CN115475745B - 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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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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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. The method obtains vanadium oxide rare earth double-doped ferrite magnetic composite film slurry 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 complete matrix coating through an improved pulling coating process and a screen printing coating process. The invention solves the problems of material inactivation caused by magnetic film detachment from a matrix, and cracking and gaps caused by uneven material division and compensation, and the like of the magnetic film material in the using process, and 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 clearly and vigorously develops the fields of 5G base stations, photovoltaics, wind power, energy storage, new energy automobiles and the like in the period of fourteen five, is a remarkable development opportunity period compared with the development of the magnetic material industry, and can preempt market demands and obtain stronger competitiveness and longer-term vitality.
Ferromagnetic metal oxide materials mainly comprise permanent magnetic ferrite materials and soft magnetic ferrite materials, and are one of the most widely used magnetic materials. Iron oxide powder is a main raw material for preparing ferromagnetic metal oxide materials, and is mainly derived from the iron and steel manufacturing industry and the chemical industry. The permanent magnetic ferrite material is a strong magnetic material with strong demagnetizing resistance and high residual magnetic induction intensity, which is manufactured by taking ferric oxide as a main raw material through a ceramic process method. 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. Ferrite soft magnetic materials are classified into manganese zinc ferrite materials, nickel zinc ferrite materials, magnesium zinc ferrite materials, and lithium zinc ferrite materials.
Because of the unique 4f electronic layer structure, the rare earth can form uniaxial magnetic anisotropy in a crystal structure combined with 3d element compounds, and has very excellent supernormal magnetic performance, such as highest magnetic energy product of rubidium-iron-boron in rare earth permanent magnets, high working temperature of samarium-cobalt permanent magnets and low temperature coefficient.
At present, research shows that the nanocrystalline dual-phase exchange coupling rare earth permanent magnet material has the advantages of better high temperature resistance and high magnetic energy product, and the dual-phase coupling rare earth permanent magnet material is obtained by exchange coupling of a rare earth permanent magnet material with high magnetocrystalline anisotropy and a soft magnetic material with high saturation magnetization in a nanoscale. The theoretical maximum magnetic energy product of the magnetic material far exceeds that of rubidium-iron-boron, and the magnetic material has a magnetostriction coefficient which is tens of times higher than that of iron-cobalt-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 has extremely high application prospects in magnetic film materials.
The magnetic film material refers to ferromagnetic (ferromagnetic and ferrimagnetic) materials with smaller thickness, and is called magnetic film material for short. The current coating methods which are commonly applied in industry mainly comprise a lifting coating method and a screen printing coating method, and the two methods have higher practical applicability due to shorter flow and lower cost, but have the problems that a magnetic film is separated from a substrate in the use process to cause material inactivation, and the magnetic film material is split and slit due to uneven division and compensation of the material due to the fact that the thermal expansion coefficients of the film material and the substrate are difficult to match.
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 the vanadium oxide material is added into the magnetic film material to adjust the thermal expansion coefficient matching property of the magnetic film material and the metal matrix material to a certain extent, so that the problems that the magnetic film material is separated from the matrix to cause material inactivation, the split and gap of the magnetic film material are caused by uneven split and supplement of the material in the use process of the magnetic film material are solved, and the performance of the magnetic film material is improved.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the preparation process and the film plating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry comprise the following steps:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 saturated solution, and placing the saturated solution in an oil bath or a water bath kettle 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 saturated solution, and placing the saturated solution in an oil bath or a water bath kettle for stirring until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: 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 -1 Ammonia water is used for adjusting the PH value to 7.5 until rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: placing the rare earth ferrite sol gel obtained in the step S1.3 into a constant temperature shaking box to shake for 10-12 hours at 80-90 ℃, taking out the vanadium oxide precursor from the constant temperature shaking box to stir uniformly, and placing the mixture into the constant temperature shaking box to shake continuously until the composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
the method for coating 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, 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 printer, placing a metal substrate on the bottom surface of the screen printer, printing and coating, wherein the mass ratio of the screen printing slurry to the substrate is 1:1, the printing times are 3, and the printing and dipping time is 10-15 min;
s2.1.2 the substrate obtained in the step S2.1.1 is put into a muffle furnace for thermal diffusion at 80-120 ℃, then calcined to form a film, the heating rate is 5-10 ℃/min, the calcining temperature is 700-750 ℃, the calcining time is 2-3 h, then annealing is carried out, the annealing rate is 10-15 ℃/min, the annealing is carried out to 300-400 ℃, the heat preservation is carried out for 2-3 h, and finally natural cooling is carried out in the air;
s2.2, pulling method:
s2.2.1 vertically suspending the substrate on a pulling machine, and carrying out pulling coating by using the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1:3, the pulling times are 5 times, and the pulling dipping time is 30-40 min;
s2.2.2 the film-coated substrate obtained in S2.2.1 is put into a muffle furnace, subjected to constant-temperature thermal diffusion at 70-100 ℃, then calcined to form a film, the calcining temperature is increased by 5-10 ℃/min, the calcining temperature is 600-650 ℃, the calcining time is 2-3 h, then annealing is carried out, the annealing rate is 10-15 ℃/min, the annealing is carried out to 200-300 ℃, the heat preservation is carried out for 2-3 h, and finally, the film is naturally cooled 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 mass n 1 Rare earth metal ion/n 2 Citric acid monohydrate is 10-11:1, and the mass n is as follows 3 Fe 3+ /n 4 Citric acid monohydrate is 10-11:1; the dispersant comprises propylene glycol and ethylene glycol, and the mass m 1 Citric acid/m hydrate 2 The dispersant is 7-8:1.
