CN101106001A - Low-temperature coefficient permanent magnet ferrite material and its production method - Google Patents

Low-temperature coefficient permanent magnet ferrite material and its production method Download PDF

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CN101106001A
CN101106001A CNA2007101276076A CN200710127607A CN101106001A CN 101106001 A CN101106001 A CN 101106001A CN A2007101276076 A CNA2007101276076 A CN A2007101276076A CN 200710127607 A CN200710127607 A CN 200710127607A CN 101106001 A CN101106001 A CN 101106001A
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temperature coefficient
permanent magnet
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ball milling
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秦福明
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Abstract

The invention relates to a material used in the ferrite magnetic material industry and the production method thereof, in particular to a low-temperature coefficient permanent magnetic ferrite material and the production method thereof. Directed at the prior art's problems such as high temperature coefficient, the addition of expensive factors including La, Co, and Bi, and high production cost, the invention provides a low-temperature coefficient permanent magnetic ferrite material and the production method thereof without adding factors such as La, Co, and Bi. The materials of the invention area: The main phase is magnetoplumbite structure, and the chemical equation is: Sr1-xAxFe12-yMyO19, wherein: A=Ca, Na, Ba, Pb, K 1-2 types, x=0.05-0.5; M=Al, Cr, Zn2/3V1/3, Zn2/3Nb1/3, Cu2/3V1/3, Cu2/3Nb1/3, Zn1/2Ge1/2, Zn1/2Si1/2, Cu1/2Ga1/2, Cu1/2Si1/2 1-3 types.

Description

Low-temperature coefficient permanent magnet ferrite material and manufacture method
Technical field
The present invention relates to employed a kind of material of a kind of ferrite magnetic material industry and manufacturing process and refer in particular to a kind of low-temperature coefficient permanent magnet ferrite material and manufacture method.
Background technology
Permanent-magnet ferrite material is that a kind of functional material range of application is very extensive.Along with development of science and technology, also more and more higher to the requirement of magnetic material.Increasing occasion, in the motor and all kinds of magnetron magnetic system as electric motor with large torque, electric motor of automobile, high and cold, deep ocean work, because external environment condition is more abominable, there are influences such as high temperature, low temperature, vibrations, impact, dc electromagnetic field interference, often need existing high magnetic field intensity, the magnetic material that good stable and reliability are arranged again has lower temperature coefficient in high performance requirement simultaneously.
In the disclosed at present permanent-magnet ferrite material patent, all added expensive La, Co, Bi element etc. in the high performance material prescription, the cost of product is very high, but performance does not but improve than the present invention is significant, and remanent magnetism temperature coefficient α BrWith HCJ temperature coefficient α HcjBe starkly lower than index of the present invention.As a kind of patent No. is the crystallite-cladded sintered magnet of CN200410099083.0 and manufacture method thereof, motor, bonded permanent magnet, its technology is: described magnet has a Curie temperature, comprise the Hxagonal ferrite principal phase that contains A, M, R and Fe, and has the molecular formula of following feature a: A1-XMxFe12-yRyO19, wherein, A represents at least a element among Sr, Ba, the Ca; The M representative is selected from least a element among rare earth element and the Bi, and must contain La; R represents at least a element among Co, Mn, Zn, Ge, the As, wherein must contain Co, it is characterized in that may further comprise the steps: a, batching: take by weighing and contain the pre-imitation frosted glass that molecular formula is AFe12O19 in the preparation method, and add the some kinds of compounds and the additive of required element in quality proportioning mode, the mixture of gained is ground, be not more than 1.20 μ m at the most until the particle mean size of crystal grain; B, moulding and sintering: the slurry of above-mentioned steps gained is carried out the water content adjustment, adjust its concentration to 55～85wt%, pressing under magnetic field then, and formed body carried out sintering; M and R ion are solid-solubilized on the crystal boundary crystal grain are formed parcel behind the sintering, or trace enters crystal grain inside.Magnet powder, sintered magnet that a kind of for another example patent No. is CN98801371.1, its manufacturing process, bonded permanent magnet, motor and magnetic recording media, his magnet powder, comprise that (wherein A represents Sr, Ba or Ca to the Hxagonal ferrite principal phase that contains A, Co and R, R represents at least a element in the set that is selected from rare earth element (comprising Y) and Bi composition), wherein, described magnet powder has at least two different Curie temperature, described two different Curie temperature are present in 400～480 ℃ the scope, its with the absolute value of difference be 5 ℃ or higher.The temperature coefficient of these two kinds of inventions does not all have temperature coefficient of the present invention low, and they have all added elements such as expensive La, Co, Bi in addition, and production cost is high.
