CN116891377A - Bias-reduction-resistant lean iron-manganese-zinc ferrite material and preparation method thereof - Google Patents

Bias-reduction-resistant lean iron-manganese-zinc ferrite material and preparation method thereof Download PDF

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CN116891377A
CN116891377A CN202310984437.2A CN202310984437A CN116891377A CN 116891377 A CN116891377 A CN 116891377A CN 202310984437 A CN202310984437 A CN 202310984437A CN 116891377 A CN116891377 A CN 116891377A
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manganese
ferrite material
bias
main component
presintering
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黄爱萍
郭皓
谭福清
姚木有
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Hubei Weishuo New Material Co ltd
Guangdong Zhaoqing Weishuo Electronics Co ltd
Wuyi University
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Hubei Weishuo New Material Co ltd
Guangdong Zhaoqing Weishuo Electronics Co ltd
Wuyi University
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Abstract

The invention relates to an anti-bias-reduction lean iron-manganese-zinc ferrite material and a preparation method thereof, wherein the ferrite material comprises a main component and an auxiliary component, and the main component is 48-49 mol% of Fe 2 O 3 Mn of 34 to 40mol% in terms of MnO 3 O 4 And 12 to 17mol% ZnO; and the auxiliary component is cobalt oxide accounting for x wt% of Co based on the total weight of the main component, wherein the value range of x is the mol% value of MnO in the main component divided by (35+/-4); the ferrite material is further doped with a material selected from SiO 2 、CaCO 3 、V 2 O 5 、Nb 2 O 5 、Bi 2 O 3 、MoO 3 Based on the total weight of the main component, siO 2 20-80 ppm CaCO 3 100 to600ppm、V 2 O 5 0 to 400ppm of Nb 2 O 5 30 to 300ppm of Bi 2 O 3 0 to 600ppm, moO 3 0 to 600ppm. The bias-reduction-resistant lean iron-manganese-zinc ferrite material can effectively reduce inductance drop of an EMI-resistant magnetic core caused by bias.

Description

Bias-reduction-resistant lean iron-manganese-zinc ferrite material and preparation method thereof
Technical Field
The invention relates to the field of soft magnetic ferrite materials, in particular to an anti-bias fall-off lean iron-manganese-zinc ferrite material and a preparation method thereof.
Background
The current society is developing from the Internet age to the Internet of things age, and if the Internet is said to be a person as a connection and service object, the Internet of things is said to extend the object of information network connection and service from person to object so as to realize 'everything interconnection'. The ubiquitous information network connection makes the space where the electronic equipment is located full of more and more electromagnetic interference, and an effective way to solve or reduce electromagnetic pollution and improve the electromagnetic interference resistance of the electronic equipment is to adopt an electromagnetic compatibility design, wherein a large amount of anti-EMI materials are needed.
Common anti-EMI materials are iron-rich manganese-zinc ferrite materials suitable for below 10MHz and nickel-zinc ferrite materials above 10 MHz. In recent years, due to the consideration of production compatibility and cost reduction, ferrite materials with low iron, manganese and zinc content, which can be used for more than 10MHz, have been developed to a certain extent. Chinese patent (Jiang Fen magnetic material CN101857426A, jiangmen An magnetic material CN111138179A, CN111138180A, CN111138181A, dong magnetic material CN110156451A, spring light CN112142457A, bao steel CN110824395A, tianyuan CN110845228A and Tianming CN 101805173A) sequentially discloses iron-manganese-zinc ferrite materials with magnetic permeability of 650-4000, greatly expands the working frequency range of the manganese-zinc ferrite materials, and partially replaces the application field of nickel-zinc ferrite. However, a problem is also found in applications, where the lean iron-manganese-zinc ferrite core has a drop in inductance of more than 50% after dc biasing or equivalent operation and is not self-recovering. The material can be reused after the magnetic neutralization treatment, and the magnetic neutralization device is impractical to add in the practical application scene, so that the application and popularization of the iron-manganese-zinc-lean ferrite material are greatly limited.
Therefore, there is a need to find a new anti-bias-drop lean iron-manganese-zinc ferrite material and a preparation method thereof to overcome the problems in the prior art.
Disclosure of Invention
The invention provides an anti-bias fall-down lean iron-manganese-zinc ferrite material and a preparation method thereof, aiming at solving the problem that the inductance of the existing lean iron-manganese-zinc ferrite cannot be recovered by itself due to the falling of the inductance after direct current bias.
