CN113744991A - Co2Z-type ferrite material and preparation method and application thereof - Google Patents

Co2Z-type ferrite material and preparation method and application thereof Download PDF

Info

Publication number
CN113744991A
CN113744991A CN202111091418.4A CN202111091418A CN113744991A CN 113744991 A CN113744991 A CN 113744991A CN 202111091418 A CN202111091418 A CN 202111091418A CN 113744991 A CN113744991 A CN 113744991A
Authority
CN
China
Prior art keywords
type
type ferrite
mixed solution
ferrite material
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111091418.4A
Other languages
Chinese (zh)
Other versions
CN113744991B (en
Inventor
单震
刘立东
朱航飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hengdian Group DMEGC Magnetics Co Ltd
Original Assignee
Hengdian Group DMEGC Magnetics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hengdian Group DMEGC Magnetics Co Ltd filed Critical Hengdian Group DMEGC Magnetics Co Ltd
Priority to CN202111091418.4A priority Critical patent/CN113744991B/en
Publication of CN113744991A publication Critical patent/CN113744991A/en
Application granted granted Critical
Publication of CN113744991B publication Critical patent/CN113744991B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4

Abstract

The invention provides a Co2Z-type ferrite material and its preparation method and application. The preparation method comprises the following steps: (1) treating the Y-type mixed solution and the M-type mixed solution by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution; (3) respectively mixing the Y-type cation mixed solution and the M-type cation mixed solution with ammonium bicarbonate, and drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor; (4) carrying out compression molding on the Y-type ferrite precursor, the M-type ferrite precursor and the binder, presintering once, and sintering twice to obtain Co2A Z-type ferrite material; the substituted metal ion includes Ba2+And/or Sr2+. The invention prepares Co with uniform mixing, smaller granularity, less impurities and higher performance by an electrodialysis method2The Z-type ferrite material is suitable for ultrahigh frequency magnetic devices, and reduces the sintering temperatureAnd the preparation process is saved.

