms the secondary mixed material slurry that mean particle size is 0.8 ~ 1.0 μm;
(7) shaping: by above-mentioned secondary mixed material slurry Temperature fall, by the time secondary mixed material slurry temperature reaches less than 50 DEG C, water content adjustment is carried out to secondary mixed material slurry, the concentration of adjustment secondary mixed material slurry is 60-80wt%, then compression moulding, obtain molding, and apply alignment magnetic field at pressing direction;
(8) sinter: first heat-treated the temperature of 100 ~ 300 DEG C by above-mentioned molding, removing moisture, then sinters in atmosphere, final acquisition strontium calcium permanent ferrite magnet;
In described step (5), secondary additive comprises CaCO
3, SrCO
3, TiO
2, BaCO
3, SiO
2, Al
2o
3, Cr
2o
3, MnCO
3, ZnO, Nd
2o
3, V
2o
5, CuO, H
3bO
3, La
2o
3, Co
3o
4, HCOOH, C
6h
14o
6and Bi
2o
3, each additive adds all in powder form, and each additive is with a Preburning material grain weight gauge, and adding proportion is: CaCO
30.2 ~ 1.0wt%, SrCO
30.2 ~ 10.6wt%, TiO
20.01 ~ 0.15wt%, BaCO
30.01 ~ 0.15wt%, SiO
20.01 ~ 0.15wt%, Al
2o
30.01 ~ 1.2wt%, Cr
2o
30.01 ~ 1.2wt%, MnCO
30.01 ~ 0.15wt%, ZnO0.01 ~ 0.15wt%, Nd
2o
30.01 ~ 0.15wt%, V
2o
50.01 ~ 0.15wt%, CuO 0.01 ~ 0.15wt%, H
3bO
30.1 ~ 0.2wt%, La
2o
30.3 ~ 0.9wt%, Co
3o
40.2 ~ 0.6wt%, HCOOH 0.2 ~ 0.5wt%, C
6h
14o
60.1 ~ 0.6wt%, Bi
2o
30.01 ~ 0.3wt%.
As a further improvement on the present invention, in step (1), the mean particle size of a Preblend raw material is 0.9 ~ 2.0 μm.
As a further improvement on the present invention, in step (2), after dehydration, the concentration of mixed slurry is 60 ~ 65%.
As a further improvement on the present invention, in step (7), the intensity of alignment magnetic field is not less than 400kA/m.
As a further improvement on the present invention, in step (8), the heat-up rate of sintering process is 120 ~ 130 DEG C/h, and sintering temperature is 1150 ~ 1250 DEG C, and soaking time is 1 ~ 2 hour
3. beneficial effect
Adopt technical scheme provided by the invention, compared with prior art, there is following unusual effect:
(1) a kind of low radial shrinkage of the present invention is than the preparation method of Permanent magnetic ferrite, use Primary batching system not add a Preblend raw material of silicon and compound thereof, (silicon-containing material added in second batch is only SiO for the silicon of second batch interpolation trace and compound thereof
2powder, and this SiO
2powder is with a Preburning material grain weight gauge, its adding proportion is only up to 0.15wt%), reduce the radial shrinkage ratio after strontium calcium permanent ferrite magnet sintering, the each shaping more number of packages of the moulding press of identical tonnage can be made, the sintering output of kiln improves on year-on-year basis simultaneously, reach the dual function enhancing productivity and reduce production cost, meet the needs of the large suitability for industrialized production of strontium calcium permanent ferrite magnet.
(2) a kind of low radial shrinkage of the present invention is than the preparation method of Permanent magnetic ferrite, secondary additive is added in second batch step, improve the intrinsic parameters (i.e. residual magnetic flux density, HCJ and rectangular degree) of strontium calcium permanent ferrite magnet, secondary additive adds the density of strontium calcium permanent ferrite magnet as sintering aid simultaneously, and prevent growing up of crystal grain, make strontium calcium permanent ferrite magnet obtain the weave construction of dense uniform.