An object of the present invention is to provide a bias-reduction resistant iron-manganese-zinc-depleted ferrite material characterized by: the ferrite material comprises a main component and an auxiliary component, wherein the main component is 48-49 mol% of Fe 2 O 3 Mn of 34 to 40mol% in terms of MnO 3 O 4 And 12 to 17mol% ZnO; and the auxiliary component is cobalt oxide with xwt% of Co based on the total weight of the main component, wherein the value range of x is the mol% value of MnO in the main component divided by (35+/-4).
The ferrite material is further doped with a material selected from SiO 2 、CaCO 3 、V 2 O 5 、Nb 2 O 5 、Bi 2 O 3 、MoO 3 Based on the total weight of the main component, siO 2 20-80 ppm CaCO 3 100 to 600ppm, V 2 O 5 0 to 400ppm of Nb 2 O 5 30 to 300ppm of Bi 2 O 3 0 to 600ppm, moO 3 0 to 600ppm.
Further, the cobalt oxide may be Co 3 O 4 、Co 2 O 3 Or any one of CoO or a mixture thereof. In the case of the mixture, it is necessary to test the Co content in advance.
Further, the cobalt oxide is Co 3 O 4 The effect is optimal. Because of Co 3 O 4 Is of a cubic spinel structure, and is easier to carry out solid solution diffusion reaction with the manganese zinc ferrite of the spinel structure.
Another object of the present invention is to provide a method for preparing the ferrite material, comprising the steps of:
1) And (3) batching: weighing main components according to design components;
2) Mixing: mixing the main components, and putting the mixture into a sand mill or a ball mill, and fully and uniformly mixing the mixture to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 850-950 ℃, the heat preservation time is 1-3 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material, and carrying out secondary grinding until the average granularity is about 1 mu m to obtain slurry;
5) Granulating: adding 8-10wt% of 8-10wt% polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.1-0.5 wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.15-0.45 wt%, adding 0.1-0.5 wt% zinc stearate based on the total weight of the obtained water-containing powder material, mixing, and pressing to form a green body product;
7) Sintering: the sintering temperature is 1280-1360 ℃, the heat preservation time is 4-8 hours, and the manganese zinc ferrite material is obtained after cooling and discharging.
Further, in the step 6), the green density of the pressed product is 3.0+ -0.2 g/cm 3 。
Further, in the step 7), air sintering is adopted from normal temperature to high temperature, a cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, wherein a takes the value 5-8, b takes the value 11000-15000, and T is absolute temperature.
The invention has the beneficial effects that:
the inductance of the existing iron-manganese-zinc ferrite core on the market falls by more than 50% after direct current bias, and the ferrite core cannot recover by itself. According to theoretical guidance, the invention combines a great amount of experimental researches to find that the iron is poorThe anti-bias drop characteristic of the manganese-zinc ferrite material has a certain correlation with the Br/Bs ratio (namely the remanence ratio), and the remanence ratio has a certain correlation with the relative proportion of MnO content and Co doping amount in the main component of the lean iron-manganese-zinc ferrite material. Because the inertia operation of the high-permeability Mn-Zn ferrite material does not pay special attention to the value of Br in the early-stage lean Fe-Mn-Zn ferrite material development process, the important parameter of the remanence ratio is ignored, and the problem that the inductance bias of the lean Fe-Mn-Zn ferrite material is reduced by more than 50% and cannot be recovered by itself is found after the lean Fe-Mn-Zn ferrite material is brought to the market. The iron-manganese-zinc ferrite material with poor content, which is obtained by the composition and the preparation method of the invention, can overcome the problem, and the Tc of the material is more than or equal to 140 ℃, and the Bs is more than or equal to 420mT and mu i =2000-4000, br/Bs is less than or equal to 0.2, and the offset drop of inductance is less than or equal to 15%, the application frequency of the iron-deficient 3K material can be higher than that of a 5K material, and the magnetic permeability of the iron-deficient 3K material is higher than that of a general nickel-zinc material.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to examples. The scope of protection claimed in the present invention is not limited to the scope of embodiments of the present invention. Unless specifically mentioned, the components and test methods mentioned in the examples of the present patent disclosure are conventional methods known to those skilled in the art.