Description

Co2Z-type ferrite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of magnetic materials, and relates to Co2Z-type ferrite material and its preparation method and application.
Background
At present, the demand for miniaturized, portable electronic devices in the ultra-high frequency band is rapidly increasing. The hexagonal ferrite exhibits excellent properties of high magnetic permeability, low loss, and high quality factor at ultra-high frequencies. At room temperature, only Y-type and Co2The Z-type and W-type hexagonal ferrite has six planesSoft magnetic properties of the ferrite of the angle system. In view of the materials of the developed antenna elements, the device design requirements of microwave antennas, magneto-optical devices and other electrical equipment still cannot be met. Spinel ferrites exhibit high magnetic permeability, but their cut-off frequency is relatively low and not suitable for frequencies above 0.3 GHz. Co2The cut-off frequency fr of the Z-type ferrite material is higher than 1GHz, and the Z-type ferrite material has very high resistivity and great application potential on ultrahigh frequency electronic components. In recent years, Co has been improved by improving the formulation and production process2The magnetic resonance frequency of Z-type ferrite materials has increased to above 3 GHz.
CN103319165A discloses a Z-type hexaferrite material and a preparation method thereof, wherein the molecular formula is Sr3xBa3(1-x)Co2GdyFe24-yO41Or Sr3xBa3(1-x)Co2SmyFe24-yO41Wherein 0.4<x<0.6，0.05<y<0.1; the preparation method comprises the following steps: preparing the raw materials into mixed powder according to a certain weight ratio; carrying out wet ball milling on the mixed powder, and then drying, sieving and presintering the powder; carrying out secondary wet ball milling on the pre-sintered powder, then carrying out spray granulation, and pressing into a magnetic cake; and sintering the obtained magnetic cake to obtain the Z-shaped hexagonal ferrite. The document adopts a solid-phase reaction method, and the prepared Z-type hexaferrite has a plurality of impure phases and low quality, and the performance of the Z-type hexaferrite is influenced.
CN106587972A discloses a preparation method of Z-type ferrite flake powder, which comprises the following steps: weighing BaCO3、Fe2O3And keeping the temperature of the molten salt at 1150-1200 ℃ for 2-4 h to obtain an M-type ferrite precursor; mixing Fe2O3And BaCl2·2H2Mixing O, adding an M-type precursor, and carrying out heat preservation for 6-10 h at 1200-1250 ℃ to obtain (001) BaFe12O19Flaky powder; mixing Y-type precursor powder with (001) BaFe12O19Mixing the flaky powder according to the molar ratio of 1:1, adding molten salt, and keeping the temperature at 1250-1300 ℃ for 6-10 h to obtain Co2A Z-type ferrite; the method needs to additionally add barium salt when preparing the M-type precursor,and barium salt cannot be completely removed from the prepared finished product, and the impurities are more.
CN106498497A discloses a method for preparing high-purity granular single-crystal Co2A method of forming a Z-type ferrite powder, the method comprising: the soluble metal salt is taken as a starting material, and the metal elements are uniformly distributed in the precursor powder by optimizing the dosage and adding mode of the composite precipitator; and then, mixing the precursor with salt, and in the heat treatment process, taking a molten salt liquid phase as an ion transmission medium to accelerate metal ion diffusion in the heat treatment process and promote formation of a target product, and promoting particle growth of the target product to tend to a crystal growth habit through liquid phase growth to show single crystallization. The method has the advantages of complex process flow and difficult component control.
Therefore, how to obtain a ferrite material suitable for ultrahigh frequency devices is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide Co2Z-type ferrite material and its preparation method and application. The invention prepares Co with uniform mixing, smaller granularity, less impurities and higher magnetic conductivity by an electrodialysis method2The Z-type ferrite material is suitable for ultrahigh frequency magnetic devices, reduces the sintering temperature and saves the preparation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a Co2A method for preparing a Z-type ferrite material, the method comprising the steps of:
(1) will contain Fe3+Soluble metal salt of (2), soluble metal salt containing substituted metal ion, soluble metal salt containing Co2+Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe3+Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) carrying out first mixing on the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out first drying to obtain a Y-type ferrite precursor;
carrying out second mixing on the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out second drying to obtain an M-type ferrite precursor;
