CN107129292B - One kind prepares the ferritic ionic association alternatives of high-performance MnZn - Google Patents
One kind prepares the ferritic ionic association alternatives of high-performance MnZn Download PDFInfo
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Abstract
The present invention provides one kind to prepare the ferritic ionic association alternatives of high-performance MnZn, mainly by adding the elements such as In, Co, Ca, Ti, lifts the ferritic high-gradient magnetism energy of MnZn.Additive amount is：In2O3：1000~4000ppm, CoO：500~2000ppm, CaO：1000~3000ppm, TiO2：1000~2500ppm, SiO2：0~2000ppm.The novelty of the present invention, which is to combine by properly mixed polybasic ion, to be substituted, influence and interionic interaction using each ion pair principal component, the MnZn Ferrite Materials being prepared saturation flux density at 25 DEG C is higher than 530mT, and 440mT, Applicable temperature scope are higher than at 100 DEG C>150 DEG C, and the ferritic magnetic conductivities of MnZn under high frequency can be improved, power attenuation is reduced, improves the temperature stability of magnetic property.
Description
Technical field
The present invention relates to prepare the ferritic ionic association alternatives of high-performance MnZn, mainly by add In, Co,
The elements such as Ca, Ti, belong to technical field of magnetic materials.
Background technology
Soft magnetic ferrite as a kind of important component material, be made predominantly into magnetic core be used for various inductors, transformer,
The manufacture of wave filter and choke coil, is widely used in the fields such as modern electric and electronic information, such as computer and its external equipment, does
Public automation equipment, digital communication and artificial traffic equipment, internet, household electrical appliance, electromagnetic compatibility equipment, green illumination dress
Put, industrial automation and automobile, Aeronautics and Astronautics and military field.Relative to other soft magnetic materials, the advantage of soft magnetic ferrite exists
Of a relatively high in resistivity, which suppress the generation of vortex, ferrite is can apply to high frequency field；It is easy to using ceramic process
A variety of shape and size are made；Chemical characteristic is stable, non-corrosive；Relatively low manufacture cost.
With industry and the continuous progress of science and technology, while ensureing excellent magnetic energy, electronic component is more becoming
In high frequency, miniaturization, it is desirable to lower working loss, broader use temperature range.In original MnZn ferrite formulations
On the basis of, the performance of material can be significantly improved with substituting by suitable ion doping, studies the iron oxygen with production at present
Body material, all contains a certain amount of additive component mostly.But for the addition of polybasic ion, study at present it is relatively fewer,
For the interaction between added ion, certain research is also lacked.The proportioning of suitable ionic species and additive amount can
To improve the magnetic property of MnZn Ferrite Materials, improperly addition can reduce the performance of original material.So pass through polybasic ion
Joint method of substitution must be furtherd investigate to improve the ferritic performance numbers of MnZn.
The content of the invention
It is an object of the invention to provide one kind to prepare the ferritic ionic association alternatives of high-performance MnZn, main logical
The elements such as addition In, Co, Ca, Ti are crossed, lift the magnetic property under material high-frequency work.