Example 1
1) And (3) batching: the components are as follows: 48.0mol% Fe 2 O 3 Mn of 40.0mol% in terms of MnO 3 O 4 And 12.0mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 850 ℃, the heat preservation time is 3 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.25wt% based on Co 2 O 3 30ppm of SiO 2 CaCO 200ppm 3 50ppm Nb 2 O 5 300ppm Bi 2 O 3 、400ppm MoO 3 Grinding to average granularity of 0.91 μm to obtain slurry;
5) Granulating: adding 8wt% of 10wt% concentration polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder material, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.1wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.35wt%, adding 0.5wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 2.8g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1360 ℃, the heat preservation time is 4 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 7.8, b takes the value 14540, T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2057，Br/Bs＝0.19，D L =15%, offset drop ratio D L Significantly less than 50%.
Example 2
1) And (3) batching: the components are as follows: 48.1mol% Fe 2 O 3 Mn of 39.4mol% in terms of MnO 3 O 4 And 12.5mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 35min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 950 ℃, the heat preservation time is 1 hour, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.22wt% based on Co 2 O 3 +Co 3 O 4 Mixture, 30ppm of SiO 2 CaCO 200ppm 3 50ppm Nb 2 O 5 400ppm MoO 3 Grinding to average granularity of 0.93 μm to obtain slurry;
5) Granulating: adding 9wt% of 10wt% concentration polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder material, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.2wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.42wt%, adding 0.3wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 2.9g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1360 ℃, the heat preservation time is 5 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.75, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2290，Br/Bs＝0.18，D L =7%, offset drop ratio D L Significantly less than 50%.
Example 3
1) And (3) batching: the components are as follows: 48.2mol% Fe 2 O 3 Mn of 38.8mol% in terms of MnO 3 O 4 And 13.0mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 40min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 880 ℃, the heat preservation time is 2.5 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: 1.18wt% CoO, 30ppm SiO based on Co 2 CaCO 200ppm 3 50ppm Nb 2 O 5 300ppm Bi 2 O 3 Grinding to average granularity of 0.95 μm to obtain slurry;
5) Granulating: adding 10wt% of 9wt% polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.5wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.37wt%, adding 0.3wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.0g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1350 ℃, the heat preservation time is 6 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes a value of 6.05, b takes a value of 12000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the Strip at 50Hz, 1200A/m and 25 ℃ with SY-8258 type B-H testerBs and Br of the sample magnetic ring are tested under the piece, and the remanence ratio Br/Bs is calculated; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2512，Br/Bs＝0.19，D L =3%, offset drop ratio D L Significantly less than 50%.
Example 4
1) And (3) batching: the components are as follows: 48.3mol% Fe 2 O 3 Mn of 38.2mol% in terms of MnO 3 O 4 And 13.5mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 860 ℃, the heat preservation time is 2.5 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.15wt% based on Co 3 O 4 30ppm of SiO 2 CaCO 200ppm 3 V at 200ppm 2 O 5 100ppm Nb 2 O 5 Grinding to average granularity of 0.97 μm to obtain slurry;
5) Granulating: adding 10wt% of 10wt% concentration polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.5wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.15wt%, adding 0.5wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.1g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1330 ℃, the heat preservation time is 6 hours, the air sintering is adopted from normal temperature to high temperature, and the cooling section adopts a small amount of nitrogen for protectionThe temperature is lowered, and the equilibrium oxygen partial pressure of the temperature lowering section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.75, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2648，Br/Bs＝0.18，D L =1%, offset drop-off ratio D L Significantly less than 50%.
Example 5
1) And (3) batching: the components are as follows: 48.4mol% Fe 2 O 3 Mn of 37.6mol% in terms of MnO 3 O 4 And 14.0mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 920 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.11wt% based on Co 3 O 4 30ppm of SiO 2 CaCO 200ppm 3 V at 100ppm 2 O 5 100ppm Nb 2 O 5 Grinding to average granularity of 0.93 μm to obtain slurry;
5) Granulating: adding 10wt% of 9wt% polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: step toAdding 0.3wt% concentration polyvinyl alcohol water solution to the granule to make the water content of the powder reach 0.35wt%, adding 0.4wt% zinc stearate based on the total weight of the obtained water-containing powder, mixing, and pressing to obtain compact with a density of 3.0g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1280 ℃, the heat preservation time is 7 hours, air sintering is adopted from normal temperature to high temperature, a cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.75, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2804，Br/Bs＝0.18，D L Less than 1%, offset drop ratio D L Significantly less than 50%.