(4) carrying out compression molding, primary presintering and secondary sintering on the Y-type ferrite precursor in the step (3), the M-type ferrite precursor in the step (3) and a binder to obtain the Co2A Z-type ferrite material;
wherein the substituted metal ion comprises Ba2+And/or Sr2+。
The preparation method is simple, the Y-type cation mixed solution and the M-type cation mixed solution are obtained in an ion exchange mode through an electrodialysis method, so that the introduction of impurities is reduced, the purity of metal ions is ensured, then the M-type ferrite precursor and the Y-type ferrite precursor are compounded, and Co is obtained through two-step sintering2The Z-type ferrite material prepared by the preparation method provided by the invention has the advantages of higher magnetic conductivity, small granularity, uniform mixing and less impurities.
In the invention, the Y-type cation mixed solution and the M-type cation mixed solution prepared by the electrodialysis method have the characteristic of good ion dispersion effect.
Compared with other preparation methods, such as a solid phase method, an electrolytic coprecipitation method and the like, the electrodialysis method has the advantages of high material purity, less impurity introduction and good metal ion dispersibility.
According to the invention, the primary presintering is carried out firstly, and then the secondary sintering is carried out, so that the full sintering is facilitated, the phase forming effect is better, the generated Z-type ferrite phase is purer, if only one step is carried out, the impurity phase is relatively more, and the generated Z-type ferrite is difficult.
Preferably, the Fe contained in step (1)3+Soluble metal ofSalt, containing Co2+The soluble metal salt of (2) and the soluble metal salt containing a substituted metal ion include any one of a chloride salt, a nitrate salt or an organic salt or a combination of at least two thereof.
Preferably, the ion exchange membrane used in the electrodialysis method in step (2) comprises any one of an anion exchange membrane, a cation exchange membrane or an ion exchange composite membrane or a combination of at least two of the anion exchange membrane, the cation exchange membrane or the ion exchange composite membrane.
Preferably, the first mixing and the second mixing in step (3) each independently comprise stirring.
Preferably, the first mixing and the second mixing in step (3) are carried out for 5-12 h, such as 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h, etc.
Preferably, the temperature of the first drying and the second drying in the step (3) is 100 to 120 ℃ independently, such as 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
Preferably, in the step (4), the molar ratio of the Y-type ferrite precursor in the step (3) to the M-type ferrite precursor in the step (3) is (1-1.1): 1, for example, 1:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, or 1.1: 1.
In the invention, the molar ratio of the Y-type ferrite precursor in the step (3) to the M-type ferrite precursor in the step (3) is too small, which is not favorable for Z-type ferrite to form a phase, and the performance is poor and too large, which leads to low material performance and low purity of Z-type ferrite.
Preferably, the product after the primary pre-burning in the step (4) is ground.
Preferably, the grinding time is 10-60 s, such as 10s, 20s, 30s, 40s, 50s or 60 s.
Preferably, the temperature of the primary pre-sintering in the step (4) is 1200-1280 ℃, such as 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃, 1250 ℃, 1260 ℃, 1270 ℃ or 1280 ℃ and the like.
In the invention, the temperature of one-time presintering is too high, which is not beneficial to sintering the Z-type ferrite into phases, the product has more impurity phases, and the temperature is too low, which can cause poor performance and more impurity phases.
Preferably, the time for the primary pre-sintering in the step (4) is 1 to 6 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or 6 hours.
Preferably, the temperature of the secondary sintering in step (4) is 1100-1200 ℃, such as 1100 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃ or 1200 ℃.
In the invention, the sintering temperature is reduced by an electrodialysis method, and in the secondary sintering process, the powder particles grow abnormally and have poor particle dispersion effect due to overhigh temperature, and the powder particles have poor phase forming effect due to overlow temperature, so that the powder performance is low.
Preferably, the time of the secondary sintering in the step (4) is 1-6 h, such as 1h, 2h, 3h, 4h, 5h or 6 h.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) will contain Fe3+Soluble metal salt of (2), soluble metal salt containing substituted metal ion containing Co2+Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe3+Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) stirring the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain a Y-type ferrite precursor;
stirring the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain an M-type ferrite precursor;