Technical scheme is as follows：
The invention discloses one kind first to prepare the ferritic ionic association alternatives of high-performance MnZn, it includes as follows
Step：
(1) Primary batching system
Weigh principal component；
(2) ball millings
Principal component is uniformly mixed, the principal component weighed is put into ball mill, 3~10h of ball milling, obtains a ball milling powder
Material；
(3) it is once sintered
Powder obtained by first time ball milling is warming up to 800~1000 with the speed of 200~300 DEG C/h in air atmosphere
DEG C, 1~3h is kept the temperature, furnace cooling obtains once sintered powder；
(4) second batch
Addition includes the accessory ingredient of In, Co, Ca, Si, Ti element in once sintered powder, based on the total amount of principal component
Accessory ingredient constituent content is：In：800~3000ppm, Co：300~1500ppm, Ca：500~2000ppm, Ti：800~
2000ppm, Si：0~15000ppm, the total amount of adding of accessory ingredient are no more than the 3wt% of sintering powder；
(5) secondary ball milling
Ball mill will be put into after the powder obtained after second batch uniformly mixing, be milled to 0.8~2 μm of powder particle size, obtains
To secondary ball milling powder；
(6) it is granulated
According to the powder gross weight after secondary ball milling, polyvinyl alcohol water solution is added, the addition of wherein polyvinyl alcohol is
3wt%~10wt% of powder gross mass, particle is ground up, sieved into after first precompressed；
(7) it is compressing
Polyvinyl alcohol water solution is added to being granulated in the particulate material of gained, wherein the addition of polyvinyl alcohol is total for particulate material
3wt%~10wt% of quality, compressing is green product, and green density will reach 2.6~3.6g/cm3；
(8) double sintering
Sintering temperature is 1200~1400 DEG C, 2~14h of insulation, makes equilibrium oxygen partial pres-sure by adding nitrogen in sintering process
Below 4%, cooling comes out of the stove to obtain MnZn soft magnetic ferrite material for control.
Preferably, the principal component is：MnaZnbFecO4, wherein a=0.6~0.8, b=0.1~0.3, c=3-a-
b。
Preferably, the addition form of In, Co, Ca, Si, Ti accessory ingredient be In, Co, Ca, Si, Ti oxide,
Carbonate, silicate and the organic compound containing the element.
Preferably, when the oxide form addition with In, Co, Ca, Si, Ti, the additive amount of each accessory ingredient is as follows：
In2O3：1000~4000ppm, CoO：500~2000ppm, CaO：1000~3000ppm, TiO2：1000~2500ppm,
SiO2：0~2000ppm.
The invention also discloses high-performance MnZn ferrites prepared by a kind of the method.
The main function mechanism of the accessory ingredient of the present invention is as follows：
CaO and SiO2Substantially do not enter in magnetic principal phase, mainly act on grain boundary portion, form CaSiO3、Ca3Si2O7、
Ca2ZnSi2O7Deng high resistance phase, Si elements often are included wherein in raw material iron oxide red, using stainless steel ball ball milling when also has
A small amount of Si elements enter in powder, so SiO2Accessory ingredient, CaO and SiO are added as choosing2Addition mainly to crystal boundary and crystal grain
Resistivity has an impact, and in general, can increase grain boundary resistivity so as to increase the resistivity of whole material so that the whirlpool of material
Stream loss can be reduced substantially；
In2O3It can enter among principal phase solid solution tissue, be substituted between original tetrahedral interstice or octahedron with CoO
Metal ion in gap, in addition to having an impact to the saturation induction density of ferrimagnetism, appropriate additive can also adjust
The magnetocrystalline anisotropy constant and magnetostriction coefficient of material entirety, so as to adjust the temperature characterisitic of material.Part high-valence state from
Son replaces original low price ion, due to keep overall electroneutral and stoichiometric ratio, can also become ferric ion
For ferrous ion, the resistivity of principal phase can also be had an impact；
TiO2Addition effect be to influence the growth of crystal microscopic structure, influence final grain size and uniformity, cause
Density, gas cell distribution, whether there is abnormal grain growth, crystal ingedient distribution and thickness etc..
The beneficial effects of the invention are as follows：
High frequency MnZn Ferrite Materials for being widely used in various components, it is often desirable that it can be in broader temperature
In the range of there is very low power attenuation, the present invention is added by adding In, Co, Ca, Ti element in second batch by difference
Add the joint replacement and the mutual mechanism of action of ion of agent ion, and the reasonable control on sintering process, obtain
Product compares material prepared by same process, is obtained for optimization in terms of magnetic property and power attenuation, at the same material using warm
Degree and frequency range are wider.The MnZn Ferrite Materials being prepared by suitable raw material ratio and process optimization are at 25 DEG C
Lower saturation flux density is higher than 530mT, and 440mT, Applicable temperature scope are higher than at 100 DEG C>150 DEG C, and can improve
The ferritic magnetic conductivities of MnZn under the high frequency condition of 0.1~5MHz, reduce power attenuation, improve the temperature stability of magnetic property.
