CN115475745A - Preparation process and coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry - Google Patents
Preparation process and coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry Download PDFInfo
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Abstract
The invention discloses a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry. According to the method, the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry is obtained through a rare earth oxide sol process, a ferrite sol process, a rare earth ferrite sol-gel process and a vanadium-doped sol-gel slurry process, and the slurry can be used for completing substrate coating through improved lifting coating and screen printing coating processes. The invention solves the problems that the magnetic film material is inactivated due to the fact that the magnetic film is separated from the matrix in the using process, cracks and gaps occur in the magnetic film material due to uneven distribution and compensation of the material, and the like, and simultaneously improves the performance of the magnetic film material.
Description
Technical Field
The invention belongs to the field of vanadium-based functional materials, and particularly relates to a ferrite magnetic composite material prepared by using vanadium oxide as a thermal expansion regulating additive and a material forming technology thereof.
Background
The country definitely develops fields such as 5G basic station, photovoltaic, wind-powered electricity generation, energy storage, new energy automobile, with the development of magnetic material trade, is the expanding opportunity period that is rare, who can preempt market demand and take the lead, who just can obtain stronger competitiveness and longer life.
Ferromagnetic metal oxide materials mainly include permanent ferrite materials and soft ferrite materials, and are one of the most widely used magnetic materials. The iron oxide powder is a main raw material for preparing ferromagnetic metal oxide materials, and mainly comes from the steel manufacturing industry and the chemical industry. The permanent magnetic ferrite material is a ferromagnetic material which is prepared by taking ferric oxide as a main raw material through a ceramic process and has strong demagnetization resistance and high residual magnetic induction intensity. The permanent magnetic ferrite material is divided into a sintered permanent magnetic ferrite material and a bonded permanent magnetic ferrite material, wherein the sintered permanent magnetic ferrite material is divided into a dry-pressed permanent magnetic ferrite material and a wet-pressed permanent magnetic ferrite material. The ferrite soft magnetic material is a ferrite material which is easy to magnetize and demagnetize under a weaker magnetic field. The ferrite soft magnetic material is divided into manganese zinc ferrite material, nickel zinc ferrite material, magnesium zinc ferrite material and lithium zinc ferrite material.
Due to the unique 4f electron layer structure of the rare earth, uniaxial magnetic anisotropy can be formed in crystal structures combined with 3d element compounds, and the rare earth has very excellent extraordinary magnetic properties, such as the highest magnetic energy product of rubidium, iron and boron in a rare earth permanent magnet, high working temperature of a samarium-cobalt permanent magnet and low temperature coefficient.
The existing research shows that the nanocrystalline two-phase exchange coupling rare earth permanent magnet material has the advantages of better high temperature resistance and high magnetic energy product, and the two-phase coupling rare earth permanent magnet material is obtained by exchanging and coupling the rare earth permanent magnet material with high magnetocrystalline anisotropy and the soft magnetic material with high saturation magnetization at the nanoscale. The theoretical maximum magnetic energy product far exceeds rubidium, iron and boron, and has a magnetostriction coefficient which is dozens of times higher than that of iron, cobalt and nickel. The rare earth oxide doped ferrite can greatly optimize the performance of the ferrite, meet the application requirements of high-end industrial production products, and particularly has extremely high application prospect in magnetic thin film materials.
The magnetic thin film material refers to a ferromagnetic (ferromagnetic and ferrimagnetic) material with a small thickness, and is referred to as a magnetic thin film material for short. At present, the coating methods which are relatively popular in industrial application mainly comprise a pulling coating method and a screen printing coating method, the two methods have higher practical applicability due to shorter flow and lower cost, but the problems that the material is inactivated because the thermal expansion coefficients of the film material and the matrix are difficult to match, the magnetic film is separated from the matrix in the use process, the crack and the gap of the magnetic film material are caused due to uneven distribution and compensation of the material and the like exist.