(4) carrying out compression molding on the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3) according to the molar ratio of (1-1.1) to 1 and a binder, carrying out primary presintering at 1200-1280 ℃ for 1-6 h, and carrying out primary presintering on the primary presintered ferrite precursorGrinding the product for 10-60 s; then carrying out secondary sintering at 1100-1200 ℃ for 1-6 h to obtain the Co2A Z-type ferrite material;
wherein the substituted metal ion comprises Ba2+And/or Sr2+。
In a second aspect, the present invention provides a Co2Preparation method of Z-type ferrite material, Co2The Z-type ferrite material is made of Co as described in the first aspect2The Z-type ferrite material is prepared by the preparation method.
In a third aspect, the invention also provides Co2Use of a Z-type ferrite material of Co as described in the second aspect2The Z-type ferrite material is used for ultrahigh frequency magnetic devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares Co with uniform mixing, smaller granularity and higher magnetic conductivity by an electrodialysis method2The ferrite material of Z type, suitable for in the ultra-high frequency magnetic device, and reduced the sintering temperature, has saved the preparation process, the ferrite material prepared by the invention, its granulometry is under 0.88 μm, and the initial permeability μ' is above 3.9, the dielectric loss tangent tan delta is under 0.045.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a Co2Z-type ferrite material, said Co2The preparation method of the Z-type ferrite material comprises the following steps:
(1) weigh 0.052mol of Ba (NO)3)20.1mol of Co (NO)3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
weigh 0.052mol of Ba (NO)3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain M-type mixed solution;
(2) electrodialysis of NO in solution3-Separating by an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 8h at normal temperature, and then placing in a drying oven at 100 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), weighing 0.03mol of the Y-type ferrite precursor and the M-type ferrite precursor according to the molar ratio of 1:1, mixing, adding 0.3 wt% of PVA (polyvinyl alcohol) binder, granulating, pressing into a block, presintering at 1250 ℃ for one time, and preserving heat for 4 hours;
(5) vibrating and grinding the product after the primary presintering for 20s, sintering at 1150 ℃, and preserving heat for 4h to obtain the Co2A Z-type ferrite material.
Example 2
The present embodiment provides a Co2Z-type ferrite material, said Co2The preparation method of the Z-type ferrite material comprises the following steps:
(1) weigh 0.052mol of Ba (NO)3)20.1mol of Co (NO)3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
0.052mol of Sr (NO) is weighed3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain M-type mixed solution;
(2) electrodialysis of NO in solution3-Separating by an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 5h at normal temperature, and then placing in a drying oven at 120 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), mixing according to the molar ratio of 1.05:1, adding 0.3 wt% of PVA binder for granulation and pressing into blocks, presintering at 1200 ℃ for one time, and preserving heat for 6 hours;
(5) vibrating and grinding the product after the primary presintering for 60s, sintering at 1100 ℃, and preserving heat for 6h to obtain the Co2A Z-type ferrite material.
Example 3
The present embodiment provides a Co2Z-type ferrite material, said Co2The preparation method of the Z-type ferrite material comprises the following steps:
(1) 0.052mol of Sr (NO) is weighed3)20.1mol of Co (NO)3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain Y-shaped mixed solution;
0.052mol of Sr (NO) is weighed3)20.6mol of Fe (NO)3)3Dissolving in 0.5L deionized water, and completely dissolving to obtain M-type mixed solution;
(2) electrodialysis of NO in solution3-Separating by an anion exchange membrane to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) respectively adding 1mol of ammonium bicarbonate into the Y-type cation mixed solution and the M-type cation mixed solution obtained in the step (2), stirring for 12h at normal temperature, and then placing in a drying oven at 110 ℃ for drying to obtain a Y-type ferrite precursor and an M-type ferrite precursor;
(4) sieving the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3), mixing according to the molar ratio of 1.1:1, adding 0.3 wt% of PVA binder for granulation and pressing into blocks, presintering at 1280 ℃ for one time, and preserving heat for 1 h;
(5) vibrating and grinding the product after the primary presintering for 40s, sintering at 1200 ℃, and preserving heat for 1h to obtain the Co2A Z-type ferrite material.
Example 4
This example and implementationExample 1 the difference is that in the step (1) of this example, the raw material of the Y-type mixed solution is 0.052mol of SrCl20.1mol of CoCl2And 0.6mol of FeCl3(ii) a The raw material of the M type mixed solution was molSrCl of 0.0522And molFeCl of 0.63。