Embodiment
It is further to the MnZn Ferrite Materials prepared by the present invention and preparation process below by specific case study on implementation
Illustrate.
Case study on implementation 1：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：In2O3：3000ppm, CoO：1000ppm, CaO：
2000ppm, TiO2：2000ppm, SiO2：1000ppm simultaneously adds suitable deionized water, secondary ball milling 4h, obtain particle diameter 0.7~
2 μm of powder granule, and particle diameter distribution Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, add poly-
Vinyl alcohol is granulated, and sieving obtains manganese-zinc ferrite powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and burns
Knot, sintering temperature are 1300 DEG C, insulation 3h, make equilibrium oxygen partial pres-sure control below 4% by adding nitrogen in sintering process, cold
But come out of the stove to obtain MnZn soft magnetic ferrite material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that case study on implementation 1 is prepared is 535mT,
Saturation induction density at 100 DEG C is 440mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
165kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 235kWm-3, the initial permeability of material is
1200, Curie temperature is 290 DEG C.
Case study on implementation 2：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：In2O3：3000ppm, CoO：1000ppm, CaO：
2500ppm, TiO2：2000ppm, SiO2：500ppm simultaneously adds suitable deionized water, and secondary ball milling 4h, obtains particle diameter 0.7~2
μm powder granule, and particle diameter distribution Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, poly- second is added
Enol is granulated, and sieving obtains manganese-zinc ferrite powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and burns
Knot, sintering temperature are 1300 DEG C, insulation 3h, make equilibrium oxygen partial pres-sure control below 4% by adding nitrogen in sintering process, cold
But come out of the stove to obtain MnZn soft magnetic ferrite material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that case study on implementation 2 is prepared is 540mT,
Saturation induction density at 100 DEG C is 445mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
170kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 250kWm-3, the initial permeability of material is
1250, Curie temperature is 285 DEG C.
Case study on implementation 3：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：In2O3：2500ppm, CoO：1500ppm, CaO：
2000ppm, TiO2：1500ppm, SiO2：1000ppm simultaneously adds suitable deionized water, secondary ball milling 4h, obtain particle diameter 0.7~
2 μm of powder granule, and particle diameter distribution Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, add poly-
Vinyl alcohol is granulated, and sieving obtains manganese-zinc ferrite powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and burns
Knot, sintering temperature are 1300 DEG C, insulation 3h, make equilibrium oxygen partial pres-sure control below 4% by adding nitrogen in sintering process, cold
But come out of the stove to obtain MnZn soft magnetic ferrite material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that case study on implementation 3 is prepared is 530mT,
Saturation induction density at 100 DEG C is 440mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
180kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 265kWm-3, the initial permeability of material is
1400, Curie temperature is 280 DEG C.
Comparison cases 1：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：In2O3：3000ppm, CoO：1000ppm, TiO2：
2000ppm simultaneously adds suitable deionized water, and secondary ball milling 4h, obtains the powder granule of 0.7~2 μm of particle diameter, and particle diameter distribution
Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, add polyvinyl alcohol and be granulated, sieving obtains MnZn iron
Ferromagnetic powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and sinters, sintering temperature is 1300 DEG C, insulation
3h, makes equilibrium oxygen partial pres-sure control cooling comes out of the stove to obtain MnZn soft magnetic ferrites below 4% in sintering process by adding nitrogen
Material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that comparison cases 1 are prepared is 530mT,
Saturation induction density at 100 DEG C is 420mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
420kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 680kWm-3, the initial permeability of material is
1200, Curie temperature is 260 DEG C.