Summary of the invention
Elements such as La, the Co that the present invention mainly is higher at the existing in prior technology temperature coefficient and interpolation is expensive, Bi, problems such as production cost height, a kind of elements such as La, Co, Bi that do not add are provided, have had lower temperature coefficient and than the low-temperature coefficient permanent magnet ferrite material and the manufacture method of high magnetic characteristics.
The present invention has also solved a large amount of energy of prior art consumption simultaneously, and the designing requirement of agglomerating plant than problems such as height, has been saved a large amount of energy, makes the designing requirement of agglomerating plant also reduce, and has further reduced production cost.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: low-temperature coefficient permanent magnet ferrite material, its principal phase are the magneto-plumbite type structures, and its chemical formula is: Sr 1-xA xFe 12-yM yO 19, wherein: A=Ca, Na, Ba, Pb, 1～2 kind of K, x=0.05～0.5; M=Al, Cr, Zn 2/3V 1/3, Zn 2/3Nb 1/3, Cu 2/3V 1/3, Cu 2/3Nb 1/3, Zn 1/2Ge 1/2, Zn 1/2Si 1/2, Cu 1/2Ga 1/2, Cu 1/2Si 1/21～3 kind, y=0.01～0.3.
As preferably, described Sr 1-xA xFe 12-yM yO 19In, be 5.2～6.2 (Fe+M) with (Sr+A) mol ratio.
As preferably, described chemical formula Sr 1-xA xFe 12-yM yO 19, wherein: A=Ca, 1～2 kind of Ba, x=0.05～0.5; M=Al, Cr, Cu 2/3V 1/3, Cu 1/2Si 1/21～3 kind, y=0.01～0.3.
According to ferritic theory to SrFe 12O 19Carrying out the compound replacement of ion is to improve the effective ways that prescription improves performance at present.Adopt two or more ion to replace in the M type ferrite the not ion of isomorphous position, the magnetic property that can improve material has obtained application.
Sr at first replaces 2+Ion is with Sr 2+Ionic radius 0.127nm is close Ba 2+, Pb 2+, Ca 2+, Na +, K +Radius is respectively 0.143nm, 0.132nm, 0.106nm, 0.133nm, 0.098nm.Therefore the ion of these elements Sr that can partly or entirely replace 2+Ion.Find in the experiment that the Ba ion can replace the Sr ion fully and occupy specific lattice position, dissolving is mutually dissolved each other fully between Ba ion and Sr ion solid phase, generates strontium, the titanate solid solution ferrite of M type.Because saturated going out of the magnetic intensity Ms of Ba is than Sr height, therefore very favourable to improving remanent magnetism Br, strontium, titanate solid solution ferrite have the effect of stable Magnetoplumbate-type crystal structure in addition, within the specific limits Hc are not caused big influence, need find the best replacement amount of Sr.
Replacement Fe 3+Ion be it is generally acknowledged, 3d transition group ion and ionic radius are the ion of the 0.06～0.10nm Fe that all can partly or entirely replace 3+Al 3+And Cr 3+Be non magnetic ion, its ionic radius is respectively 0.057nm, 0.062nm.Cr 3+The radius of ion and Fe 3+(0.065nm) more approaching.Al 3+, Ga 3+, Cr 3+In the influence of plasma replacement to the ferromagnetic resonance field, Al 3+Replacement can obtain higher coercivity H j.The replacement of these ions causes the variation of magnetic moment and Curie temperature, Al 3+Preferentially enter the brilliant position of 2a, enter the brilliant position of 12k then; Ga 3+Preferentially enter brilliant position of 12k and 4f 1Brilliant position.Replacement mainly is to increase single domain critical dimension Rc, thereby causes under the condition of identical particle size, Hcj increases.Al 3+, Ga 3+, Cr 3+Replacement Fe 3+Except increasing Rc, also can increase magnetocrystalline anisotropy field H ABecause of H A=2K 1/ μ 0Ms, H AIncrease mainly be because reducing of Ms and K 1Variation does not cause very much.The theoretical method that M type permanent-magnet ferrite temperature characterisitic is played the improvement effect is (M 1 2++ M 2 4+) replacement 2Fe 3+(2M 1 2++ M 2 5+) replacement 3Fe 3+
The preparation method of low-temperature coefficient permanent magnet ferrite material, this method may further comprise the steps:
1) raw material mixing and ball milling: use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CuO, V 2O 5Be raw material, according to Fe 2O 3Be 70～88mol%, SrCO 3Be 9～20mol%, BaCO 3Be 1.5～4.5mol%, CuO is 1～3.5mol%, V 2O 5Be the ratio of 0.5～2mol%, raw material is added in the ball mill, and add steel ball and water, one time ball milling mixes;