Disclosure of Invention
The invention aims to provide a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry. The vanadium oxide material has the effect of refining grains, and the proper amount of vanadium oxide material is added into the magnetic film material, so that the matching of the thermal expansion coefficients of the magnetic film material and the metal matrix material can be adjusted to a certain degree, the problems that the magnetic film is separated from the matrix in the use process of the magnetic film material to cause material inactivation, the split and gap of the magnetic film material are caused by uneven distribution of the material and the like are solved, and the performance of the magnetic film material is improved.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprise the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving rare earth nitrate into water to form a saturated solution, adding a dispersing agent and a complexing agent, stirring to uniformly disperse the rare earth nitrate, and placing the mixture into an oil bath pot or a water bath pot to stir until sol is generated to obtain rare earth oxide sol;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form a saturated solution, adding a dispersing agent and a complexing agent, stirring to uniformly disperse the ferric nitrate, and placing the mixture in an oil bath pot or a water bath pot to stir until sol is generated to obtain ferrite sol;
s1.3, a rare earth ferrite sol-gel process: mixing and stirring the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2, and simultaneously adding 1mol L of the rare earth oxide sol and the ferrite sol -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, vanadium-doped sol-gel slurry process: uniformly stirring the rare earth ferrite sol gel obtained in the step S1.3, placing the sol gel in a constant-temperature oscillation box, oscillating for 10-12 h at 80-90 ℃, taking out the sol gel from the constant-temperature oscillation box, adding a vanadium oxide precursor, uniformly stirring, placing the sol gel in the constant-temperature oscillation box, and continuing oscillating until composite gel is formed to obtain vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating a film:
the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 comprises a screen printing method and a pulling method, and comprises the following operation steps:
s2.1, a screen printing method:
s2.1.1, placing the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 on the surface of a screen printing machine, placing a metal substrate on the bottom surface of the screen printing machine, and performing printing and film coating, wherein the mass ratio of the screen printing slurry to the substrate is 1;
s2.1.2, placing the coated substrate obtained in the step S2.1.1 into a muffle furnace, performing constant temperature thermal diffusion at the temperature of 80-120 ℃, then calcining to form a film, wherein the heating rate is 5-10 ℃/min, the calcining temperature is 700-750 ℃, the calcining time is 2-3 h, then annealing, the annealing rate is 10-15 ℃/min, annealing is performed to 300-400 ℃, heat preservation is performed for 2-3 h, and finally, natural cooling is performed in the air;
s2.2, a pulling method:
s2.2.1, vertically suspending the substrate on a pulling machine, and performing pulling coating by using the slurry of the vanadium oxide rare earth double-doped ferrite magnetic composite film in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1;
s2.2.2, placing the coated substrate obtained in the S2.2.1 into a muffle furnace, performing constant-temperature thermal diffusion at 70-100 ℃, then calcining to form a film, wherein the calcining temperature rise rate is 5-10 ℃/min, the calcining temperature is 600-650 ℃, the calcining time is 2-3 h, then annealing, the annealing rate is 10-15 ℃/min, annealing is performed to 200-300 ℃, heat preservation is performed for 2-3 h, and finally, natural cooling is performed in the air.
The rare earth nitrate comprises cerium nitrate, samarium nitrate, yttrium nitrate, zirconium nitrate and lanthanum nitrate; the complexing agent is citric acid monohydrate, and the amount n of the substance 1 Rare earth metal ion/n 2 10-11 parts of citric acid monohydrate, and n is the amount of the substance 3 Fe 3+ /n 4 10-11 parts of citric acid monohydrate; the dispersant comprises propylene glycol and ethylene glycol, and the mass m of the dispersant is 1 Citric acid monohydrate/m 2 The dispersant is 7-8.
The temperature of the oil bath kettle and the water bath kettle is 80-100 ℃, and the stirring speed is 70-100 r/min.
The addition amount of the rare earth oxide sol and the ferrite sol is calculated according to the molar ratio of the rare earth element to the iron element of 1-1.2.
The vanadium oxide precursor comprises vanadyl sulfate, and the mass ratio of the rare earth oxide sol to the vanadium oxide precursor is 0-1 and is (5-6).
Compared with the prior art, the invention has the beneficial effects that:
(1) The performance of the magnetic material can be greatly improved by adding the composite rare earth;
(2) According to the invention, two traditional coating processes of silk-screen printing and dip coating are optimized, and the obtained coating has excellent performance;
(3) The vanadium oxide precursor is adopted to adjust the matching property of the thermal expansion coefficients of the film material and the matrix, so that the problems that the magnetic film is separated from the matrix to cause material inactivation, and the magnetic film material has cracks, gaps and the like due to uneven distribution of the material are avoided.
Drawings
FIG. 1 is an XRD pattern of a yttrium zirconium rare earth oxide film.
Fig. 2 is a XRD pattern of the samarium cerium rare earth oxide film layer.
Detailed Description
The invention discloses a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry, and the following embodiment is adopted to illustrate the specific implementation mode and the implementation effect of the invention.
[ example 1 ] of the present invention:
a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving yttrium nitrate and zirconium nitrate into water to form saturated solution according to the amount n of the substances 1 Rare earth metal ion (yttrium ion + zirconium ion)/n 2 Citric acid monohydrate 10.5 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form saturated solution according to the amount n of the substance 3 Fe 3+ /n 4 Citric acid monohydrate 10.5 adding a complexing agent citric acid monohydrate to the solution of citric acid monohydrate, according to mass m 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.3, a rare earth ferrite sol-gel process: mixing and stirring the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2 according to a molar ratio 1 of the rare earth element to the iron element of 1 -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, vanadium-doped sol-gel slurry process: stirring the rare earth ferrite sol-gel obtained in the step S1.3 uniformly (70 r/min), placing the sol-gel in a constant-temperature shaking box to shake for 10-12 h at 80-90 ℃, then taking out the sol-gel from the constant-temperature shaking box to add vanadyl sulfate, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1;
s2, coating a film:
s2.1, a screen printing method:
s2.1.1, placing the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 on the surface of a screen printing machine, placing a metal substrate on the bottom surface of the screen printing machine, and performing printing and film coating, wherein the mass ratio of the screen printing slurry to the substrate is 1, the printing times are 3, and the printing and dipping time is 10min;
s2.1.2, placing the coated substrate obtained in the step S2.1.1 into a muffle furnace, performing constant-temperature thermal diffusion at 80 ℃, then calcining to form a film, wherein the heating rate is 5 ℃/min, the calcining temperature is 700 ℃, the calcining time is 2h, then annealing is performed, the annealing rate is 10 ℃/min, the annealing is performed to 300 ℃, the temperature is kept for 2h, and finally, the substrate is naturally cooled in the air.
[ example 2 ]:
a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving yttrium nitrate and zirconium nitrate into water to form saturated solution according to the amount n of the substances 1 Rare earth metal ion (yttrium ion + zirconium ion)/n 2 Citric acid monohydrate 10.5 adding a complexing agent citric acid monohydrate to the solution of citric acid monohydrate, according to mass m 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form saturated solution according to the amount n of the substance 3 Fe 3+ /n 4 Citric acid monohydrate 10.5 adding a complexing agent citric acid monohydrate to the solution of citric acid monohydrate, according to mass m 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.3, a rare earth ferrite sol-gel process: mixing and stirring the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2 according to a molar ratio 1 of the rare earth element to the iron element of 1 -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, vanadium-doped sol-gel slurry process: stirring (70 r/min) the rare earth ferrite sol-gel obtained in the step S1.3 uniformly, placing the mixture in a constant-temperature oscillation box, oscillating for 10-12 h at 80-90 ℃, then taking out the mixture from the constant-temperature oscillation box, adding vanadyl sulfate, and placing the mixture in the constant-temperature oscillation box to continuously oscillate until composite gel is formed after stirring (70 r/min) uniformly, so as to obtain vanadium-doped sol-gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating a film:
s2.2, a pulling method:
s2.2.1, vertically suspending the substrate on a pulling machine, and performing pulling coating by using the slurry of the vanadium oxide rare earth double-doped ferrite magnetic composite film in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1;
s2.2.2, placing the coated substrate obtained in the S2.2.1 into a muffle furnace, performing constant-temperature thermal diffusion at 100 ℃, then calcining to form a film, wherein the calcining temperature rise rate is 5 ℃/min, the calcining temperature is 600 ℃, the calcining time is 2 hours, then annealing, the annealing rate is 10 ℃/min, annealing is performed to 200 ℃, the temperature is kept for 2 hours, and finally, the coated substrate is naturally cooled in the air.
[ example 3 ]:
a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving cerium nitrate and samarium nitrate into water to form saturated solution according to the amount n of the substances 1 Rare earth metal ion (cerium ion + samarium ion)/n 2 Citric acid monohydrate 10.5 1 Citric acid monohydrate/m 2 Adding propylene glycol 7.2 as a dispersant into the mixture 1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath kettle at the temperature of 80 ℃ to stir (70 r/min) until sol is generated to obtain rare earth oxide sol;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form saturated solution according to the amount n of the substance 3 Fe 3+ /n 4 Citric acid monohydrate 10.5 adding a complexing agent citric acid monohydrate to the solution of citric acid monohydrate, according to mass m 1 Citric acid monohydrate/m 2 Propylene glycol 7.2, adding a dispersant propylene glycol into the mixture 1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath kettle at the temperature of 80 ℃ to stir (70 r/min) until sol is generated to obtain ferrite sol;
s1.3, a rare earth ferrite sol-gel process: will step S1.1 instituteObtaining rare earth oxide sol and ferrite sol obtained by S1.2, mixing and stirring (70 r/min) according to the molar ratio of the rare earth element to the iron element of 1 -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: stirring the rare earth ferrite sol-gel obtained in the step S1.3 uniformly (70 r/min), placing the sol-gel in a constant-temperature shaking box to shake for 10-12 h at 80-90 ℃, then taking out the sol-gel from the constant-temperature shaking box to add vanadyl sulfate, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1;
s2, coating a film:
s2.1, a screen printing method:
s2.1.1, placing the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 on the surface of a screen printing machine, placing a metal substrate on the bottom surface of the screen printing machine, and performing printing and film coating, wherein the mass ratio of the screen printing slurry to the substrate is 1, the printing times are 3, and the printing and dipping time is 10min;
s2.1.2, placing the coated substrate obtained in the step S2.1.1 into a muffle furnace, performing constant-temperature thermal diffusion at 80 ℃, then calcining to form a film, wherein the heating rate is 5 ℃/min, the calcining temperature is 700 ℃, the calcining time is 2h, then annealing, the annealing rate is 10 ℃/min, annealing is performed to 300 ℃, the temperature is kept for 2h, and finally, the substrate is naturally cooled in the air.
Example 4:
a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving cerium nitrate and samarium nitrate into water to form saturated solution according to the amount n of the substances 1 Rare earth metal ion (cerium ion + samarium ion)/n 2 Citric acid monohydrate 10.5 adding complexing agent citric acid monohydrate,according to mass m 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form saturated solution according to the amount n of the substance 3 Fe 3+ /n 4 Citric acid monohydrate 10.5 adding a complexing agent citric acid monohydrate to the solution of citric acid monohydrate, according to mass m 1 Citric acid monohydrate/m 2 Adding propylene glycol as a dispersant into propylene glycol 7.2;
s1.3, a rare-earth ferrite sol-gel process: mixing and stirring the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2 according to the molar ratio of the rare earth element to the iron element of 1 -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, vanadium-doped sol-gel slurry process: stirring the rare earth ferrite sol-gel obtained in the step S1.3 uniformly (70 r/min), placing the sol-gel in a constant-temperature shaking box to shake for 10-12 h at 80-90 ℃, then taking out the sol-gel from the constant-temperature shaking box to add vanadyl sulfate, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1;
s2, coating a film:
s2.2, a pulling method:
s2.2.1, vertically suspending the substrate on a pulling machine, and performing pulling coating by using the slurry of the vanadium oxide rare earth double-doped ferrite magnetic composite film in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1;
s2.2.2, placing the coated substrate obtained in the S2.2.1 into a muffle furnace, performing constant-temperature thermal diffusion at 100 ℃, then calcining to form a film, wherein the calcining temperature rise rate is 5 ℃/min, the calcining temperature is 600 ℃, the calcining time is 2 hours, then annealing, the annealing rate is 10 ℃/min, annealing is performed to 200 ℃, the temperature is kept for 2 hours, and finally, the coated substrate is naturally cooled in the air.