The temperature of the oil bath pot and the water bath pot 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 mol ratio of the rare earth element to the iron element of 1-1.2:0.8-1.
The vanadium oxide precursor comprises vanadyl sulfate, and the mass ratio of the rare earth oxide sol to the vanadium oxide precursor is 0-1:5-6.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention adopts the composite rare earth to greatly improve the performance of the magnetic material;
(2) The invention optimizes the screen printing and the lifting coating of two traditional coating processes, and the obtained coating has excellent performance;
(3) The matching property of the thermal expansion coefficient of the film material and the matrix is regulated by adopting the vanadium oxide precursor, so that the problems of material inactivation caused by the separation of the magnetic film from the matrix, split and gap caused by uneven division and compensation of the material and the like of the magnetic film material are avoided.
Drawings
Fig. 1 is an XRD pattern of yttrium zirconium rare earth oxide film.
Fig. 2 is an XRD pattern of samarium-cerium rare earth oxide film.
Detailed Description
The invention relates to a preparation process and a coating method of vanadium oxide rare earth double-doped ferrite magnetic composite film slurry, and adopts the following embodiment to exemplify the specific implementation mode and implementation effect of the invention.
[ example 1 ]:
the preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 mass n 1 Rare earth metal ion (yttrium ion + zirconium ion)/n 2 Citric acid monohydrate 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the propylene glycol, and then placing the mixture into an oil bath at 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 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath at 80 ℃ to stir (70 r/min) until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: 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 mol ratio of the rare earth element to the iron element of 1:1 (70 r/min), and simultaneously adding 1mol L -1 Ammonia water is used for adjusting the PH value to 7.5 until rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: uniformly stirring (70 r/min) the rare earth ferrite sol gel obtained in the step S1.3, placing the mixture in a constant-temperature vibration box, vibrating for 10-12 h at 80-90 ℃, taking out the mixture from the constant-temperature vibration box, adding vanadyl sulfate into the mixture, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1:5, uniformly stirring (70 r/min), placing the mixture in the constant-temperature vibration box, and continuously vibrating the mixture until composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
s2.1, 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 printer, placing a metal substrate on the bottom surface of the screen printer, printing and coating, wherein the mass ratio of the screen printing slurry to the substrate is 1:1, the printing times are 3, and the printing dipping time is 10min;
s2.1.2 the substrate obtained in the step S2.1.1 is placed into a muffle furnace, subjected to constant-temperature thermal diffusion at 80 ℃, then calcined to form a film, the heating rate is 5 ℃/min, the calcining temperature is 700 ℃, the calcining time is 2h, then annealing is carried out, the annealing rate is 10 ℃/min, the annealing is carried out to 300 ℃, the heat is preserved for 2h, and finally, the substrate is naturally cooled in the air.