2) once sintered: with the material behind ball milling dewater to water content below 10wt%, make particle, the stove of putting into oxidizing atmosphere carries out once sintered, once sintered temperature is 1240～1280 ℃, is incubated to cool off with stove after 0.5～3 hour;
3) add the additive secondary ball milling; Primary sintered material is carried out adding additive after the dry type fragmentation, and additive is CaCO 3Or K 2CO 3Or Na 2CO 3Or PbO, SiO 2Or GeO 2, Al 2O 3Or Ga 2O 3Or Cr 2O 3, SrSO 4Or SrCO 3, H 3BO 3, adding kind is 1～5 kind, its degree is 0.01～5wt%; The additive of primary sintered material and corresponding proportion is put into ball mill, and add steel ball and water; Carry out secondary ball milling;
4) moulding and double sintering: with the secondary ball milling slurry dewatering to water content at 30～40wt%, compression moulding in the time of externally-applied magnetic field; The stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1180～1240 ℃, is incubated and cools to room temperature with the furnace after 0.5～3 hour.
As preferably, in the described first step, the raw material wet-mixed is according to material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling 1～5 hour.
As preferably, in described second step, the granular size of making behind ball milling is Φ 5～10 μ m.
As preferably, in described the 3rd step, primary sintered material is carried out dry type be crushed to particle mean size≤3 μ m.
As preferably, in described the 3rd step, secondary ball milling is in material: ball: the ratio of water=1: 5～7: 1.2 adds steel ball and water carries out, and ball milling to slip granularity is the about 0.85 μ m of average diameter and becomes normal distribution, and the integration number 〉=95% o'clock discharging of 0.5～1.4 μ m.
As preferably, in described the 4th step, moulding is the alignment magnetic field that the slip after the dehydration adds 650～950kA/m, adds the pressure compression moulding of 300～600kgf/cm2 simultaneously.
Therefore, it is reasonable that the present invention has technology, has lower temperature coefficient and higher magnetic property, and the stability of material and reliability improve, and range of application enlarges; Do not make the cost of raw material reduce owing to wherein do not contain La, Co, Bi element.Because once sintered temperature and double sintering temperature reduce, and have saved a large amount of energy, make the designing requirement of agglomerating plant also reduce, and have further reduced production cost.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment one:
Use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CaCO 3, SiO 2, Al 2O 3, CuO, V 2O 5Be raw material.Various raw material particle mean sizes all＜3 μ m.
1. according to Fe 2O 3Be 83.2mol%, SrCO 3Be 12mol%, BaCO 3Be 2.5mol%, CuO is 1.5mol%, V 2O 5Calculate and take by weighing the raw material of corresponding weight for 0.8mol%.
2. the raw material that takes by weighing is packed in the ball mill, and by weight material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling discharging after 3 hours.When slip dewaters to water content 6～10wt%, make the particle of Φ 5～10 μ m.
3. Φ 5～10 μ m particulate material of making are put into air furnace and carried out once sinteredly, sintering temperature is 1250 ℃, is incubated to cool off with stove after 1 hour.Oxygen atmosphere needs abundance during sintering.Fe in the primary sintered material that obtains 2+Content＜0.11wt%.
4. primary sintered material is carried out the dry type corase grind earlier and be broken to particle mean size≤3 μ m, add CaCO then 30.6wt%, SiO 20.25wt%, Al 2O 30.4wt%.CaCO 3, SiO 2, Al 2O 3The particle mean size of particle all≤3 μ m.
5. will roughly grind to primary sintered material and the described additive of step 4 of particle mean size≤3 μ m and put into ball mill, and by weight material: ball: the ratio of water=1: 6: 1.2 adds steel ball and water, secondary ball milling discharging after 7 hours.In the mechanical milling process ball mill is cooled off, keep slurry temperature below 30 ℃.The slip pH value that obtains is less than 9; The slip granularity that obtains, the about 0.85 μ m of average diameter also becomes normal distribution, and integration number 〉=95% of 0.5～1.4 μ m.