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between this example and example 1 is that in step (1) of this example, the raw material of the Y-type mixed solution is 0.052mol of BaCl20.1mol of CoCl2And 0.6mol of FeCl3(ii) a The raw material of the M-type mixed solution was molBaCl of 0.0522And molFeCl of 0.63。
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between this example and example 1 is that the primary calcination temperature in step (4) of this example is 1350 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the primary calcination temperature in step (4) of this example is 1150 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
The difference between this example and example 1 is that the sintering temperature in step (5) of this example is 1250 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The Z-type ferrite is prepared by the coprecipitation method according to the comparative example, and the specific implementation mode is as follows:
(1) 0.15mol of Ba (NO) was weighed3)20.1mol of Co (NO)3)21.2mol of Fe (NO)3)3Dissolving in 0.5L deionized water to obtain a mixed solution;
(2) adding 2mol of sodium carbonate into the mixed solution obtained in the step (1), stirring for 8h at normal temperature, and standing;
(3) and (3) centrifuging the mixture obtained in the step (2), filtering and drying to obtain a precipitate.
(4) Adding 0.3 wt% of PVA binder, granulating, pressing into blocks, presintering at 1250 ℃ for one time, and preserving heat for 4 hours;
(5) vibrating and grinding the product after the primary presintering for 20s, sintering at 1150 ℃, and preserving heat for 4h to obtain the Co2A Z-type ferrite material.
Comparative example 2
The comparative example prepares the Z-type ferrite according to a solid phase method, and the specific implementation mode is as follows:
(1) 0.15mol of BaCO3, 0.1mol of CoO, 0.6mol of Fe were weighed out2O3Ball milling and mixing for 2 h;
(2) drying and presintering at 1250 ℃ for 2 h;
(3) performing secondary ball milling for 2 hours, and drying;
(4) and (4) after drying, carrying out vibromilling for 20s, sintering at 1150 ℃ and preserving heat for 4h to obtain the Z-type ferrite.
Comparative example 3
The comparative example is different from example 1 in that the secondary sintering was directly performed without primary calcination.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The comparative example is different from example 1 in that only one firing is performed and secondary sintering is not performed.
The remaining preparation methods and parameters were in accordance with example 1.
Co prepared in examples 1 to 8 and comparative examples 1 to 42The Z-type ferrite material was mixed with a 6 wt% PVA solution, pressed into an annular blank, and then calcined at 1280 ℃ to prepare a sample, and the initial permeability μ' and loss tangent tan δ of the sample were measured.
Co obtained in examples 1 to 2 and comparative examples 1 to 4 was measured by a scanning electron microscope and a laser particle size analyzer2Particle size of the Z-type ferrite material. Particle size, initial permeability μ' and dielectric loss angleThe results of the tangent tan. delta. are shown in Table 1.
TABLE 1
Figure BDA0003267635220000111
From the data results of example 1 and examples 6 and 7, it is known that the temperature of one-time pre-sintering is too high, which is not favorable for subsequent crushing, the particles are large, the loss is too high, and the temperature is too low, which causes phase difference and lowers the powder magnetic permeability.
From the data results of examples 1 and 8, it is understood that the particle size is increased and the loss is increased due to the excessively high temperature of the secondary sintering.
As can be seen from the data results of examples 1-8 and comparative examples 1-2, Co prepared by the preparation method provided by the present invention2The Z-type ferrite material has relatively small granularity and small dielectric loss tangent.
As is clear from the data results of example 1 and comparative examples 3 and 4, it was found that the high purity Z-type ferrite could not be efficiently prepared by only performing the primary pre-firing or the secondary sintering.
In conclusion, the invention prepares Co with uniform mixing, smaller granularity and higher magnetic permeability by an electrodialysis method2The ferrite material of Z type, suitable for in the ultra-high frequency magnetic device, and reduced the sintering temperature, has saved the preparation process, the ferrite material prepared by the invention, its granulometry is under 0.88 μm, and the initial permeability μ' is above 3.9, the dielectric loss tangent tan delta is under 0.045.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. Co2Z-type ferrite materialThe preparation method is characterized by comprising the following steps:
(1) will contain Fe3+Soluble metal salt of (2), soluble metal salt containing substituted metal ion, soluble metal salt containing Co2+Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe3+Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) carrying out first mixing on the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out first drying to obtain a Y-type ferrite precursor;