Example 6
1) And (3) batching: the components are as follows: 48.5mol% Fe 2 O 3 Mn of 37.0mol% in terms of MnO 3 O 4 And 14.5mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 870 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.08wt% based on Co 3 O 4 50ppm of SiO 2 CaCO 200ppm 3 50ppm Nb 2 O 5 Grinding to average granularity of 0.9 μm to obtain slurry;
5) Granulating: adding 10wt% of 10wt% concentration polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.1wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.45wt%, adding 0.5wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.1g/cm 3 Is a green product of (a);
7) Sintering: sintering temperature is 1290 ℃, heat preservation time is 7 hours, air sintering is adopted from normal temperature to high temperature, a cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.55, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝2975，Br/Bs＝0.18，D L Less than 1%, offset drop ratio D L Significantly less than 50%.
Example 7
1) And (3) batching: the components are as follows: 48.6mol% Fe 2 O 3 Mn of 36.4mol% in terms of MnO 3 O 4 And 15.0mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 900 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.05wt% based on Co 3 O 4 30ppm of SiO 2 300ppm CaCO 3 50ppm Nb 2 O 5 Grinding to average granularity of 0.9 μm to obtain slurry;
5) Granulating: adding 10wt% of 10wt% concentration polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.5wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.35wt%, adding 0.2wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.0g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1320 ℃, the heat preservation time is 6 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.65, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝3153，Br/Bs＝0.18，D L Less than 1%, offset drop ratio D L Significantly less than 50%.
Example 8
1) And (3) batching: the components are as follows: 48.7mol% Fe 2 O 3 Mn of 35.8mol% in terms of MnO 3 O 4 And 15.5mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 910 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: co 1.02wt% based on Co 3 O 4 30ppm of SiO 2 300ppm CaCO 3 100ppm Nb 2 O 5 Grinding to average granularity of 0.9 μm to obtain slurry;
5) Granulating: adding 10wt% of 10wt% concentration polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.3wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.35wt%, adding 0.3wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.1g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1310 ℃, the heat preservation time is 7 hours, air sintering is adopted from normal temperature to high temperature, a cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.55, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the Test of sample magnetism with SY-8258 type B-H tester under conditions of 50Hz, 1200A/m and 25 DEG CBs and Br of the ring, calculating remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝3300，Br/Bs＝0.19，D L =2% offset by a drop ratio D L Significantly less than 50%.
Example 9
1) And (3) batching: the components are as follows: 48.8mol% Fe 2 O 3 Mn of 35.2mol% in terms of MnO 3 O 4 And 16.0mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 930 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: 0.97wt% CoO, 30ppm SiO calculated as Co 2 300ppm CaCO 3 200ppm Nb 2 O 5 Grinding to average granularity of 0.9 μm to obtain slurry;
5) Granulating: adding 9wt% of 10wt% concentration polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder material, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.5wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.35wt%, adding 0.5wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with the density of 3.0g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1320 ℃, the heat preservation time is 6 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T calculation, whichWherein a has a value of 6.55, b has a value of 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝3476，Br/Bs＝0.19，D L =4%, offset drop ratio D L Significantly less than 50%.
Example 10
1) And (3) batching: the components are as follows: 48.9mol% Fe 2 O 3 Mn of 34.6mol% in terms of MnO 3 O 4 And 16.5mol% ZnO, weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 910 ℃, the heat preservation time is 2 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: 0.93wt% CoO, 30ppm SiO calculated as Co 2 400ppm CaCO 3 300ppm Nb 2 O 5 Grinding to average granularity of 0.91 μm to obtain slurry;
5) Granulating: adding 10wt% of 9wt% polyvinyl alcohol aqueous solution into the slurry obtained in the step 4) based on the total weight of the powder, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.3wt% concentration polyvinyl alcohol water solution into the granule material obtained in step 5) to make the water content of the powder material reach 0.35wt%, and based on the total weight of the obtained water-containing powder material,adding 0.5wt% zinc stearate for mixing, and pressing to obtain compact with density of 3.1g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1300 ℃, the heat preservation time is 7 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes the value 6.65, b takes the value 13000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝3735，Br/Bs＝0.19，D L =12%, offset drop-off ratio D L Significantly less than 50%.