6. with the secondary ball milling slurry dewatering to water content at 30～40wt%, add the alignment magnetic field of 800kA/m then, moulding pressure is 500kgf/cm 2, compression moulding.Make the density of moulded blank reach 3.3～3.4g/cm 3
7. the stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1210 ℃, is incubated and cools to room temperature with the furnace after 1.5 hours.
The magnetic property that the sample that obtains is measured after mill processing: remanent magnetism Br (mT), coercivity H b (kA/m), HCJ Hcj (kA/m), maximum magnetic energy product (BH) max (kJ/m 3), remanent magnetism temperature coefficient α Br(%K -1), HCJ temperature coefficient α Hcj(%K -1) as table 1.
The magnetic parameter of table 1 example one magnet
Remanent magnetism Br (mT) Coercivity H b (kA/m) HCJ Hcj (kA/m) Maximum magnetic energy product (BH) max (kJ/m 3) Remanent magnetism temperature coefficient α Br (％K -1) HCJ temperature coefficient α Hcj(％K -1)
420 310.8 333.1 34.1 -0.14 0.15
Embodiment two:
Use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CaCO 3, SiO 2, Al 2O 3, CuO, V 2O 5Be raw material.Various raw material particle mean sizes all＜3 μ m.
1. according to Fe 2O 3Be 81.2mol%, SrO is 11mol%, and BaO is 3.5mol%, and CuO is 2.2mol%, V 2O 5Calculate and take by weighing the raw material of corresponding weight for 1.1mol%.
2. the raw material that takes by weighing is packed in the ball mill, and by weight material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling discharging after 5 hours.When slip dewaters to water content 6～10wt%, make the particle of Φ 5～10 μ m.
3. Φ 5～10 μ m particulate material of making are put into air furnace and carried out once sinteredly, sintering temperature is 1240 ℃, is incubated to cool off with stove after 3 hours.Oxygen atmosphere needs abundance during sintering.Fe in the primary sintered material that obtains 2+Content＜0.11wt%.
4. primary sintered material is carried out the dry type corase grind earlier and be broken to particle mean size≤3 μ m, add CaCO then 30.7wt%, SiO 20.30wt%, Al 2O 30.5wt%.CaCO 3, SiO 2, Al 2O 3The particle mean size of particle all≤3 μ m.
5. will roughly grind to primary sintered material and the described additive of step 4 of particle mean size≤3 μ m and put into ball mill, and by weight material: ball: the ratio of water=1: 5: 1.2 adds steel ball and water, secondary ball milling discharging after 7 hours.In the mechanical milling process ball mill is cooled off, keep slurry temperature below 30 ℃.The slip pH value that obtains is less than 9; The slip granularity that obtains, the about 0.85 μ m of average diameter also becomes normal distribution, and integration number 〉=95% of 0.5～1.4 μ m.
6. with the secondary ball milling slurry dewatering to water content at 30～40wt%, add the alignment magnetic field of 650kA/m then, moulding pressure is 300kgf/cm 2, compression moulding.Make the density of moulded blank reach 3.3～3.4g/cm 3
7. the stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1180 ℃, is incubated and cools to room temperature with the furnace after 3 hours.
The magnetic property that the sample that obtains is measured after mill processing: remanent magnetism Br (mT), coercivity H b (kA/m), HCJ Hcj (kA/m), maximum magnetic energy product (BH) max (kJ/m 3), remanent magnetism temperature coefficient α Br(%K -1), HCJ temperature coefficient α Hcj(%K -1) as table 2.
The magnetic parameter of table 2 example two magnets
Remanent magnetism Br (mT) Coercivity H b (kA/m) HCJ Hcj (kA/m) Maximum magnetic energy product (BH) max (kJ/m 3) Remanent magnetism temperature coefficient α Br (％K -1) HCJ temperature coefficient α Hcj(％K -1)
423 305.2 320.3 34.5 -0.11 0.11
Embodiment three:
Use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CaCO 3, SiO 2, Al 2O 3, CuO, V 2O 5Be raw material.Various raw material particle mean sizes all＜3 μ m.
1. according to Fe 2O 3Be 80.1mol%, SrO is 10.6mol%, and BaO is 4.5mol%, and CuO is 3.2mol%, V 2O 5Calculate and take by weighing the raw material of corresponding weight for 1.61mol%.