In order to prove that the process can obtain a perfect rare earth phase, the invention researches the phase of a film layer obtained by rare earth (cerium nitrate and samarium nitrate)/(yttrium nitrate and zirconium nitrate) through the whole preparation process. The specific method is that a matrix film is prepared through S1.1, S1.3 (no addition of oxidized ferrite sol), S1.4 (no addition of vanadyl sulfate) and S2.1, in-situ high-temperature XRD detection is carried out on the film layer in different intervals, and the yttrium zirconium rare earth oxide film layer is shown in figure 1 and the samarium cerium rare earth oxide film layer is shown in figure 2. The figure shows that the obtained film layer metal oxide presents a perfect phase structure, no other impurity phase is generated, and the comparison result of the in-situ high-temperature XRD test shows that the obtained oxide film has good thermochemical stability.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. A preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are characterized by comprising the following steps:
s1, a preparation process of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprises the following steps:
s1.1, rare earth oxide sol process: dissolving rare earth nitrate into water to form saturated solution, adding a dispersant and a complexing agent, stirring to uniformly disperse the solution, and placing the solution in an oil bath pot or a water bath pot to stir until sol is generated to obtain rare earth oxide sol;
s1.2, ferrite sol process: dissolving ferric nitrate into water to form a saturated solution, adding a dispersing agent and a complexing agent, stirring to uniformly disperse the ferric nitrate, and placing the mixture in an oil bath pot or a water bath pot to stir until sol is generated to obtain ferrite sol;
s1.3, a rare-earth ferrite sol-gel process: mixing and stirring the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2, and simultaneously adding 1mol L of the rare earth oxide sol and the ferrite sol -1 Adjusting the pH value to 7.5 by ammonia water until the rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: uniformly stirring the rare earth ferrite sol gel obtained in the step S1.3, placing the sol gel in a constant-temperature shaking box to shake for 10-12 h at 80-90 ℃, then taking out the sol gel from the constant-temperature shaking box, adding a vanadium oxide precursor into the sol gel, uniformly stirring, placing the sol gel in the constant-temperature shaking box, and continuously shaking until composite gel is formed to obtain vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating a film:
the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 comprises a screen printing method and a pulling method, and comprises the following operation steps:
s2.1, a screen printing method:
s2.1.1, placing the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4 on the surface of a screen printing machine, placing a metal substrate on the bottom surface of the screen printing machine, and performing printing and film coating, wherein the mass ratio of the screen printing slurry to the substrate is 1;
s2.1.2, placing the coated substrate obtained in the step S2.1.1 into a muffle furnace, performing constant temperature thermal diffusion at the temperature of 80-120 ℃, then calcining to form a film, wherein the heating rate is 5-10 ℃/min, the calcining temperature is 700-750 ℃, the calcining time is 2-3 h, then annealing, the annealing rate is 10-15 ℃/min, annealing is performed to 300-400 ℃, heat preservation is performed for 2-3 h, and finally, natural cooling is performed in the air;
s2.2, a pulling method:
s2.2.1, vertically suspending the substrate on a pulling machine, and performing pulling coating by using the slurry of the vanadium oxide rare earth double-doped ferrite magnetic composite film obtained in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1;
s2.2.2, placing the coated substrate obtained in the S2.2.1 into a muffle furnace, performing constant-temperature thermal diffusion at 70-100 ℃, then calcining to form a film, wherein the calcining temperature rise rate is 5-10 ℃/min, the calcining temperature is 600-650 ℃, the calcining time is 2-3 h, then annealing, the annealing rate is 10-15 ℃/min, annealing is performed to 200-300 ℃, the temperature is kept for 2-3 h, and finally, the substrate is naturally cooled in the air.
2. The preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry according to claim 1, wherein the rare earth nitrate comprises cerium nitrate, samarium nitrate, yttrium nitrate, zirconium nitrate and lanthanum nitrate; the complexing agent is citric acid monohydrate, and the amount n of the substance 1 Rare earth metal ion/n 2 10-11 parts of citric acid monohydrate, and n is the amount of the substance 3 Fe 3+ /n 4 10-11 parts of citric acid monohydrate; the dispersant comprises propylene glycol and ethylene glycol, and the mass m of the dispersant is 1 Citric acid monohydrate/m 2 The dispersant is 7-8.
3. The preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry according to claim 1, wherein the temperature of the oil bath kettle and the water bath kettle is 80-100 ℃, and the stirring speed is 70-100 r/min.
4. The preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry according to claim 1, wherein the addition amounts of the rare earth oxide sol and the ferrite sol are calculated according to the molar ratio of the rare earth element to the iron element of 1-1.2.
5. The preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry according to claim 1, wherein the vanadium oxide precursor comprises vanadyl sulfate, and the mass ratio of the rare earth oxide sol to the vanadium oxide precursor is 0-1.
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