(3) a kind of low radial shrinkage of the present invention is than the preparation method of Permanent magnetic ferrite, just adds rare precious metals cobalt, be conducive to obtaining high performance strontium calcium permanent ferrite magnet in Primary batching system step.
(4) the low radial shrinkage of one of the present invention is than Permanent magnetic ferrite, has Br:4200 Gs ~ 4600 Gs, Hcj:4000Oe ~ 5600 Oe, rectangular degree Hk/Hcj higher than 0.90 high magnetic characteristics.
Embodiment
Below by embodiment, technical scheme of the present invention is further described in detail, but the present invention is not limited to these embodiments.
Embodiment 1
Primary batching system operation select each ingredient requirement and corresponding weight as follows:
1. ferric oxide (Fe
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 0.9 μm), weight 1271.0Kg;
2. calcium carbonate (CaCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), weight 60.7Kg;
3. Strontium carbonate powder (SrCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), weight 44.3Kg;
4. lanthanum trioxide (La
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.0 μm), weight 99.8Kg;
5. cobalt oxide (Co
3o
4) powder (purity is with the original mean particle containing cobalt gauge calculation>=72.0%, particle: 1.0 μm), weight 25.1Kg.(raw material granularity is too small, will cause fine grain generation, and be unfavorable for shaping after pre-burning and ball milling; Raw material granularity is excessive, and pre-burning is then insufficient.In the present embodiment, the mean particle size of each raw material is between 0.9 ~ 2.0 μm, is conducive to well shaping and abundant pre-burning.)
Above-mentioned load weighted starting material are joined in 1.5T ball mill, do not add any additive, add water 1.5 tons, ball milling 5 hours, then be that the mixed slurry of 0.9 μm dewaters by being pumped into centrifuge by the mean particle size formed after ball milling, mixed slurry concentration after dehydration was 60% (referring to that the Solute mass percentage composition in mixed slurry is 60%), again by dehydration after mixed slurry by being pumped into pre-burning in rotary kiln, rotary kiln length is 39 meters, calcined temperature 1250 DEG C, burn-in time is 5 hours, obtains a Preburning material particle after pre-burning; A Preburning material particle enters tuber grinder and carries out pulverizing acquisition Preburning material powder, and the mean particle size of a Preburning material powder is 2.0 μm, detects a Preburning material powder and has ferritic principal phase formula and can be expressed as Sr
0.2ca
0.4la
0.4fe
10.5co
0.2.It should be noted that, a Preburning material powder bringing into because of siliceous impurity in preparation process, cause containing element silicon in a Preburning material powder, in a Preburning material powder of the present embodiment, the analytical value of silicone content is about 0.04wt%.What deserves to be explained is, in the present invention, should 0.05wt% be not more than in principle for its silicone content of Preburning material powder.
Then, take the Preburning material powder 1300kg produced in a manner described, add secondary additive in weight proportion mode, wherein add the calcium carbonate (CaCO of 0.2wt%
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.2wt% SrCO
3the TiO of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.01wt%
2the BaCO of powder (original mean particle of purity>=99.0wt%, particle: 12 μm), 0.15wt%
3the SiO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.01wt%
2powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.06wt%Al
2o
3the Cr of powder (original mean particle of purity>=99.0wt%, particle: 4.0 μm), 1.2wt%
2o
3the MnCO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.01wt%
3the ZnO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.15wt%, the Nd of 0.15wt%
2o
3the V of (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.08wt%
2o
5the CuO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm), 0.01wt%, the H of 0.1wt%wt%
3bO
3lanthanum trioxide (the La of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.6wt%
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.0 μm), 0.6wt% Co
3o
4the HCOOH powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm) of powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.2wt%, the C of 0.1wt%
6h
14o
6powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.01wt%Bi
2o
3powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), adds water 1700 liters and carries out ball milling, ball milling 15 hours, forms secondary mixed material slurry after ball milling, and the mean particle size of this secondary mixed material slurry is 0.87 μm.