carrying out second mixing on the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate, and carrying out second drying to obtain an M-type ferrite precursor;
(4) carrying out compression molding, primary presintering and secondary sintering on the Y-type ferrite precursor in the step (3), the M-type ferrite precursor in the step (3) and a binder to obtain the Co2A Z-type ferrite material;
wherein the substituted metal ion comprises Ba2+And/or Sr2+。
2. Co according to claim 12The preparation method of the Z-type ferrite material is characterized in that the Fe contained in the step (1)3+Soluble metal salt of (2), Co-containing2+The soluble metal salt of (2) and the soluble metal salt containing a substituted metal ion include any one of a chloride salt, a nitrate salt or an organic salt or a combination of at least two thereof.
3. Co according to claim 1 or 22The preparation method of the Z-type ferrite material is characterized in that the ion exchange membrane used in the electrodialysis method in the step (2) comprises an anion exchange membrane, a cation exchange membrane or ion exchangeAny one of or a combination of at least two of the composite films.
4. Co according to any one of claims 1 to 32A method for preparing a Z-type ferrite material, wherein the first mixing and the second mixing in step (3) each independently comprise stirring;
preferably, the first mixing and the second mixing in the step (3) are respectively and independently 5-12 h;
preferably, the temperature of the first drying and the second drying in the step (3) is 100-120 ℃ independently.
5. Co according to any one of claims 1 to 42The preparation method of the Z-type ferrite material is characterized in that in the step (4), the molar ratio of the Y-type ferrite precursor in the step (3) to the M-type ferrite precursor in the step (3) is (1-1.1): 1.
6. Co according to any one of claims 1 to 52The preparation method of the Z-type ferrite material is characterized in that the product obtained after the primary presintering in the step (4) is ground;
preferably, the grinding time is 10-60 s.
7. Co according to any one of claims 1 to 62The preparation method of the Z-type ferrite material is characterized in that the temperature of the primary presintering in the step (4) is 1200-1280 ℃;
preferably, the time of the primary pre-sintering in the step (4) is 1-6 h;
preferably, the temperature of the secondary sintering in the step (4) is 1100-1200 ℃;
preferably, the time of the secondary sintering in the step (4) is 1-6 h.
8. Co according to any one of claims 1 to 72The preparation method of the Z-type ferrite material is characterized by comprising the following steps of:
(1) will contain Fe3+Soluble metal salt of (2), soluble metal salt containing substituted metal ion containing Co2+Mixing the soluble metal salt with a solvent to obtain a Y-shaped mixed solution;
will contain Fe3+Mixing the soluble metal salt, the soluble metal salt containing the substituted metal ions and the solvent to obtain an M-type mixed solution;
(2) treating the Y-type mixed solution in the step (1) and the M-type mixed solution in the step (1) respectively by adopting an electrodialysis method to obtain a Y-type cation mixed solution and an M-type cation mixed solution;
(3) stirring the Y-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain a Y-type ferrite precursor;
stirring the M-type cation mixed solution obtained in the step (2) and ammonium bicarbonate for 5-12 hours, and drying at 100-120 ℃ to obtain an M-type ferrite precursor;
(4) carrying out compression molding on the Y-type ferrite precursor in the step (3) and the M-type ferrite precursor in the step (3) by using a binder according to a molar ratio of (1-1.1) to 1, presintering for 1-6 h at 1200-1280 ℃, and grinding a product after the presintering for 10-60 s; then carrying out secondary sintering at 1100-1200 ℃ for 1-6 h to obtain the Co2A Z-type ferrite material;
wherein the substituted metal ion comprises Ba2+And/or Sr2+。
9. Co2The preparation method of the Z-type ferrite material is characterized in that the Co is2The Z-type ferrite material is made of Co as claimed in any one of claims 1 to 82The Z-type ferrite material is prepared by the preparation method.
10. Co2Use of a Z-type ferrite material, characterized in that Co as claimed in claim 9 is used2The Z-type ferrite material is used for ultrahigh frequency magnetic devices.
CN202111091418.4A 2021-09-17 2021-09-17 Co2Z type ferrite material and preparation method and application thereof Active CN113744991B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111091418.4A CN113744991B (en) 2021-09-17 2021-09-17 Co2Z type ferrite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111091418.4A CN113744991B (en) 2021-09-17 2021-09-17 Co2Z type ferrite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113744991A true CN113744991A (en) 2021-12-03
CN113744991B CN113744991B (en) 2022-10-11