[ example 2 ]:
the preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 mass n 1 Rare earth metal ion (yttrium ion + zirconium ion)/n 2 Citric acid monohydrate 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the propylene glycol, and then placing the mixture into an oil bath at 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 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath at 80 ℃ to stir (70 r/min) until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: 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 mol ratio of the rare earth element to the iron element of 1:1 (70 r/min), and simultaneously adding 1mol L -1 Ammonia water is used for adjusting the PH value to 7.5 until rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: uniformly stirring (70 r/min) the rare earth ferrite sol gel obtained in the step S1.3, placing the mixture in a constant-temperature vibration box, vibrating for 10-12 h at 80-90 ℃, taking out the mixture from the constant-temperature vibration box, adding vanadyl sulfate into the mixture, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1:5, uniformly stirring (70 r/min), placing the mixture in the constant-temperature vibration box, and continuously vibrating the mixture until composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
s2.2, pulling method:
s2.2.1 vertically suspending the substrate on a pulling machine, and carrying out pulling coating by using the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1:3, the pulling times are 5 times, and the pulling dipping time is 30min;
s2.2.2 the coating substrate obtained in S2.2.1 is placed into a muffle furnace, and is subjected to constant-temperature thermal diffusion at 100 ℃, then calcined to form a film, the calcining temperature is increased at 5 ℃/min, the calcining temperature is 600 ℃, the calcining time is 2h, then the annealing is performed at 10 ℃/min, the annealing is performed to 200 ℃, the heat is preserved for 2h, and finally the film is naturally cooled in the air.
[ example 3 ]:
the preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 mass n 1 Rare earth metal ion (cerium ion+samarium ion)/n 2 Citric acid monohydrate 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the propylene glycol, and then placing the mixture into an oil bath at 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 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath at 80 ℃ to stir (70 r/min) until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: the rare earth oxide sol obtained in the step S1.1 and the ferrite sol obtained in the step S1.2 are mixed according to rare earth elements and ironThe elements are mixed and stirred (70 r/min) in a molar ratio of 1:1, and 1mol L is added at the same time -1 Ammonia water is used for adjusting the PH value to 7.5 until rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: uniformly stirring (70 r/min) the rare earth ferrite sol gel obtained in the step S1.3, placing the mixture in a constant-temperature vibration box, vibrating for 10-12 h at 80-90 ℃, taking out the mixture from the constant-temperature vibration box, adding vanadyl sulfate into the mixture, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1:5, uniformly stirring (70 r/min), placing the mixture in the constant-temperature vibration box, and continuously vibrating the mixture until composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
s2.1, 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 printer, placing a metal substrate on the bottom surface of the screen printer, printing and coating, wherein the mass ratio of the screen printing slurry to the substrate is 1:1, the printing times are 3, and the printing dipping time is 10min;
s2.1.2 the substrate obtained in the step S2.1.1 is placed into a muffle furnace, subjected to constant-temperature thermal diffusion at 80 ℃, then calcined to form a film, the heating rate is 5 ℃/min, the calcining temperature is 700 ℃, the calcining time is 2h, then annealing is carried out, the annealing rate is 10 ℃/min, the annealing is carried out to 300 ℃, the heat is preserved for 2h, and finally, the substrate is naturally cooled in the air.
[ example 4 ]:
the preparation process and the coating method of the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry are carried out according to the following steps:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 mass n 1 Rare earth metal ion (cerium ion+samarium ion)/n 2 Citric acid monohydrate 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Propylene glycol 7.2:1 addition splitStirring propylene glycol powder (70 r/min) to disperse uniformly, and then placing in an oil bath kettle at 80 ℃ and stirring (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 10.5:1 complexing agent citric acid monohydrate was added according to mass m 1 Citric acid/m hydrate 2 Adding propylene glycol as a dispersant into propylene glycol at a ratio of 7.2:1, stirring (70 r/min) to uniformly disperse the mixture, and then placing the mixture in an oil bath at 80 ℃ to stir (70 r/min) until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: 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 mol ratio of the rare earth element to the iron element of 1:1 (70 r/min), and simultaneously adding 1mol L -1 Ammonia water is used for adjusting the PH value to 7.5 until rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: uniformly stirring (70 r/min) the rare earth ferrite sol gel obtained in the step S1.3, placing the mixture in a constant-temperature vibration box, vibrating for 10-12 h at 80-90 ℃, taking out the mixture from the constant-temperature vibration box, adding vanadyl sulfate into the mixture, wherein the mass ratio of the rare earth oxide sol to the vanadyl sulfate is 1:5, uniformly stirring (70 r/min), placing the mixture in the constant-temperature vibration box, and continuously vibrating the mixture until composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
s2.2, pulling method:
s2.2.1 vertically suspending the substrate on a pulling machine, and carrying out pulling coating by using the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1:3, the pulling times are 5 times, and the pulling dipping time is 30min;
s2.2.2 the coating substrate obtained in S2.2.1 is placed into a muffle furnace, and is subjected to constant-temperature thermal diffusion at 100 ℃, then calcined to form a film, the calcining temperature is increased at 5 ℃/min, the calcining temperature is 600 ℃, the calcining time is 2h, then the annealing is performed at 10 ℃/min, the annealing is performed to 200 ℃, the heat is preserved for 2h, and finally the film is naturally cooled in the air.