By above-mentioned secondary mixed material slurry Temperature fall, by the time when secondary mixed material slurry temperature reaches 20 DEG C, then water content adjustment is carried out to secondary mixed material slurry, the concentration that secondary mixed material is starched is adjusted to 65%, then compression moulding, applying magneticstrength at pressing direction is the alignment magnetic field of 500kA/m, with forming pressure 0.5ton/cm
3carry out compressed moulding, gained molding is the right cylinder of diameter 40cm, height 13cm.
Heat-treat molding the temperature of 100 DEG C, removing moisture, then sinter in air atmosphere, the heat-up rate of sintering process is 120 DEG C/h, 1200 DEG C of insulations 1.5 hours, and final acquisition strontium calcium permanent ferrite magnet.
The strontium calcium permanent ferrite magnet sample randomly drawing embodiment 1 gained carries out upper and lower surface grinding, measure its residual magnetic flux density (Br) and HCJ (Hcj), measure its rectangular degree Hk/Hcj, radial shrinkage ratio and silicone content, detailed data is as shown in table 1 simultaneously:
Table 1
From above-mentioned testing inspection result, in the present embodiment, Primary batching system is used not add a Preblend raw material of silicon and compound thereof, second batch adds silicon and the compound thereof of trace, coordinate the use of secondary additive in the present embodiment simultaneously, obtain residual magnetic flux density Br higher than 4500 Gs, HCJ Hcj higher than 4700 Oe, rectangular degree Hk/Hcj is not less than 0.92, and radial shrinkage is than the high-performance strontium calcium permanent ferrite magnet of average out to 1.11.
Comparative example 1:
Primary batching system operation select each ingredient requirement and corresponding weight as follows:
1. ferric oxide (Fe
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 0.9 μm), weight 1271.0Kg;
2. calcium carbonate (CaCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), weight 60.7Kg;
3. Strontium carbonate powder (SrCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), weight 44.3Kg;
4. lanthanum trioxide (La
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.0 μm), weight 99.8Kg;
5. cobalt oxide (Co
3o
4) powder (purity is with the original mean particle containing cobalt gauge calculation>=72.0%, particle: 1.0 μm), weight 25.1Kg.
Above-mentioned load weighted starting material are joined in 1.5T ball mill, adds sintering aid SiO
2powder (original mean particle of purity>=99.0wt%, particle: 20 μm) 3.0kg, add water 1.5 tons, ball milling 5 hours, then be that the mixed slurry of 0.9 μm dewaters by being pumped into centrifuge by the mean particle size formed after ball milling, mixed slurry concentration after dehydration was 60% (referring to that the Solute mass percentage composition in mixed slurry is 60%), again by dehydration after mixed slurry by being pumped into pre-burning in rotary kiln, rotary kiln length is 39 meters, calcined temperature 1250 DEG C, burn-in time 5 hours, obtains a Preburning material particle after pre-burning; A Preburning material particle enters tuber grinder and carries out pulverizing acquisition Preburning material powder, and the mean particle size of a Preburning material powder is 2.0 μm, detects a Preburning material powder and has ferritic principal phase formula and can be expressed as Sr
0.2ca
0.4la
0.4fe
10.5co
0.2.
Then, take the Preburning material powder 1300kg produced in a manner described, add 1.2wt% calcium carbonate (CaCO in weight proportion mode
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.3wt% silicon-dioxide (SiO
2) powder (purity>=99.0wt%), 0.5wt%Cr
2o
3powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), adds water 1700 liters and carries out ball milling, ball milling 15 hours, forms secondary mixed material slurry after ball milling, and the mean particle size of this secondary mixed material slurry is 0.85 μm.