Example 11
1) And (3) batching: the components are as follows: 49.0mol% Fe 2 O 3 Mn of 34.0mol% in terms of MnO 3 O 4 And 17.0mol% ZnO, and weighing the main component;
2) Mixing: mixing the main components, and placing into a sand mill or a ball mill, and mixing for 30min to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 950 ℃, the heat preservation time is 1 hour, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material: 0.90wt% Co based on Co 2 O 3 30ppm of SiO 2 CaCO 200ppm 3 300ppm Nb 2 O 5 Grinding to average granularity of 0.9 μm to obtain slurry;
5) Granulating: adding 10wt% of polyvinyl alcohol aqueous solution with the concentration of 8wt% into the slurry obtained in the step 4) based on the total weight of the powder, uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.2wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.35wt%, adding 0.5wt% zinc stearate based on the total weight of the obtained water-containing powder material to mix, and pressing to form a pressed compact with a density of 3.2g/cm 3 Is a green product of (a);
7) Sintering: the sintering temperature is 1280 ℃, the heat preservation time is 8 hours, the air sintering is adopted from normal temperature to high temperature, the cooling section adopts a small amount of nitrogen for protection cooling, and the equilibrium oxygen partial pressure of the cooling section is calculated according to the formula lg (P (O) 2 ) a-b/T, where a takes a value of 5.35, b takes a value of 11000, and T is absolute temperature. Cooling and discharging to obtain the Mn-Zn ferrite material.
8) And (3) testing: measuring normal temperature inductance L of sample magnetic ring under 10kHz and 0.25V by adopting HP4284A LCR tester 0 Calculating the initial permeability mu of the material i The method comprises the steps of carrying out a first treatment on the surface of the The Bs and Br of the sample magnetic ring are tested by a SY-8258 type B-H tester at 50Hz, 1200A/m and 25 ℃ to calculate the remanence ratio Br/Bs; after the DC bias test of 30A/m is carried out on the sample magnetic ring by using the HP4284A matched with the HP42841A DC bias source, the magnetic neutralization treatment is not carried out, and then the normal temperature inductance L of the sample magnetic ring under the conditions of 10kHz and 0.25mT is measured 1 Calculating the offset drop ratio D L ＝(L 0 -L 1 )/L 0 。
The results were measured: mu (mu) i ＝3899，Br/Bs＝0.19，D L =14%, offset drop ratio D L Significantly less than 50%.
Comparative examples 1 to 4
The doping component ratios and preparation methods and tests of comparative examples 1 to 4 were the same as those of example 6, except that the main component ratios of comparative examples 1 to 4 were different, as shown in Table 1.
Comparative examples 5 to 6
Comparative examples 5 to 6 were identical to example 6 in the main component and doping component ratio and in the preparation and test methods, except that the auxiliary component ratios of comparative examples 5 to 6 were different, as shown in Table 1.
Comparative examples 7 to 12
Comparative examples 7 to 12 were identical to example 6 in the main component and auxiliary component ratio and the preparation and test methods, except that comparative examples 7 to 12 were different in the doping component ratio, as shown in Table 1.
Table 1 comparative example ingredient ratios
Comparative examples 7 to 12 were doped in a proportion outside the range of the present invention, and all samples were abnormally crystallized, except that the crystallization was different in each case, such as MoO 3 Excessive amount causes crystal spots on the surface of the sample, while Bi 2 O 3 The excess causes crystallization inside the sample.
The main component ratio of comparative examples 1 to 4 was outside the main component range of the present invention (Fe 2 O 3 ：48～49mol％、Mn 3 O 4 (in terms of MnO): 34 to 40mol percent of ZnO:12 to 17 mol%) of Fe of comparative example 1 2 O 3 The proportion is ultralow, and excessive cation vacancies accelerate grain growth, so that the sample is crystallized; fe of comparative example 2 2 O 3 The proportion is near the positive division range, and a small amount of Fe is generated in the atmosphere sintering process 2+ Ions greatly reduce the resistivity of the sample, increase eddy current loss, and lead the sample to be unavailable for high frequency of more than 10 MHz; the ZnO proportion of comparative example 3 is ultra-low, and the magnetic permeability is lower than the range of the invention; the ZnO ratio of comparative example 4 was ultra-high, the permeability was higher than the range of the present invention, and the Curie temperature, bs were lower than the range of the present invention.