Comparison cases 2：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：In2O3：3000ppm, CoO：1000ppm, CaO：
2500ppm, SiO2：500ppm simultaneously adds suitable deionized water, and secondary ball milling 4h, obtains the powder of 0.7~2 μm of particle diameter
Grain, and particle diameter distribution Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, add polyvinyl alcohol and be granulated,
Sieving obtains manganese-zinc ferrite powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and sinters, sintering temperature
For 1300 DEG C, 3h is kept the temperature, makes equilibrium oxygen partial pres-sure control by adding nitrogen cooling comes out of the stove to obtain below 4% in sintering process
MnZn soft magnetic ferrite material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that comparison cases 2 are prepared is 535mT,
Saturation induction density at 100 DEG C is 410mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
320kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 405kWm-3, the initial permeability of material is
1200, Curie temperature is 265 DEG C.
Comparison cases 3：
The content of the principal component of selection is calculated as with oxide：Fe2O3：71.64wt%, ZnO：5.46wt%, MnO：Surplus,
Principal component is subjected to a ball milling 1h, black powder is obtained in 930 DEG C of pre-burning 2h；The black powder that pre-burning is obtained is added by master
The accessory ingredient of the total amount meter of component, accessory ingredient content are calculated as with oxide：CaO：2000ppm, TiO2：1500ppm, SiO2：
1000ppm simultaneously adds suitable deionized water, and secondary ball milling 4h, obtains the powder granule of 0.7~2 μm of particle diameter, and particle diameter distribution
Normal Distribution；By grinding distribution after the particle drying after secondary ball milling, add polyvinyl alcohol and be granulated, sieving obtains MnZn iron
Ferromagnetic powder；Obtained powder pressing shaping will be granulated, be put into atmosphere sintering furnace and sinters, sintering temperature is 1300 DEG C, insulation
3h, makes equilibrium oxygen partial pres-sure control cooling comes out of the stove to obtain MnZn soft magnetic ferrites below 4% in sintering process by adding nitrogen
Material.
Saturation induction density during its 25 DEG C of the MnZn soft magnetic ferrite material that comparison cases 3 are prepared is 505mT,
Saturation induction density at 100 DEG C is 390mT, and under 30mT, 100 DEG C, the test condition of 1MHz, its power attenuation is
380kWm-3, under 10mT, 100 DEG C, the test condition of 3MHz, its power attenuation is 420kWm-3, the initial permeability of material is
900, Curie temperature is 240 DEG C.
Comparative example 1 and comparative example 1 are it can be found that CaO and SiO2Addition shadow is produced to crystal boundary and grain resistance rate
Ring, in general, grain boundary resistivity can be increased so as to increase the resistivity of whole material so that the eddy-current loss of material can be bright
It is aobvious to reduce；
It is not added with CaO and SiO21 material of comparative example, its power attenuation is higher, is unfavorable for material and uses in high frequency.
Comparative example 2 and comparative example 2 are it can be found that TiO2Addition can improve the saturation induction density of material,
The high frequency power loss of material is reduced, its dominant mechanism is can to improve the ferritic patterns of MnZn, makes crystal grain more homogeneous, together
The TiO of Shi Duoyu2Grain boundaries can be enriched in, can also play the role of reducing eddy-current loss, the addition of tetravalence Ti elements is favourable
In the content for improving divalence Fe ions, the lifting of suitable divalence Fe ion pair material properties is favourable.
Comparative example 3 and comparative example 3 are it can be found that In2O3With the addition of CoO, it can largely increase material
Saturation induction density and magnetic conductivity, can ensure to ensure that material is not present such that magnetic property because of other non magnetic additives
Destroyed, main function mechanism is In2O3It can be entered among principal phase solid solution tissue with CoO, substitute original tetrahedral interstice
Or the metal ion in octahedral interstice, in addition to having an impact to the saturation induction density of ferrimagnetism, appropriate addition
Agent can also adjust the magnetocrystalline anisotropy constant and magnetostriction coefficient of material entirety, so as to adjust the temperature characterisitic of material.
Part highly charged ions replace original low price ion, due to keep overall electroneutral and stoichiometric ratio, can also make
Ferric ion is changed into ferrous ion, and the resistivity of principal phase can also be had an impact.