By above-mentioned secondary mixed material slurry Temperature fall, by the time when secondary mixed material slurry temperature reaches 20 DEG C, then water content adjustment is carried out to secondary mixed material slurry, the concentration that secondary mixed material is starched is adjusted to 65%, then compression moulding, applying magneticstrength at pressing direction is the alignment magnetic field of 500kA/m, with forming pressure 0.5ton/cm
3carry out compressed moulding, gained molding is the right cylinder of diameter 40cm, height 13cm.
Heat-treat molding the temperature of 100 DEG C, removing moisture, then sinter in air atmosphere, the heat-up rate of sintering process is 120 DEG C/h, 1200 DEG C of insulations 1.5 hours, and final acquisition strontium calcium permanent ferrite magnet.
The strontium calcium permanent ferrite magnet sample randomly drawing comparative example 1 gained carries out upper and lower surface grinding, measure its residual magnetic flux density (Br) and HCJ (Hcj), measure its rectangular degree (Hk/Hcj), radial shrinkage ratio and silicone content, detailed data is as shown in table 2 simultaneously:
Table 2
From above-mentioned testing inspection result, in this comparative example, silicon and the compound thereof of specified amount is added according to a conventional method in Primary batching system, second batch, add conventional secondary additive and the strontium calcium permanent ferrite magnet prepared simultaneously, its residual magnetic flux density (Br), HCJ (Hcj) and rectangular degree (Hk/Hcj) are obviously on the low side compared to embodiment 1, and its radial shrinkage is than increasing about 5% compared to embodiment 1.
Embodiment 2
Primary batching system operation select each ingredient requirement and corresponding weight as follows:
1. ferric oxide (Fe
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.1 μm), weight 1264.0Kg;
2. calcium carbonate (CaCO
3) powder (original mean particle of purity>=98.5wt%, particle: 2.0 μm), weight 45.1Kg;
3. Strontium carbonate powder (SrCO
3) powder (original mean particle of purity>=98.5wt%, particle: 2.0 μm), weight 66.8Kg;
4. lanthanum trioxide (La
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm), weight 99.5Kg;
5. cobalt oxide (Co
3o
4) powder (purity is with the original mean particle containing cobalt gauge calculation>=72.0%, particle: 2.0 μm), weight 25.1Kg.
Above-mentioned load weighted starting material are joined in 1.5T ball mill, do not add any additive, add water 1.5 tons, ball milling 5 hours, then be that the mixed slurry of 1.1 μm dewaters by being pumped into centrifuge by the mean particle size formed after ball milling, mixed slurry concentration after dehydration was 65% (referring to that the Solute mass percentage composition in mixed slurry is 65%), again by dehydration after mixed slurry by being pumped into pre-burning in rotary kiln, rotary kiln length is 39 meters, calcined temperature is 1350 DEG C, burn-in time 7 hours, obtains a Preburning material particle after pre-burning; A Preburning material particle enters tuber grinder and carries out pulverizing acquisition Preburning material powder, and the mean particle size of a Preburning material powder is 6.0 μm, detects a Preburning material powder and has ferritic principal phase formula and can be expressed as Sr
0.3ca
0.3la
0.4fe
10.5co
0.2.It should be noted that, a Preburning material powder bringing into because of siliceous impurity in preparation process, cause containing element silicon in a Preburning material powder, in a Preburning material powder of the present embodiment, the analytical value of silicone content is about 0.03wt%.
Then, take the Preburning material powder 1300kg produced in a manner described, add secondary additive in weight proportion mode, wherein add the calcium carbonate (CaCO of 0.6wt%
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 5.7wt% SrCO
3the TiO of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.08wt%
2the BaCO of powder (original mean particle of purity>=99.0wt%, particle: 12 μm), 0.08wt%
3the SiO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.08wt%
2powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.01wt%Al
2o
3the Cr of powder (original mean particle of purity>=99.0wt%, particle: 4.0 μm), 0.01wt%
2o
3the MnCO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.08wt%
3the ZnO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.01wt%, the Nd of 0.08wt%
2o
3the V of (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.15wt%
2o
5the CuO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm), 0.08wt%, the H of 0.15wt%wt%
3bO
3lanthanum trioxide (the La of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.3wt%
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.0 μm), 0.4wt% Co
3o
4the HCOOH powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm) of powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.3wt%, the C of 0.3wt%
6h
14o
6powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.015wt%Bi
2o
3powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), adds water 1700 liters and carries out ball milling, ball milling 15 hours, forms secondary mixed material slurry after ball milling, and the mean particle size of this secondary mixed material slurry is 0.93 μm.
By above-mentioned secondary mixed material slurry Temperature fall, by the time when secondary mixed material slurry temperature reaches 30 DEG C, then water content adjustment is carried out to secondary mixed material slurry, the concentration that secondary mixed material is starched is adjusted to 75%, then compression moulding, applying magneticstrength at pressing direction is the alignment magnetic field of 500kA/m, with forming pressure 0.5ton/cm
3carry out compressed moulding, gained molding is the right cylinder of diameter 40cm, height 13cm.
Heat-treat molding the temperature of 300 DEG C, removing moisture, then sinter in air atmosphere, the heat-up rate of sintering process is 130 DEG C/h, 1250 DEG C of insulations 2 hours, and final acquisition strontium calcium permanent ferrite magnet.
The strontium calcium permanent ferrite magnet sample randomly drawing embodiment 2 gained carries out upper and lower surface grinding, measure its residual magnetic flux density (Br) and HCJ (Hcj), measure its rectangular degree Hk/Hcj, radial shrinkage ratio and silicone content, detailed data is as shown in table 3 simultaneously:
Table 3
From above-mentioned testing inspection result, in the present embodiment, Primary batching system is used not add a Preblend raw material of silicon and compound thereof, second batch adds silicon and the compound thereof of trace, coordinate the use of secondary additive in the present embodiment simultaneously, obtain residual magnetic flux density Br higher than 4500 Gs, HCJ Hcj higher than 4600 Oe, rectangular degree Hk/Hcj is not less than 0.92, and radial shrinkage is than the high-performance strontium calcium permanent ferrite magnet of average out to 1.12.
Embodiment 3
Primary batching system operation select each ingredient requirement and corresponding weight as follows:
1. ferric oxide (Fe
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.5 μm), weight 1271.0Kg;
2. calcium carbonate (CaCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.4 μm), weight 60.7Kg;
3. Strontium carbonate powder (SrCO
3) powder (original mean particle of purity>=98.5wt%, particle: 1.6 μm), weight 44.3Kg;
4. lanthanum trioxide (La
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.3 μm), weight 99.8Kg;
5. cobalt oxide (Co
3o
4) powder (purity is with the original mean particle containing cobalt gauge calculation>=72.0%, particle: 1.7 μm), weight 25.1Kg.
Above-mentioned load weighted starting material are joined in 1.5T ball mill, do not add any additive, add water 1.5 tons, ball milling 5 hours, then be that the mixed slurry of 1 μm dewaters by being pumped into centrifuge by the mean particle size formed after ball milling, mixed slurry concentration after dehydration was 62% (referring to that the Solute mass percentage composition in mixed slurry is 62%), again by dehydration after mixed slurry by being pumped into pre-burning in rotary kiln, rotary kiln length is 39 meters, calcined temperature 1300 DEG C, burn-in time is 6 hours, obtains a Preburning material particle after pre-burning; A Preburning material particle enters tuber grinder and carries out pulverizing acquisition Preburning material powder, and the mean particle size of a Preburning material powder is 4.0 μm, detects a Preburning material powder and has ferritic principal phase formula and can be expressed as Sr
0.2ca
0.4la
0.4fe
10.5co
0.2.It should be noted that, a Preburning material powder bringing into because of siliceous impurity in preparation process, cause containing element silicon in a Preburning material powder, in a Preburning material powder of the present embodiment, the analytical value of silicone content is about 0.03wt%.
Then, take the Preburning material powder 1300kg produced in a manner described, add secondary additive in weight proportion mode, wherein add the calcium carbonate (CaCO of 1.0wt%
3) powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 10.6wt% SrCO
3the TiO of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.15wt%
2the BaCO of powder (original mean particle of purity>=99.0wt%, particle: 12 μm), 0.01wt%
3the SiO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.15wt%
2powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 1.2wt%Al
2o
3the Cr of powder (original mean particle of purity>=99.0wt%, particle: 4.0 μm), 0.6wt%
2o
3the MnCO of powder (original mean particle of purity>=99.0wt%, particle: 5.0 μm), 0.15wt%
3the ZnO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.08wt%, the Nd of 0.01wt%
2o
3the V of (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.01wt%
2o
5the CuO powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm) of powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm), 0.15wt%, the H of 0.2wt%wt%
3bO
3lanthanum trioxide (the La of powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), 0.9wt%
2o
3) powder (original mean particle of purity>=99.0wt%, particle: 1.0 μm), 0.2wt% Co
3o
4the HCOOH powder (original mean particle of purity>=99.0wt%, particle: 2.0 μm) of powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.5wt%, the C of 0.6wt%
6h
14o
6powder (original mean particle of purity>=98.5wt%, particle: 1.0 μm), 0.3wt%Bi
2o
3powder (original mean particle of purity>=99.0wt%, particle: 3.0 μm), adds water 1700 liters and carries out ball milling, ball milling 15 hours, forms secondary mixed material slurry after ball milling, and the mean particle size of this secondary mixed material slurry is 0.84 μm.
By above-mentioned secondary mixed material slurry Temperature fall, by the time when secondary mixed material slurry temperature reaches 20 DEG C, then water content adjustment is carried out to secondary mixed material slurry, the concentration that secondary mixed material is starched is adjusted to 70%, then compression moulding, applying magneticstrength at pressing direction is the alignment magnetic field of 500kA/m, with forming pressure 0.5ton/cm
3carry out compressed moulding, gained molding is the right cylinder of diameter 40cm, height 13cm.
Heat-treat molding the temperature of 100 DEG C, removing moisture, then sinter in air atmosphere, the heat-up rate of sintering process is 125 DEG C/h, 1250 DEG C of insulations 1 hour, and final acquisition strontium calcium permanent ferrite magnet.
The strontium calcium permanent ferrite magnet sample randomly drawing embodiment 3 gained carries out upper and lower surface grinding, measure its residual magnetic flux density (Br) and HCJ (Hcj), measure its rectangular degree Hk/Hcj, radial shrinkage ratio and silicone content, detailed data is as shown in table 4 simultaneously:
Table 4
From above-mentioned testing inspection result, in the present embodiment, Primary batching system is used not add a Preblend raw material of silicon and compound thereof, second batch adds silicon and the compound thereof of trace, coordinate the use of secondary additive in the present embodiment simultaneously, obtain residual magnetic flux density Br higher than 4400 Gs, HCJ Hcj higher than 4700 Oe, rectangular degree Hk/Hcj is not less than 0.93, and radial shrinkage is than the high-performance strontium calcium permanent ferrite magnet of average out to 1.11.
Claims (7)
1. low radial shrinkage is than a Permanent magnetic ferrite, it is characterized in that, the composition of a Preblend raw material of this strontium calcium permanent ferrite magnet is Sr by atomic ratio
xca
yla
1-x-yfe
zco
m, wherein: 0.2≤x≤0.8,0.1≤y≤0.4,9.0≤z≤11.0,0.1≤m≤0.2 and 1.5≤u/m≤2.0, the secondary additive of this strontium calcium permanent ferrite magnet comprises CaCO
3, SrCO
3, TiO
2, BaCO
3, SiO
2, Al
2o
3, Cr
2o
3, MnCO
3, ZnO, Nd
2o
3, V
2o
5, CuO, H
3bO
3, La
2o
3, Co
3o
4, HCOOH, C
6h
14o
6and Bi
2o
3, each additive adds all in powder form, and each additive is with a Preburning material grain weight gauge, and adding proportion is: CaCO
30.2 ~ 1.0wt%, SrCO
30.2 ~ 10.6wt%, TiO
20.01 ~ 0.15wt%, BaCO
30.01 ~ 0.15wt%, SiO
20.01 ~ 0.15wt%, Al
2o
30.01 ~ 1.2wt%, Cr
2o
30.01 ~ 1.2wt%, MnCO
30.01 ~ 0.15wt%, ZnO 0.01 ~ 0.15wt%, Nd
2o
30.01 ~ 0.15wt%, V
2o
50.01 ~ 0.15wt%, CuO0.01 ~ 0.15wt%, H
3bO
30.1 ~ 0.2wt%, La
2o
30.3 ~ 0.9wt%, Co
3o
40.2 ~ 0.6wt%, HCOOH0.2 ~ 0.5wt%, C
6h
14o
60.1 ~ 0.6wt%, Bi
2o
30.01 ~ 0.3wt%.
2. the low radial shrinkage of one according to claim 1 compares Permanent magnetic ferrite, it is characterized in that, this strontium calcium permanent ferrite magnet has the principal phase of structure of hexagonal crystal, and there is Br:4200Gs ~ 4600Gs, Hcj:4000Oe ~ 5600Oe, rectangular degree Hk/Hcj higher than 0.90 high magnetic characteristics.
3. low radial shrinkage is than a preparation method for Permanent magnetic ferrite, it is characterized in that, concrete steps are as follows,
(1) Primary batching system: by atomic ratio Sr
xca
yla
1-x-yfe
zco
mcalculate the calcium carbonate powders, strontium carbonate powder, lanthanum oxide powder, cobalt oxide powder and the croci that weigh containing required element, obtain a Preblend raw material, wherein: 0.2≤x≤0.8,0.1≤y≤0.4,9.0≤z≤11.0,0.1≤m≤0.2 and 1.5≤y/m≤2.0;
(2) mix: an above-mentioned Preblend raw material is mixed by wet ball-milling technique, form the mixed slurry that mean particle size is 0.9 ~ 1.1 μm, then mixed slurry is dewatered;
(3) pre-burning: the mixed slurry after above-mentioned dehydration is carried out pre-burning, calcined temperature is 1250 ~ 1350 DEG C, and burn-in time is 5 ~ 7 hours, obtains a Preburning material particle after pre-burning;
(4) coarse reduction: become by an above-mentioned Preburning material particulate abrasive mean particle size to be the powder of 2.0 ~ 6.0 μm, obtain a Preburning material powder;
(5) second batch: take an above-mentioned Preburning material powder, and add secondary additive in weight proportion mode, forms second batch mixture;
(6) secondary ball milling: above-mentioned second batch mixture is adopted the mixing of wet ball-milling technique, mixed second batch mixture forms the secondary mixed material slurry that mean particle size is 0.8 ~ 1.0 μm;
(7) shaping: by above-mentioned secondary mixed material slurry Temperature fall, by the time secondary mixed material slurry temperature reaches less than 50 DEG C, water content adjustment is carried out to secondary mixed material slurry, the concentration of adjustment secondary mixed material slurry is 60-80wt%, then compression moulding, obtain molding, and apply alignment magnetic field at pressing direction;