The auxiliary component ratio of comparative examples 5 to 6 is outside the range of the present invention (x wt% of cobalt oxide based on the total weight of the main component in terms of Co, where x is the value of mol% of MnO in the main component divided by (35.+ -. 4), i.e., 0.95 to 1.19 wt%), where Co addition ratio of comparative example 5 is extremely low, co 2+ Under compensation, the remanence ratio reaches 0.46, and the bias is reduced by 45%; co addition ratio was ultra-high for comparative example 6, co 2+ Overcompensation, the remanence ratio reaches 0.53,the offset was reduced by 49%.
The invention has been described above by means of preferred embodiments, but it should be understood that these preferred embodiments are not intended to limit the scope of the invention. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. An anti-bias fall-off lean iron-manganese-zinc ferrite material, characterized in that: the ferrite material comprises a main component and an auxiliary component, wherein the main component is 48-49 mol% of Fe 2 O 3 Mn of 34 to 40mol% in terms of MnO 3 O 4 And 12 to 17mol% ZnO; and the auxiliary component is cobalt oxide accounting for x wt% of Co based on the total weight of the main component, wherein the value range of x is the mol% value of MnO in the main component divided by (35+/-4).
2. A bias-reduction resistant iron-manganese-zinc-depleted ferrite material according to claim 1, wherein: the cobalt oxide is Co 3 O 4 、Co 2 O 3 Or a mixture of one or more of CoO.
3. The bias-reduction resistant iron-manganese-zinc-depleted ferrite material of claim 1, further doped with a material selected from the group consisting of SiO 2 、CaCO 3 、V 2 O 5 、Nb 2 O 5 、Bi 2 O 3 、MoO 3 Based on the total weight of the main component, siO 2 20-80 ppm CaCO 3 100 to 600ppm, V 2 O 5 0 to 400ppm of Nb 2 O 5 30 to 300ppm of Bi 2 O 3 0 to 600ppm, moO 3 0 to 600ppm.
4. A bias-reducing lean iron manganese zinc ferrite material according to claim 2, wherein the materialTc≥140℃、Bs≥420mT、μ i =2000 to 4000, br/Bs is less than or equal to 0.2, and the offset drop of the inductance is less than or equal to 15%.
5. A method of preparing an anti-biased-fall iron-manganese-zinc-depleted ferrite material as claimed in any one of claims 1 to 4, comprising the steps of:
1) And (3) batching: weighing main components according to design components;
2) Mixing: mixing the main components, and putting the mixture into a sand mill or a ball mill, and fully and uniformly mixing the mixture to obtain powder;
3) Presintering: presintering the obtained powder, wherein the presintering temperature is 850-950 ℃, the heat preservation time is 1-3 hours, and naturally cooling and discharging to obtain presintering materials;
4) And (2) secondary grinding: adding auxiliary components into the presintered material, and carrying out secondary grinding until the average granularity is about 1 mu m to obtain slurry;
5) Granulating: adding 8-10wt% of 8-10wt% polyvinyl alcohol aqueous solution based on the total weight of the powder of the slurry obtained in the step 4), uniformly mixing and granulating to obtain granules for forming;
6) And (3) forming: adding 0.1-0.5 wt% concentration polyvinyl alcohol water solution to the granule material obtained in the step 5) to make the water content of the powder material reach 0.15-0.45 wt%, adding 0.1-0.5 wt% zinc stearate based on the total weight of the obtained water-containing powder material, mixing, and pressing to form a green body product;
7) Sintering: the sintering temperature is 1280-1360 ℃, the heat preservation time is 4-8 hours, and the manganese zinc ferrite material is obtained after cooling and discharging.
6. The method according to claim 5, wherein in the step 6), the green density of the pressed product is 3.0.+ -. 0.2g/cm 3 。
7. The method according to claim 5, wherein in step 7), the temperature is raised from normal temperature to high temperature by air sintering, the temperature lowering section is cooled by a small amount of nitrogen protection, and the equilibrium oxygen partial pressure of the temperature lowering section is calculated according to the formula lg (P (O) 2 ) a-b/T meter)Calculating, wherein the value of a is 5-8, the value of b is 11000-15000, and T is absolute temperature.
CN202310984437.2A 2023-08-07 2023-08-07 Bias-reduction-resistant lean iron-manganese-zinc ferrite material and preparation method thereof Pending CN116891377A (en)

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