Claims (4)
1. one kind prepares the ferritic ionic association alternatives of high-performance MnZn, it is characterised in that：
（1）Primary batching system
Weigh principal component；
（2）Ball milling
Principal component is uniformly mixed, the principal component weighed is put into ball mill, 3 ~ 10h of ball milling, obtains a ball milling powder；
（3）It is once sintered
Powder obtained by first time ball milling is warming up to 800 ~ 1000 DEG C with the speed of 200 ~ 300 DEG C/h in air atmosphere, is protected
1 ~ 3h of temperature, furnace cooling obtain once sintered powder；
（4）Second batch
Addition include the accessory ingredient of In, Co, Ca, Si, Ti element in once sintered powder, the pair based on the total amount of principal component into
Point constituent content is：In：800 ~ 3000ppm, Co：300 ~ 1500ppm, Ca：500 ~ 2000ppm, Ti：800 ~ 2000ppm, Si：0
~ 15000ppm, the total amount of adding of accessory ingredient are no more than 3 wt% of sintering powder；
（5）Secondary ball milling
Ball mill will be put into after the powder obtained after second batch uniformly mixing, be milled to 0.8 ~ 2 μm of powder particle size, obtains secondary
Ball milling powder；
（6）It is granulated
According to the powder gross weight after secondary ball milling, polyvinyl alcohol water solution is added, the wherein addition of polyvinyl alcohol is powder
The wt% of 3 wt% of gross mass ~ 10, particle is ground up, sieved into after first precompressed;
（7）It is compressing
Polyvinyl alcohol water solution is added to being granulated in the particulate material of gained, the wherein addition of polyvinyl alcohol is particulate material gross mass
The wt% of 3 wt% ~ 10, compressing is green product, and green density will reach 2.6 ~ 3.6 g/cm3
（8）Double sintering
Sintering temperature is 1200 ~ 1400 DEG C, 2 ~ 14h of insulation, equilibrium oxygen partial pres-sure control is existed by adding nitrogen in sintering process
Less than 4%, cooling comes out of the stove to obtain MnZn soft magnetic ferrite material.
2. one kind according to claim 1 prepares the ferritic ionic association alternatives of high-performance MnZn, its feature exists
It is in the principal component：Mn a Zn b Fe c O 4 , wherein a=0.6 ~ 0.8, b=0.1 ~ 0.3, c=3-a-b.
3. one kind according to claim 1 prepares the ferritic ionic association alternatives of high-performance MnZn, its feature exists
In oxide, carbonate, silicate that the addition form of In, Co, Ca, Si, Ti accessory ingredient is In, Co, Ca, Si, Ti
And the organic compound containing the element.
A kind of 4. high-performance MnZn ferrites prepared such as any one of claim 1-3 the method.
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|---|---|---|---|---|
| CN1649039A (en) * | 2004-01-30 | 2005-08-03 | Tdk株式会社 | Method for producing Mn-Zn ferrite |
| CN1749209A (en) * | 2005-08-04 | 2006-03-22 | 浙江大学 | High saturated magnetic flux density and low loss manganese-zinc ferrite material and its preparing method |
| CN104591711A (en) * | 2014-12-19 | 2015-05-06 | 江门安磁电子有限公司 | Low-loss manganese zinc ferrite material for temperature of 40 DEG C below zero to 160 DEG C and manufacturing method thereof |
| CN105036726A (en) * | 2015-07-24 | 2015-11-11 | 天长市中德电子有限公司 | High-performance Mn-Zn ferrite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649039A (en) * | 2004-01-30 | 2005-08-03 | Tdk株式会社 | Method for producing Mn-Zn ferrite |
| CN1749209A (en) * | 2005-08-04 | 2006-03-22 | 浙江大学 | High saturated magnetic flux density and low loss manganese-zinc ferrite material and its preparing method |
| CN104591711A (en) * | 2014-12-19 | 2015-05-06 | 江门安磁电子有限公司 | Low-loss manganese zinc ferrite material for temperature of 40 DEG C below zero to 160 DEG C and manufacturing method thereof |
| CN105036726A (en) * | 2015-07-24 | 2015-11-11 | 天长市中德电子有限公司 | High-performance Mn-Zn ferrite material and preparation method |
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