CN119920614A - Method for preparing nano-grade NdFeB permanent magnet material by aerosol jet printing technology - Google Patents
Method for preparing nano-grade NdFeB permanent magnet material by aerosol jet printing technology Download PDFInfo
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Abstract
本发明公开了一种气溶胶喷射打印技术制备纳米级钕铁硼永磁材料的方法。本发明采用气溶胶技术结合溶胶凝胶法制备纳米级钕铁硼永磁材料，方法简单，实施难度低，液相下的原料混合更充分，促进络合反应的进行，形成稳定均一的溶胶体系。随着凝胶化进程的推进，形成的空间网络结构还有效控制了颗粒尺寸，保证了所得磁性材料的性能一致性与优良的可控性，制备出的磁粉颗粒均匀、尺寸可控、磁性能较高，大大降低了退火时的温度，为高性能NdFeB永磁纳米粒子的工业化生产提供了一条突破性的路径。
The present invention discloses a method for preparing nano-grade NdFeB permanent magnetic materials by aerosol jet printing technology. The present invention adopts aerosol technology combined with sol-gel method to prepare nano-grade NdFeB permanent magnetic materials. The method is simple, easy to implement, and the raw materials in the liquid phase are mixed more fully, which promotes the complexation reaction and forms a stable and uniform sol system. With the advancement of the gelation process, the formed spatial network structure also effectively controls the particle size, ensures the performance consistency and excellent controllability of the obtained magnetic material, and the prepared magnetic powder particles are uniform, the size is controllable, and the magnetic properties are high, which greatly reduces the temperature during annealing, and provides a breakthrough path for the industrial production of high-performance NdFeB permanent magnetic nanoparticles.
Description
Technical Field
The invention relates to the field of magnetic materials, in particular to a method for preparing a nano-scale neodymium iron boron permanent magnetic material by an aerosol jet printing technology.
Background
The rare earth permanent magnet material has very wide market potential due to the wide application range. Neodymium iron boron (NdFeB) permanent magnet material is a rare earth permanent magnet material, and research in the field has been mainly focused on the development of sintering, bonding NdFeB and more rare earth permanent magnet materials so far. Magnetic powder is an indispensable basis for preparing both bonded magnets, sintered magnets and magnetoelastics.
The main physical preparation modes of the NdFeB magnetic powder are powder metallurgy, quick quenching and the like, and the production of the conventional micron-sized NdFeB magnetic powder depends on spin quenching, crushing, ball milling and HDDR (Hydrogen Disproportionation Desorption and Reconstruction, hydrogenation-decomposition-dehydrogenation-recrystallization) technologies, but the technologies have high energy consumption and high purity requirements on initial raw materials. The nanoscale permanent magnetic nanoparticles have application potential in the fields of anisotropy, exchange coupling, single domain particles, ferrofluid, cooling systems, high-density storage and the like due to unique morphology and size distribution. As is well known, chemical synthesis has its unique advantages in the preparation of nanomaterials, and currently, chemical methods mainly include reduction of neodymium salts and iron salts using sodium borohydride, and reduction with polyols, but efficient and environmentally friendly preparation of nanoparticles is a great challenge due to the high electrode potential of rare earth elements and the easily oxidizable nature of NdFeB alloys.
The document with the application number 201410181298.0 discloses a method for preparing neodymium iron boron permanent magnetic nano particles, which uses neodymium acetylacetonate, ferric acetylacetonate and ethyl borate as raw materials to avoid the difficulty in removing chlorine elements introduced when using neodymium chloride hexahydrate, ferric chloride hexahydrate and boric acid as raw materials, thereby influencing the performance of products and harm to production equipment and personnel. However, this increases the cost of raw materials and reduces the economic applicability.
In view of the above, the conventional preparation method of NdFeB permanent magnetic nanoparticles exposes the problems of insufficient product performance, low efficiency, limited yield, high raw material cost, limited selection, serious environmental pollution and the like, and a new method with high efficiency, high yield, low cost and environmental friendliness is urgently needed to meet the requirements of industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a nano NdFeB permanent magnet material by an aerosol jet printing technology.
The technical scheme for solving the technical problems is that the invention provides a method for preparing a nano NdFeB permanent magnet material by an aerosol jet printing technology, which is characterized by comprising the following steps:
Step 1, dissolving metal salt and boric acid in deionized water to obtain a mixed solution, wherein the metal salt comprises neodymium chloride hexahydrate and ferric chloride hexahydrate;
Step 2, uniformly mixing the citric acid/glycol aqueous solution with the mixed solution obtained in the step 1 to obtain sol-ink mother solution;
step 3, ageing the sol-ink mother liquor obtained in the step 2 to obtain sol;
Step 4, uniformly mixing the organic dispersing agent, deionized water and the sol obtained in the step 3 to adjust the viscosity of the system, so as to adjust the atomization stability of the sol and obtain sol ink;
Step 5, atomizing the sol ink obtained in the step 4 to form liquid drops, and conveying the liquid drops to an aerosol jet printing device, conveying the liquid drops to a printing nozzle through carrier gas, and forming aerosol jet flow by the carrier gas, the constraint gas and the liquid drops together to be ejected from the printing nozzle;
Step 6, annealing the oxide gel powder obtained in the step 5 under a mixed atmosphere of hydrogen and argon, and carrying out reduction reaction to obtain the micro-nano grade neodymium iron boron permanent magnet material;
And 7, dispersing the micro-nano level neodymium iron boron permanent magnet material obtained in the step 6 into an insoluble solvent, sieving by using a nano level filter membrane, continuously flushing until filtrate is clear, and drying the filtrate to obtain the nano level neodymium iron boron permanent magnet material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention combines the aerosol technology with the sol-gel method to prepare the nano-scale neodymium iron boron permanent magnet material, has simple method, low implementation difficulty, more complete raw material mixing under the liquid phase, promotes the complex reaction to be carried out, and forms a stable and uniform sol system. With the promotion of gelation progress, the formed space network structure also effectively controls the particle size, ensures the uniformity and excellent controllability of the performance of the obtained magnetic material, prepares the magnetic powder with uniform particles, controllable size and higher magnetic performance, greatly reduces the temperature during annealing, and provides a breakthrough path for the industrial production of the high-performance NdFeB permanent magnet nano particles.
(2) The invention innovatively combines the aerosol technology, and the aerosol technology enables the size of the sol particles to be smaller, and remarkably increases the specific surface area, thereby increasing the size uniformity and the magnetic performance of the magnetic powder.
(3) The aerosol technology produces aerosol with small particle size and large surface energy, and this reduces the activation energy in high temperature reaction and thus greatly reduces the annealing reduction temperature.
(4) According to the invention, the problem that the magnetic performance of nano-scale neodymium iron boron magnetic powder is affected due to excessive chlorine residues in products when neodymium chloride hexahydrate, ferric chloride hexahydrate and boric acid are used as raw materials is solved by an aerosol technology, and the residual chlorine is removed by constraint gas by a heating device in the aerosol technology, so that the residual chlorine amount is less, and the cost is reduced, so that the method is more suitable for industrialization.
(5) The invention controls the size of the aerosol by adjusting the flow rates of carrier gas and constraint gas in the aerosol technology, thereby regulating and controlling the size and the microscopic morphology of the nano-scale NdFeB magnetic powder prepared by the method.
Drawings
FIG. 1 is a hysteresis loop diagram of a nano-scale NdFeB permanent magnet material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a nano-scale NdFeB permanent magnet material prepared in example 1 of the present invention;
FIG. 3 is a hysteresis loop diagram of the nano-scale NdFeB permanent magnet material prepared in example 2 of the present invention;
FIG. 4 is an SEM image of a nano-scale NdFeB permanent magnet material prepared in example 2 of the present invention;
FIG. 5 is a hysteresis loop diagram of the nano-scale NdFeB permanent magnet material prepared in example 3 of the present invention;
FIG. 6 is a hysteresis loop diagram of the nano-scale NdFeB permanent magnet material prepared in example 4 of the present invention;
Fig. 7 is a hysteresis loop diagram of the nano-scale neodymium iron boron permanent magnet material prepared in example 5 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only for further detailed description of the present invention and do not limit the scope of the invention.
The invention provides a method for preparing a nano NdFeB permanent magnet material by aerosol jet printing technology (short for method), which is characterized by comprising the following steps:
Step 1, dissolving metal salt and boric acid in deionized water to obtain a mixed solution, wherein the metal salt comprises neodymium chloride hexahydrate and ferric chloride hexahydrate;
preferably, in the step 1, the proportion of the elements neodymium, iron and boron is added according to the amount of substances of nominal components in the chemical formula of Nd 15Fe77.5B7.5, and the concentration of chloride ions is 3-10 mol/L.
Step 2, uniformly mixing the citric acid/glycol aqueous solution with the mixed solution obtained in the step 1 to obtain sol-ink mother solution;
preferably, in the step2, the mole ratio of the citric acid to the glycol to the metal salt is 2-50:2-50:1, and the volume ratio of the citric acid/glycol aqueous solution to the mixed solution is 1:1.
In the step 2, the uniform mixing is performed by stirring, wherein the stirring process is performed at the rotating speed of 100-1000 r/min, the temperature of 0-40 ℃ and the time of 10-60 min.
Step 3, ageing the sol-ink mother liquor obtained in the step 2 to obtain sol;
preferably, in the step 3, the aging time is 12-72 h, the aging temperature is room temperature, and the aging ensures that the citric acid, the glycol and the metal ions are more thoroughly complexed, thereby ensuring that the sol particles are more thoroughly generated and the sol particles are more uniform in the solution.
Step 4, uniformly mixing the organic dispersing agent, deionized water and the sol obtained in the step 3 to adjust the viscosity of the system, so as to adjust the atomization stability of the sol and obtain sol ink;
Preferably, in the step 4, the volume ratio of deionized water to sol is 1-10:1-5, and the ratio of the mass of the organic dispersing agent to the volume of sol is 1 g:100-1000 ml.
Preferably, in step 4, the organic dispersant is one of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid or gum arabic.
In the step 4, the uniform mixing is performed by stirring, wherein the stirring process is performed at the rotating speed of 100-1000 r/min, the temperature of 0-40 ℃ and the time of 10-60 min.
Preferably, in the step 4, the viscosity of the sol ink is 1-20 cp.
Step 5, atomizing the sol ink obtained in the step 4 to form liquid drops, and conveying the liquid drops to an aerosol jet printing device through a gas conveying pipe, conveying the liquid drops to a printing nozzle through a carrier gas, jetting the carrier gas, constraint gas and the liquid drops together to form an aerosol jet from the printing nozzle, changing the flow of the carrier gas and the constraint gas to regulate the breadth and the jetting speed of the aerosol jet, jetting the aerosol jet to a substrate through a heating device, changing the printing height and the temperature of the heating device to regulate the solvent evaporation behavior of the aerosol jet in the air, and changing the printing speed, the printing layer number and the temperature of the substrate to regulate the oxidation process of the aerosol on the substrate to obtain oxide gel powder;
preferably, in the step 5, the atomization process is ultrasonic atomization, and the ultrasonic frequency is 1.5-2.5 MHz.
Preferably, in the step 5, the flow rate of the carrier gas is 200-500 sccm, and the flow rate of the constraint gas is 50-150 sccm.
Preferably, in step 5, the carrier gas and the confining gas are nitrogen or inert gas, and the inert gas is argon.
Preferably, in the step 5, the printing height is 5-10 mm, the temperature of the heating device is 150-350 ℃, the printing speed is 5-50 mm/s, the number of printing layers is 50-500, and the temperature of the substrate is 40-180 ℃.
Preferably, in step 5, the substrate is a glass plate, a ceramic plate or a plastic plate.
Step 6, annealing the oxide gel powder obtained in the step 5 under a mixed atmosphere of hydrogen and argon, performing a high-temperature reduction reaction, and cooling to obtain the micro-nano grade NdFeB permanent magnet material;
Preferably, in the step 6, the temperature of the reduction reaction is 550-700 ℃ and the time is 3-6 hours.
Preferably, in the step 6, the volume ratio of the hydrogen to the argon is 1-25:75-99 (preferably 5:95), and the sum of the volume ratio is 100%.
And 7, dispersing the micro-nano level neodymium iron boron permanent magnet material obtained in the step 6 into an insoluble solvent, sieving by using a nano level filter membrane, continuously flushing until filtrate is clear, and drying the filtrate to obtain the nano level neodymium iron boron permanent magnet material.
Preferably, in the step 7, the insoluble solvent is a solvent incapable of dissolving the micro-nano grade neodymium iron boron permanent magnetic material, and specifically DMF, acetone or tetrahydrofuran.
Preferably, in the step 7, the pore diameter of the nano-scale filter membrane is 0.05-0.22 μm.
Preferably, in the step 7, the drying temperature is 60-100 ℃ and the drying time is 0.5-24 h.
Example 1 (1) neodymium chloride hexahydrate, iron chloride hexahydrate and boric acid were dissolved in 100ml of deionized water in accordance with the amounts of substances of the nominal components in the chemical formula of Nd 15Fe77.5B7.5, and the chloride ion concentration in the mixed solution was controlled to 5mol/L;
(2) Uniformly mixing 100ml of citric acid/glycol aqueous solution with the mixed solution, stirring at a rotating speed of 200r/min, a temperature of 15 ℃ and a time of 15min, and controlling the molar ratio of citric acid to glycol to metal salt to be 2:2:1 to obtain sol ink mother solution;
(3) Aging the sol-ink mother solution at room temperature for 24 hours to obtain sol;
(4) Adding 200ml deionized water into the sol, adding 0.4g polyvinyl alcohol to regulate atomization stability, uniformly stirring, wherein the stirring speed is 200r/min, the temperature is 15 ℃, the time is 15min, and the viscosity is regulated to 5cP to obtain sol ink;
(5) Atomizing the sol ink to form liquid drops with the ultrasonic frequency of 1.9MHz, conveying the liquid drops to a printing spray head through carrier gas, forming aerosol jet by the carrier gas, constraint gas and the liquid drops together, setting the flow rate of the carrier gas to be 350sccm and the flow rate of the constraint gas to be 75sccm for regulating and controlling the breadth and the jet speed of the aerosol jet, spraying the aerosol jet on a 50 ℃ substrate through a 200 ℃ heating device, printing the aerosol jet to be 5mm in height, regulating and controlling the solvent evaporation speed of the aerosol jet in the air, setting the printing speed to be 10mm/s, and regulating and controlling the oxidation process of the aerosol on the substrate by the printing layer number to be 100 layers to obtain oxide gel powder, wherein the carrier gas and the constraint gas both adopt nitrogen;
(6) Annealing the oxide gel powder under a mixed atmosphere of hydrogen and argon (the volume ratio of the hydrogen to the argon is 5:95), carrying out reduction reaction at 675 ℃ for 3.5 hours, and cooling to obtain the micro-nano grade neodymium iron boron permanent magnet material;
(7) Dispersing the micro-nano level NdFeB permanent magnet material into DMF, sieving with a nano level filter membrane, continuously washing until the filtrate is clear, and drying the filtrate at 60 ℃ for 24 hours to obtain the nano level NdFeB permanent magnet material.
As can be seen from FIG. 1, the saturation magnetization of the obtained nano-scale NdFeB permanent magnet material is 63.4emu/g, the residual magnetization is 21.8emu/g, and the coercivity is 1874Oe.
As can be seen from fig. 2, the obtained nano-scale neodymium iron boron permanent magnet material is magnetic powder and has an ellipsoidal shape.
Example 2 (1) neodymium chloride hexahydrate, iron chloride hexahydrate and boric acid were dissolved in 200ml of deionized water in accordance with the amounts of substances of the nominal components in the chemical formula of Nd 15Fe77.5B7.5, and the chloride ion concentration in the mixed solution was controlled to 3mol/L;
(2) Uniformly mixing 200ml of citric acid/glycol aqueous solution with the mixed solution, stirring at a rotation speed of 400r/min, a temperature of 25 ℃ and a time of 30min, and controlling the molar ratio of citric acid to glycol to metal salt to be 50:50:1 to obtain sol ink mother liquor;
(3) Aging the sol-ink mother solution at room temperature for 48 hours to obtain sol;
(4) Adding 80ml deionized water into the sol, adding 2.4g polyvinylpyrrolidone to regulate atomization stability, uniformly stirring at 400r/min at 25 ℃ for 30min, and regulating viscosity to 3cP to obtain sol ink;
(5) Atomizing the sol ink to form liquid drops with the ultrasonic frequency of 2.3MHz, conveying the liquid drops to a printing spray head through carrier gas, forming aerosol jet by the carrier gas, constraint gas and the liquid drops together, setting the flow rate of the carrier gas to be 500sccm, the flow rate of the constraint gas to be 150sccm for regulating and controlling the breadth and the jet speed of the aerosol jet, spraying the aerosol jet on an 80 ℃ substrate through a 250 ℃ heating device, and regulating and controlling the solvent evaporation speed of the aerosol jet in the air, setting the printing speed to be 20mm/s, and regulating and controlling the oxidation process of the aerosol on the substrate by 150 layers to obtain oxide gel powder, wherein the carrier gas and the constraint gas both adopt argon;
(6) Annealing the oxide gel powder under a mixed atmosphere of hydrogen and argon (the volume ratio of the hydrogen to the argon is 5:95), carrying out reduction reaction at 600 ℃ for 6 hours, and cooling to obtain the micro-nano grade neodymium iron boron permanent magnet material;
(7) Dispersing the micro-nano level NdFeB permanent magnet material into acetone, sieving with a nano level filter membrane, continuously flushing until the filtrate is clear, and drying the filtrate at 80 ℃ for 10 hours to obtain the nano level NdFeB permanent magnet material.
As can be seen from FIG. 3, the saturation magnetization of the obtained nano-scale NdFeB permanent magnet material is 61.9emu/g, the residual magnetization is 20.7emu/g, and the coercivity is 1765Oe.
As can be seen from fig. 4, the obtained nano-scale neodymium iron boron permanent magnet material is magnetic powder and has an ellipsoidal shape.
Example 3 (1) neodymium chloride hexahydrate, iron chloride hexahydrate and boric acid were dissolved in 500ml of deionized water in accordance with the amounts of substances of the nominal composition in the chemical formula of Nd 15Fe77.5B7.5, and the chloride ion concentration in the mixed solution was controlled to 8mol/L;
(2) Uniformly mixing 500ml of citric acid/glycol water solution with the mixed solution, stirring at 600r/min at 40 ℃ for 40min, and controlling the molar ratio of citric acid to glycol to metal salt to be 25:25:1 to obtain sol ink mother liquor;
(3) Aging the sol-ink mother solution at room temperature for 72 hours to obtain sol;
(4) Adding 2L of deionized water into the sol, adding 10g of polyacrylic acid to adjust atomization stability, uniformly stirring, wherein the stirring speed is 600r/min, the temperature is 40 ℃, the time is 40min, and the viscosity is adjusted to 10cP to obtain sol ink;
(5) Atomizing the sol ink to form liquid drops with the ultrasonic frequency of 1.7MHz, conveying the liquid drops to a printing spray head through carrier gas, forming aerosol jet by the carrier gas, constraint gas and the liquid drops together, setting the flow of the carrier gas to be 250sccm, setting the flow of the constraint gas to be 125sccm to regulate the breadth and the jet speed of the aerosol jet, spraying the aerosol jet on a 120 ℃ substrate through a 275 ℃ heating device, regulating the solvent evaporation speed of the aerosol jet in the air to be 6.5mm, setting the printing speed to be 25mm/s, and setting the printing layer number to be 200 to regulate the oxidation process of the aerosol on the substrate to obtain oxide gel powder, wherein the carrier gas and the constraint gas both adopt nitrogen;
(6) Annealing the oxide gel powder under a mixed atmosphere of hydrogen and argon (the volume ratio of the hydrogen to the argon is 5:95), carrying out reduction reaction at 550 ℃ for 5 hours, and cooling to obtain the micro-nano grade neodymium iron boron permanent magnet material;
(7) Dispersing the micro-nano level NdFeB permanent magnet material into acetone, sieving with a nano level filter membrane, continuously flushing until the filtrate is clear, and drying the filtrate at 100 ℃ for 1h to obtain the nano level NdFeB permanent magnet material.
As can be seen from FIG. 5, the saturation magnetization of the obtained nano-scale NdFeB permanent magnet material is 58.9emu/g, the residual magnetization is 22.3emu/g, and the coercivity is 1803Oe.
Example 4 (1) neodymium chloride hexahydrate, iron chloride hexahydrate and boric acid were dissolved in 300ml of deionized water in accordance with the amounts of substances of the nominal composition in the chemical formula of Nd 15Fe77.5B7.5, and the chloride ion concentration in the mixed solution was controlled to 10mol/L;
(2) Uniformly mixing 300ml of citric acid/glycol aqueous solution with the mixed solution, stirring at a rotating speed of 500r/min, a temperature of 35 ℃ and a time of 50min, and controlling the molar ratio of citric acid to glycol to metal salt to be 15:15:1 to obtain sol ink mother solution;
(3) Aging the sol-ink mother solution at room temperature for 60 hours to obtain sol;
(4) Adding 5L of deionized water into the sol, adding 56g of gum arabic to regulate atomization stability, uniformly stirring, wherein the stirring speed is 500r/min, the temperature is 35 ℃ and the time is 50min, and regulating the viscosity to 18cP to obtain sol ink;
(5) Atomizing the sol ink to form liquid drops with the ultrasonic frequency of 2.5MHz, conveying the liquid drops to a printing spray head through carrier gas, forming aerosol jet by the carrier gas, constraint gas and the liquid drops together, setting the flow rate of the carrier gas to be 450sccm, setting the flow rate of the constraint gas to be 100sccm, regulating the breadth and the jet speed of the aerosol jet, spraying the aerosol jet on a 150 ℃ substrate through a 300 ℃ heating device, regulating the solvent evaporation speed of the aerosol jet in the air, setting the printing speed to be 45mm/s, and regulating the oxidation process of the aerosol on the substrate by the printing layer number to be 300 layers to obtain oxide gel powder, wherein the carrier gas and the constraint gas both adopt nitrogen;
(6) Annealing the oxide gel powder under a mixed atmosphere of hydrogen and argon (the volume ratio of the hydrogen to the argon is 5:95), carrying out reduction reaction at 700 ℃ for 4 hours, and cooling to obtain the micro-nano grade neodymium iron boron permanent magnet material;
(7) Dispersing the micro-nano level NdFeB permanent magnet material into tetrahydrofuran, sieving with a nano level filter membrane, continuously flushing until the filtrate is clear, and drying the filtrate at 90 ℃ for 2 hours to obtain the nano level NdFeB permanent magnet material.
As can be seen from FIG. 6, the saturation magnetization of the obtained nano-scale NdFeB permanent magnet material is 42.1emu/g, the residual magnetization is 12.6emu/g, and the coercivity is 1896Oe.
Example 5 (1) neodymium chloride hexahydrate, iron chloride hexahydrate and boric acid were dissolved in 200ml of deionized water in accordance with the amounts of substances of the nominal composition in the chemical formula of Nd 15Fe77.5B7.5, and the chloride ion concentration in the mixed solution was controlled to 6mol/L;
(2) Uniformly mixing 200ml of citric acid/glycol aqueous solution with the mixed solution, stirring at a rotating speed of 800r/min, a temperature of 5 ℃ and a time of 60min, and controlling the molar ratio of citric acid to glycol to metal salt to be 40:40:1 to obtain sol ink mother solution;
(3) Aging the sol-ink mother solution at room temperature for 36 hours to obtain sol;
(4) Adding 4L of deionized water into the sol, adding 4.4g of polyethylene glycol to adjust atomization stability, uniformly stirring at a rotation speed of 800r/min, a temperature of 5 ℃ and a time of 60min, and adjusting the viscosity to 14cP to obtain sol ink;
(5) Atomizing the sol ink to form liquid drops with the ultrasonic frequency of 2.1MHz, conveying the liquid drops to a printing spray head through carrier gas, forming aerosol jet by the carrier gas, constraint gas and the liquid drops together, setting the flow rate of the carrier gas to be 200sccm, setting the flow rate of the constraint gas to be 50sccm, regulating the breadth and the jet speed of the aerosol jet, spraying the aerosol jet on a 180 ℃ substrate through a 150 ℃ heating device, regulating the solvent evaporation speed of the aerosol jet in the air, setting the printing speed to be 50mm/s, and regulating the oxidation process of the aerosol on the substrate by 500 layers to obtain oxide gel powder, wherein the carrier gas and the constraint gas both adopt nitrogen;
(6) Annealing the oxide gel powder under a mixed atmosphere of hydrogen and argon (the volume ratio of the hydrogen to the argon is 5:95), carrying out reduction reaction at 650 ℃ for 3 hours, and cooling to obtain the micro-nano grade neodymium iron boron permanent magnet material;
(7) Dispersing the micro-nano level NdFeB permanent magnet material into DMF, sieving with a nano level filter membrane, continuously washing until the filtrate is clear, and drying the filtrate at 90 ℃ for 0.5h to obtain the nano level NdFeB permanent magnet material.
As can be seen from FIG. 7, the saturation magnetization of the obtained nano-scale NdFeB permanent magnet material is 55.3emu/g, the residual magnetization is 19.9emu/g, and the coercivity is 1931Oe.
The invention is applicable to the prior art where it is not described.
Claims (10)
1. The method for preparing the nano NdFeB permanent magnet material by the aerosol jet printing technology is characterized by comprising the following steps of:
Step 1, dissolving metal salt and boric acid in deionized water to obtain a mixed solution, wherein the metal salt comprises neodymium chloride hexahydrate and ferric chloride hexahydrate;
Step 2, uniformly mixing the citric acid/glycol aqueous solution with the mixed solution obtained in the step 1 to obtain sol-ink mother solution;
step 3, ageing the sol-ink mother liquor obtained in the step 2 to obtain sol;
Step 4, uniformly mixing the organic dispersing agent, deionized water and the sol obtained in the step 3 to adjust the viscosity of the system, so as to adjust the atomization stability of the sol and obtain sol ink;
Step 5, atomizing the sol ink obtained in the step 4 to form liquid drops, and conveying the liquid drops to an aerosol jet printing device, conveying the liquid drops to a printing nozzle through carrier gas, and forming aerosol jet flow by the carrier gas, the constraint gas and the liquid drops together to be ejected from the printing nozzle;
Step 6, annealing the oxide gel powder obtained in the step 5 under a mixed atmosphere of hydrogen and argon, and carrying out reduction reaction to obtain the micro-nano grade neodymium iron boron permanent magnet material;
And 7, dispersing the micro-nano level neodymium iron boron permanent magnet material obtained in the step 6 into an insoluble solvent, sieving by using a nano level filter membrane, continuously flushing until filtrate is clear, and drying the filtrate to obtain the nano level neodymium iron boron permanent magnet material.
2. The method for preparing the nano-scale neodymium-iron-boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 1, the proportion of elemental neodymium, iron and boron is added according to the amount of substances of nominal components in a chemical formula of Nd 15Fe77.5B7.5, and the concentration of chloride ions is 3-10 mol/L.
3. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 2, the mole ratio of citric acid to glycol to metal salt is 2-50:2-50:1, and the volume ratio of citric acid/glycol aqueous solution to mixed solution is 1:1.
4. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 3, the aging time is 12-72 h, and the aging temperature is room temperature.
5. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 4, the volume ratio of deionized water to sol is 1-10:1-5, and the volume ratio of the mass of the organic dispersing agent to the volume of the sol is 1 g:100-1000 ml;
In the step 2 and the step 4, uniformly mixing and stirring, wherein the stirring process comprises the steps of rotating at 100-1000 r/min, at 0-40 ℃ and for 10-60 min;
In the step 4, the viscosity of the sol ink is 1-20 cP.
6. The method for preparing nano-scale neodymium iron boron permanent magnet material according to claim 1 or 5, wherein in step 4, the organic dispersing agent is one of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyacrylic acid or gum arabic.
7. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 5, the atomization process is ultrasonic atomization, and the ultrasonic frequency is 1.5-2.5 MHz.
8. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 5, the flow of carrier gas and constraint gas are changed to regulate the breadth and the jet speed of aerosol jet, the flow of carrier gas is 200-500 sccm, and the flow of constraint gas is 50-150 sccm;
In the step 5, the printing height and the temperature of a heating device are changed to regulate and control the solvent evaporation behavior of aerosol jet flow in the air, wherein the printing height is 5-10 mm, and the temperature of the heating device is 150-350 ℃;
In the step 5, the oxidation process of the aerosol on the substrate is regulated and controlled by changing the printing speed, the printing layer number and the temperature of the substrate, wherein the printing speed is 5-50 mm/s, the printing layer number is 50-500, and the temperature of the substrate is 40-180 ℃.
9. The method for preparing nano-scale neodymium iron boron permanent magnet materials by aerosol jet printing technology according to claim 1, wherein in step 5, the carrier gas and the constraint gas are nitrogen or inert gas, and the inert gas is argon.
10. The method for preparing the nano-scale neodymium iron boron permanent magnet material by the aerosol jet printing technology according to claim 1, wherein in the step 6, the temperature of the reduction reaction is 550-700 ℃ and the time is 3-6 hours;
in the step 6, the volume ratio of the hydrogen to the argon is 1-25:75-99, and the sum of the volume ratio of the hydrogen to the argon is 100%;
in the step 7, the insoluble solvent is DMF, acetone or tetrahydrofuran;
in the step 7, the aperture of the nano-scale filter membrane is 0.05-0.22 mu m;
In the step 7, the drying temperature is 60-100 ℃ and the drying time is 0.5-24 h.
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