2. the raw material that takes by weighing is packed in the ball mill, and by weight material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling discharging after 1 hour.When slip dewaters to water content 6～10wt%, make the particle of Φ 5～10 μ m.
3. Φ 5～10 μ m particulate material of making are put into air furnace and carried out once sinteredly, sintering temperature is 1280 ℃, is incubated to cool off with stove after 0.5 hour.Oxygen atmosphere needs abundance during sintering.Fe in the primary sintered material that obtains 2+Content＜0.11wt%.
4. primary sintered material is carried out the dry type corase grind earlier and be broken to particle mean size≤3 μ m, add CaCO then 30.5wt%, SiO 20.20wt%, Al 2O 30.3wt%.CaCO 3, SiO 2, Al 2O 3The particle mean size of particle all≤3 μ m.
5. will roughly grind to primary sintered material and the described additive of step 4 of particle mean size≤3 μ m and put into ball mill, and by weight material: ball: water=l: 7: 1.2 ratio adds steel ball and water, secondary ball milling discharging after 7 hours.In the mechanical milling process ball mill is cooled off, keep slurry temperature below 30 ℃.The slip pH value that obtains is less than 9; The slip granularity that obtains, the about 0.85 μ m of average diameter also becomes normal distribution, and integration number 〉=95% of 0.5～1.4 μ m.
6. with the secondary ball milling slurry dewatering to water content at 30～40wt%, add the alignment magnetic field of 9500kA/m then, moulding pressure is 600kgf/cm 2, compression moulding.Make the density of moulded blank reach 3.3～3.4g/cm 3
7. the stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1240 ℃, is incubated and cools to room temperature with the furnace after 0.5 hour.
The magnetic property that the sample that obtains is measured after mill processing: remanent magnetism Br (mT), coercivity H b (kA/m), HCJ Hcj (kA/m), maximum magnetic energy product (BH) max (kJ/m 3), remanent magnetism temperature coefficient α Br(%K -1), HCJ temperature coefficient α Hcj(%K -1) as table 3.
The magnetic parameter of table 3 example three magnets
Remanent magnetism Br (mT) Coercivity H b (kA/m) HCJ Hcj (kA/m) Maximum magnetic energy product (BH) max (kJ/m 3) Remanent magnetism temperature coefficient α Br (％K -1) HCJ temperature coefficient α Hcj(％K -1)
430 280.5 291.2 35.0 -0.06 0.08
Embodiment four:
Use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CaCO 3, Al 2O 3, CuO, V 2O 5Be raw material.Various raw material particle mean sizes all＜3 μ m.
1. be 88mol% according to Fe2O3, SrCO3 is 9mol%, and BaCO3 is 1.5mol%, and CuO is 1mol%, and V2O5 is the raw material that 0.5mol% calculated and took by weighing corresponding weight.
2. the raw material that takes by weighing is packed in the ball mill, and by weight material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling discharging after 3 hours.When slip dewaters to water content 6～10wt%, make the particle of Φ 5～10 μ m.
3. Φ 5～10 μ m particulate material of making are put into air furnace and carried out once sinteredly, sintering temperature is 1250 ℃, is incubated to cool off with stove after 1 hour.Oxygen atmosphere needs abundance during sintering.Fe in the primary sintered material that obtains 2+Content＜0.11wt%.
4. primary sintered material is carried out the dry type corase grind earlier and be broken to particle mean size≤3 μ m, add CaCO then 30.6wt%, Al 2O 30.4wt%.CaCO 3, Al 2O 3The particle mean size of particle all≤3 μ m.
5. will roughly grind to primary sintered material and the described additive of step 4 of particle mean size≤3 μ m and put into ball mill, and by weight material: ball: the ratio of water=1: 6: 1.2 adds steel ball and water, secondary ball milling discharging after 7 hours.In the mechanical milling process ball mill is cooled off, keep slurry temperature below 30 ℃.The slip pH value that obtains is less than 9; The slip granularity that obtains, the about 0.85 μ m of average diameter also becomes normal distribution, and integration number 〉=95% of 0.5～1.4 μ m.
6. with the secondary ball milling slurry dewatering to water content at 30～40wt%, add the alignment magnetic field of 800kA/m then, moulding pressure is 500kgf/cm 2, compression moulding.Make the density of moulded blank reach 3.3～3.4g/cm 3
7. the stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1210 ℃, is incubated and cools to room temperature with the furnace after 1.5 hours.
The magnetic property that the sample that obtains is measured after mill processing: remanent magnetism Br (mT), coercivity H b (kA/m), HCJ Hcj (kA/m), maximum magnetic energy product (BH) max (kJ/m 3), remanent magnetism temperature coefficient α Br(%K -1), HCJ temperature coefficient α Hcj(%K -1) as table 4.
The magnetic parameter of table 4 example four magnets
Remanent magnetism Br (mT) Coercivity H b (kA/m) HCJ Hcj (kA/m) Maximum magnetic energy product (BH) max (kJ/m 3) Remanent magnetism temperature coefficient α Br (％K -1) HCJ temperature coefficient α Hcj(％K -1)
380 159 199 27 -0.04 0.05
Embodiment five:
Use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CaCO 3, SiO 2, Al 2O 3, CuO, Cr 2O 3, SrSO 4, SrCO 3, H 3BO 3, V 2O 5Be raw material.Various raw material particle mean sizes all＜3 μ m.
1. according to Fe 2O 3Be 83.2mol%, SrCO 3Be 12mol%, BaCO 3Be 2.5mol%, CuO is 1.5mol%, V 2O 5Calculate and take by weighing the raw material of corresponding weight for 0.8mol%.
2. the raw material that takes by weighing is packed in the ball mill, and by weight material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling discharging after 3 hours.When slip dewaters to water content 6～10wt%, make the particle of Φ 5～10 μ m.
3. Φ 5～10 μ m particulate material of making are put into air furnace and carried out once sinteredly, sintering temperature is 1250 ℃, is incubated to cool off with stove after 1 hour.Oxygen atmosphere needs abundance during sintering.Fe in the primary sintered material that obtains 2+Content＜0.11wt%.
4. primary sintered material is carried out the dry type corase grind earlier and be broken to particle mean size≤3 μ m, add CaCO then 30.6wt%, SiO 20.25wt%, Al 2O 30.4wt%, Cr 2O 30.3wt%, SrSO 40.2wt%, SrCO 30.1wt%, H 3BO 30.1wt%.CaCO 3, SiO 2, Al 2O 3, Cr 2O 3, SrSO 4, SrCO 3, H 3BO 3The particle mean size of particle all≤3 μ m.
5. will roughly grind to primary sintered material and the described additive of step 4 of particle mean size≤3 μ m and put into ball mill, and by weight material: ball: the ratio of water=1: 6: 1.2 adds steel ball and water, secondary ball milling discharging after 7 hours.In the mechanical milling process ball mill is cooled off, keep slurry temperature below 30 ℃.The slip pH value that obtains is less than 9; The slip granularity that obtains, the about 0.85 μ m of average diameter also becomes normal distribution, and integration number 〉=95% of 0.5～1.4 μ m.
6. with the secondary ball milling slurry dewatering to water content at 30～40wt%, add the alignment magnetic field of 800kA/m then, moulding pressure is 500kgf/cm 2, compression moulding.Make the density of moulded blank reach 3.3～3.4g/cm 3
7. the stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1210 ℃, is incubated and cools to room temperature with the furnace after 1.5 hours.
The magnetic property that the sample that obtains is measured after mill processing: remanent magnetism Br (mT), coercivity H b (kA/m), HCJ Hcj (kA/m), maximum magnetic energy product (BH) max (kJ/m 3), remanent magnetism temperature coefficient α Br(%K -1), HCJ temperature coefficient α Hcj(%K -1) as table 5.
The magnetic parameter of table 5 example five magnets
Remanent magnetism Br (mT) Coercivity H b (kA/m) HCJ Hcj (kA/m) Maximum magnetic energy product (BH) max (kJ/m 3) Remanent magnetism temperature coefficient α Br (％K -1) HCJ temperature coefficient α Hcj(％K -1)
440 319 335 36 -0.15 0.15
Draw from above embodiment, the magnetic property of magnet material of the present invention is as follows: remanent magnetism Br=380～440mT; B, magnetic induction coercivity H b=159～319kA/m; C, HCJ Hcj=199～335kA/m; D, magnetic energy product [BH] max=27～36kJ/m 3E, remanent magnetism temperature coefficient α Br〉=-0.15%K -1F, HCJ temperature coefficient α Hcj≤ 0.15%K -1
Specific embodiment described herein only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.

Claims (9)

1. low-temperature coefficient permanent magnet ferrite material, its principal phase is the magneto-plumbite type structure, its chemical formula is: Sr 1-xA xFe 12-yM yO 19, wherein: A=Ca, Na, Ba, Pb, 1～2 kind of K, x=0.05～0.5; M=Al, Cr, Zn 2/3V 1/3, Zn 2/3Nb 1/3, Cu 2/3V 1/3, Cu 2/3Nb 1/3, Zn 1/2Ge 1/2, Zn 1/2Si 1/2, Cu 1/2Ga 1/2, Cu 1/2Si 1/21～3 kind, y=0.01～0.3.
2. low-temperature coefficient permanent magnet ferrite material according to claim 1 is characterized in that: described Sr 1-xA xFe 12-yM yO 19In, be 5.2～6.2 (Fe+M) with (Sr+A) mol ratio.
3. low-temperature coefficient permanent magnet ferrite material according to claim 1 is characterized in that: described chemical formula Sr 1-xA xFe 12-yM yO 19, wherein: A=Ca, 1～2 kind of Ba, x=0.05～0.5; M=Al, Cr, Cu 2/3V 1/3, Cu 1/2Si 1/21～3 kind, y=0.01～0.3.
4. the preparation method of a low-temperature coefficient permanent magnet ferrite material, this method may further comprise the steps:
1) raw material mixing and ball milling: use commercially pure Fe 2O 3, SrCO 3, BaCO 3, CuO, V 2O 5Be raw material, according to Fe 2O 3Be 70～88mol%, SrCO 3Be 9～20mol%, BaCO 3Be 1.5～4.5mol%, CuO is 1～3.5mol%, V 2O 5Be the ratio of 0.5～2mol%, raw material is added in the ball mill, and add steel ball and water, one time ball milling mixes;
2) once sintered: with the material behind ball milling dewater to water content below 10wt%, make particle, the stove of putting into oxidizing atmosphere carries out once sintered, once sintered temperature is 1240～1280 ℃, is incubated to cool off with stove after 0.5～3 hour;
3) add the additive secondary ball milling; Primary sintered material is carried out adding additive after the dry type fragmentation, and additive is CaCO 3, SiO 2, Al 2O 3, Cr 2O 3, SrSO 4, SrCO 3, H 3BO 3, adding kind is 1～5 kind; The additive of primary sintered material and corresponding proportion is put into ball mill, and add steel ball and water; Carry out secondary ball milling;
4) moulding and double sintering: with the secondary ball milling slurry dewatering to water content at 30～40wt%, compression moulding in the time of externally-applied magnetic field; The stove of the blank of compression moulding being put into oxidizing atmosphere carries out double sintering, and the double sintering temperature is 1180～1240 ℃, is incubated and cools to room temperature with the furnace after 0.5～3 hour.
5. the preparation method of low-temperature coefficient permanent magnet ferrite material according to claim 4 is characterized in that: in the described first step, the raw material wet-mixed is according to material: ball: the ratio of water=1: 3: 1.2 adds steel ball and water, ball milling 1～5 hour.
6. the preparation method of low-temperature coefficient permanent magnet ferrite material according to claim 4 is characterized in that: in described second step, the granular size of making behind ball milling is Φ 5～10 μ m.
7. the preparation method of low-temperature coefficient permanent magnet ferrite material according to claim 4 is characterized in that: in described the 3rd step, primary sintered material is carried out dry type be crushed to particle mean size≤3 μ m.
8. the preparation method of low-temperature coefficient permanent magnet ferrite material according to claim 4, it is characterized in that: in described the 3rd step, secondary ball milling is in material: ball: the ratio of water=1: 5～7: 1.2 adds steel ball and water carries out, ball milling to slip granularity is the about 0.85 μ m of average diameter and becomes normal distribution, and the integration number 〉=95% o'clock discharging of 0.5～1.4 μ m.
9. the preparation method of low-temperature coefficient permanent magnet ferrite material according to claim 4 is characterized in that: in described the 4th step, moulding is the alignment magnetic field that the slip after the dehydration adds 650～950kA/m, adds 300～600kgf/cm simultaneously 2Pressure compression moulding.
CNA2007101276076A 2006-06-19 2007-06-18 Low-temperature coefficient permanent magnet ferrite material and its production method Pending CN101106001A (en)

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