(8) sinter: first heat-treated the temperature of 100 ~ 300 DEG C by above-mentioned molding, removing moisture, then sinters in atmosphere, final acquisition strontium calcium permanent ferrite magnet;
In described step (6), secondary additive comprises CaCO
3, SrCO
3, TiO
2, BaCO
3, SiO
2, Al
2o
3, Cr
2o
3, MnCO
3, ZnO, Nd
2o
3, V
2o
5, CuO, H
3bO
3, La
2o
3, Co
3o
4, HCOOH, C
6h
14o
6and Bi
2o
3, each additive adds all in powder form, and each additive is with a Preburning material grain weight gauge, and adding proportion is: CaCO
30.2 ~ 1.0wt%, SrCO
30.2 ~ 10.6wt%, TiO
20.01 ~ 0.15wt%, BaCO
30.01 ~ 0.15wt%, SiO
20.01 ~ 0.15wt%, Al
2o
30.01 ~ 1.2wt%, Cr
2o
30.01 ~ 1.2wt%, MnCO
30.01 ~ 0.15wt%, ZnO0.01 ~ 0.15wt%, Nd
2o
30.01 ~ 0.15wt%, V
2o
50.01 ~ 0.15wt%, CuO 0.01 ~ 0.15wt%, H
3bO
30.1 ~ 0.2wt%, La
2o
30.3 ~ 0.9wt%, Co
3o
40.2 ~ 0.6wt%, HCOOH 0.2 ~ 0.5wt%, C
6h
14o
60.1 ~ 0.6wt%, Bi
2o
30.01 ~ 0.3wt%.
4. a kind of low radial shrinkage according to claim 3 or 4, than the preparation method of Permanent magnetic ferrite, is characterized in that, in step (1), the mean particle size of a Preblend raw material is 0.9 ~ 2.0 μm.
5. a kind of low radial shrinkage according to claim 3 is than the preparation method of Permanent magnetic ferrite, it is characterized in that, in step (2), after dehydration, the concentration of mixed slurry is 60 ~ 65%.
6. a kind of low radial shrinkage according to claim 3 is than the preparation method of Permanent magnetic ferrite, it is characterized in that, in step (7), the intensity of alignment magnetic field is not less than 400kA/m.
7. a kind of low radial shrinkage according to claim 3 is than the preparation method of Permanent magnetic ferrite, it is characterized in that, in step (8), the heat-up rate of sintering process is 120 ~ 130 DEG C/h, and sintering temperature is 1150 ~ 1250 DEG C, and soaking time is 1 ~ 2 hour.
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CN106699155A (en) * | 2016-12-21 | 2017-05-24 | 马鞍山起劲磁塑科技有限公司 | Strontium ferrite magnetic powder additive |
CN111423226A (en) * | 2020-03-17 | 2020-07-17 | 江门江益磁材有限公司 | Permanent magnetic ferrite and preparation method and application thereof |
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CN111995385A (en) * | 2020-07-29 | 2020-11-27 | 横店集团东磁股份有限公司 | Permanent magnetic ferrite material with high radial and axial shrinkage consistency and preparation method thereof |
CN112645719A (en) * | 2020-12-29 | 2021-04-13 | 横店集团东磁股份有限公司 | Method for improving radial shrinkage of permanent magnetic ferrite magnet |
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CN111423226A (en) * | 2020-03-17 | 2020-07-17 | 江门江益磁材有限公司 | Permanent magnetic ferrite and preparation method and application thereof |
CN111995385A (en) * | 2020-07-29 | 2020-11-27 | 横店集团东磁股份有限公司 | Permanent magnetic ferrite material with high radial and axial shrinkage consistency and preparation method thereof |
CN112645719A (en) * | 2020-12-29 | 2021-04-13 | 横店集团东磁股份有限公司 | Method for improving radial shrinkage of permanent magnetic ferrite magnet |
CN112645719B (en) * | 2020-12-29 | 2022-04-19 | 横店集团东磁股份有限公司 | Method for improving radial shrinkage of permanent magnetic ferrite magnet |
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