In order to prove that the process can obtain an intact rare earth phase, the invention researches the phase of a film layer obtained by the whole preparation process of rare earth (cerium nitrate and samarium nitrate)/(yttrium nitrate and zirconium nitrate). The specific method is that a matrix film is prepared by S1.1, S1.3 (without adding oxide ferrite sol), S1.4 (without adding vanadyl sulfate) and S2.1, and the film layer is subjected to in-situ high-temperature XRD detection in different intervals, wherein the yttrium zirconium rare earth oxide film layer is shown in the figure 1 and the samarium cerium rare earth oxide film layer is shown in the figure 2. The graph shows that the obtained film metal oxide has a perfect phase structure, no other impurity phase is generated, and the comparison of in-situ high-temperature XRD test results shows that the obtained oxide film has good thermochemical stability.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (2)
1. The preparation process of the vanadium oxide rare earth double-doped ferrite magnetic composite film is characterized by comprising the following steps of:
s1, preparing a vanadium oxide rare earth double-doped ferrite magnetic composite film slurry by 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 saturated solution, and placing the saturated solution in an oil bath or a water bath kettle 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 saturated solution, and placing the saturated solution in an oil bath or a water bath kettle for stirring until sol is generated to obtain ferrite sol;
s1.3, rare earth ferrite sol-gel technology: 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 1 mol.L -1 Ammonia water regulatorpH is regulated to 7.5, and the rare earth ferrite sol gel is formed;
s1.4, a vanadium-doped sol-gel slurry process: placing the rare earth ferrite sol gel obtained in the step S1.3 into a constant temperature shaking box to shake for 10-12 hours at 80-90 ℃, taking out the vanadium oxide precursor from the constant temperature shaking box to stir uniformly, and placing the mixture into the constant temperature shaking box to shake continuously until the composite gel is formed, thus obtaining vanadium-doped sol gel slurry, namely vanadium oxide rare earth double-doped ferrite magnetic composite film slurry;
s2, coating:
the plating 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;
the rare earth nitrate comprises cerium nitrate, samarium nitrate, yttrium nitrate and lanthanum nitrate; the complexing agent is citric acid monohydrate, and the mass n 1 Rare earth metal ion/n 2 Citric acid monohydrate is 10-11:1, and the mass n is as follows 3 Fe 3+ /n 4 Citric acid monohydrate is 10-11:1; the dispersant comprises propylene glycol and ethylene glycol, and the mass m 1 Citric acid/m hydrate 2 The dispersing agent is 7-8:1;
the temperature of the oil bath pot and the water bath pot 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 1-1.2:0.8-1;
the vanadium oxide precursor comprises vanadyl sulfate, rare earth oxide sol and vanadium oxide precursor with the mass ratio of X 1 : X 2 And 0 < X 1 ≤1，5≤X 2 ≤6。
2. The preparation process of the vanadium oxide rare earth double-doped ferrite magnetic composite film according to claim 1, wherein the coating operation steps are as follows:
s2.1, 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 printer, placing a metal substrate on the bottom surface of the screen printer, printing and coating, wherein the mass ratio of the screen printing slurry to the substrate is 1:1, the printing times are 3, and the printing and dipping time is 10-15 min;
s2.1.2 the substrate obtained in the step S2.1.1 is placed in a muffle furnace to be subjected to constant-temperature thermal diffusion at 80-120 ℃, then calcined to form a film, the heating rate is 5-10 ℃/min, the calcining temperature is 700-750 ℃, the calcining time is 2-3 h, then annealing is carried out, the annealing rate is 10-15 ℃/min, the annealing is carried out to 300-400 ℃, the heat preservation is carried out for 2-3 h, and finally natural cooling is carried out in air;
s2.2, pulling method:
s2.2.1 vertically suspending the substrate on a pulling machine, and carrying out pulling coating by using the vanadium oxide rare earth double-doped ferrite magnetic composite film slurry obtained in the step S1.4, wherein the mass ratio of the slurry to the substrate is 1:3, the pulling times are 5 times, and the pulling dipping time is 30-40 min;
s2.2.2 the coating substrate obtained in S2.2.1 is placed into a muffle furnace, constant-temperature thermal diffusion is carried out at 70-100 ℃, then the coating substrate is calcined to form a film, the calcining temperature is increased by 5-10 ℃/min, the calcining temperature is 600-650 ℃, the calcining time is 2-3 h, the annealing is carried out again, the annealing rate is 10-15 ℃/min, the annealing is carried out to 200-300 ℃, the heat preservation is carried out for 2-3 h, and finally the coating substrate is naturally cooled in the air.
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