Family

ID=78739603

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111091418.4A Active CN113744991B (en) 2021-09-17 2021-09-17 Co2Z type ferrite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113744991B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116396069A (en) * 2023-03-24 2023-07-07 电子科技大学 Preparation method of non-magnetic field oriented textured hexaferrite material
WO2024001355A1 (en) * 2022-06-30 2024-01-04 横店集团东磁股份有限公司 Co2z-type ferrite magnetic powder, method for preparing same, and magnetic-plastic composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313617A (en) * 2001-02-07 2002-10-25 Sumitomo Special Metals Co Ltd Permanent magnet and its manufacturing method
JP2008133166A (en) * 2006-10-25 2008-06-12 Hitachi Metals Ltd Hexagonal z-type ferrite sintered body and manufacturing method thereof
CN106498497A (en) * 2016-12-09 2017-03-15 扬州大学 A kind of method for preparing granule single crystallization Co2Z hexad ferrite powder body
CN108329022A (en) * 2018-03-27 2018-07-27 电子科技大学 A kind of preparation method for the Z-type hexad ferrite substrate being orientated self
CN112851325A (en) * 2021-01-29 2021-05-28 无锡杰夫电声股份有限公司 Z-type hexaferrite powder with high saturation magnetization and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002313617A (en) * 2001-02-07 2002-10-25 Sumitomo Special Metals Co Ltd Permanent magnet and its manufacturing method
JP2008133166A (en) * 2006-10-25 2008-06-12 Hitachi Metals Ltd Hexagonal z-type ferrite sintered body and manufacturing method thereof
CN106498497A (en) * 2016-12-09 2017-03-15 扬州大学 A kind of method for preparing granule single crystallization Co2Z hexad ferrite powder body
CN108329022A (en) * 2018-03-27 2018-07-27 电子科技大学 A kind of preparation method for the Z-type hexad ferrite substrate being orientated self
CN112851325A (en) * 2021-01-29 2021-05-28 无锡杰夫电声股份有限公司 Z-type hexaferrite powder with high saturation magnetization and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024001355A1 (en) * 2022-06-30 2024-01-04 横店集团东磁股份有限公司 Co2z-type ferrite magnetic powder, method for preparing same, and magnetic-plastic composite material
CN116396069A (en) * 2023-03-24 2023-07-07 电子科技大学 Preparation method of non-magnetic field oriented textured hexaferrite material
CN116396069B (en) * 2023-03-24 2024-01-26 电子科技大学 Preparation method of non-magnetic field oriented textured hexaferrite material

Also Published As

Publication number Publication date
CN113744991B (en) 2022-10-11

Similar Documents

Publication Publication Date Title
KR101229611B1 (en) Magnesium oxide particle aggregate, and method for production thereof
CN113744991B (en) Co2Z type ferrite material and preparation method and application thereof
CN112851344B (en) Microwave dielectric ceramic with medium dielectric constant and preparation method thereof
CN102260072A (en) Method for synthesizing high-performance barium ferrite by using molten salt as flux and reaction medium
CN114349493B (en) Copper ion doped calcium silicate microwave dielectric ceramic and preparation method thereof
CN111138193B (en) Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof
CN107188557A (en) A kind of microwave dielectric ceramic materials and preparation method thereof
WO2019126969A1 (en) Dielectric ceramic material and method for preparing same
CN105693243A (en) Preparation method of dielectric constant high-performance microwave dielectric ceramic
CN102875143A (en) Method for preparing microwave dielectric ceramic material
CN113968732A (en) Preparation method of high-stability low-loss microwave dielectric ceramic material and microwave dielectric ceramic material prepared by applying same
CN103626485B (en) Production method of permanent magnetic ferrite pre-sintering material
CA1207981A (en) Production of fine ferrimagnetic spinels
CN111747745A (en) Dielectric powder for 5G filter and preparation method thereof
CN106587972A (en) Preparation method of Z-type ferrite plate-like powder
CN102815936B (en) Preparation method for copper calcium titanate multiphase ceramic with high potential gradient
CN109437901A (en) A kind of microwave-medium ceramics of perovskite structure and preparation method thereof
CN110746188B (en) Microwave dielectric ceramic composition, preparation method and application thereof, microwave dielectric ceramic, preparation method and application thereof, and microwave device
CN112794368A (en) Composite material with high magnetic permeability and low dielectric constant as well as preparation method and application thereof
CN103396110A (en) Barium titanate-nickel zinc ferrite composite ceramic material and preparation method thereof
CN117228734B (en) Chemical coprecipitation preparation method of 18H hexaferrite
JP7473713B2 (en) Lithium-cobalt composite oxide particles and their manufacturing method, lithium-cobalt composite oxide particle composition and their manufacturing method
WO2021125344A1 (en) Amorphous lithium ion-conductive oxide powder, method for producing same, and method for producing lithium ion-conductive oxide powder having nasicon crystal structure
KR20120061358A (en) Y-type ferrite and molded article manufactured with the same
KR20060102928A (en) Manufacturing method of barium titanate powder

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant