CN112746186A - Preparation method and use method of Dy monatomic permeate - Google Patents

Preparation method and use method of Dy monatomic permeate Download PDF

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CN112746186A
CN112746186A CN201911392729.7A CN201911392729A CN112746186A CN 112746186 A CN112746186 A CN 112746186A CN 201911392729 A CN201911392729 A CN 201911392729A CN 112746186 A CN112746186 A CN 112746186A
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任金华
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Langfang Jingci Precision Material Co ltd
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Abstract

The invention discloses a preparation method and a use method of Dy single-atom permeate, which specifically comprise the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Keeping the temperature for 1h in the environment to obtain solid powder, namely Dy monogenA sub-permeate; wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5. The invention prepares the monatomic Dy permeate by a chemical method, further reduces the size of heavy rare earth, homogenizes grains, and performs high-temperature permeation in vacuum to improve the coercive force of the magnet and avoid the limitation of the thickness of the magnet, thereby overcoming the technical problems that the prior permeation technology has high requirements on the thickness of the permeated magnet, and the phenomena of great powder waste and uneven grain size occur when nano-scale or micron-scale powder is manufactured.

Description

Preparation method and use method of Dy monatomic permeate
Technical Field
The invention relates to the technical field of penetration of magnetic materials. More particularly, the present invention relates to a method for preparing a Dy single atom permeate and a method for using the same.
Background
Intrinsic coercive force and residual magnetism of the rare earth permanent magnet are two important parameters for measuring the performance of the permanent magnet, and at the present stage, a large amount of heavy rare earth is mostly added in a method for improving the coercive force, but the situation of reducing the residual magnetism can occur along with the increase of the content of the heavy rare earth. The currently frequently used ways of adding heavy rare earth can be divided into two categories, one is to add neodymium iron boron in the formula during the production process, and the other is to perform secondary tempering and infiltration on the heavy rare earth at the high temperature of 900-1000 ℃ by means of infiltration after sintering. Both of these methods can improve the intrinsic coercivity of the permanent magnet to different degrees.
At present, the commonly used infiltration technology adopts dysprosium oxide or dysprosium fluoride, the two powders are used for coating the magnet in a micron or nanometer form, but because the infiltration has high requirements on the thickness of the infiltrated magnet, the surface performance of the magnet can be ensured to be consistent with the performance of the central part when the thickness is 3mm, and the performance of two end surfaces can be different from the performance of the center of the magnet when the thickness is 5mm, thereby generating obstacles in the task of producing thicker magnets, and in addition, the phenomena of great powder waste and uneven grain size can occur when nano-scale or micron-scale powder is manufactured.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
It is still another object of the present invention to provide a method for preparing a Dy monatomic permeate, which is a method for preparing a monatomic Dy permeate by a chemical method, further reducing the size of heavy rare earth, homogenizing the grains, and performing high-temperature permeation under vacuum to achieve improvement of the coercive force of a magnet without being limited by the thickness of the magnet, and which overcomes the technical problems of the prior art of permeation that the thickness of the magnet is highly required, and that a large amount of powder is wasted and the grain size is not uniform when nano-sized or micro-sized powder is manufactured.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a Dy single atom permeate, which comprises: adding ZIF-8 powder to carbonic acidDysprosium solution, placing into NH with the temperature of 900 DEG C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5.
Preferably, in the preparation method of the Dy monatomic permeate, the adhesive is an aqueous solution of polyvinyl alcohol PVA: mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃, and heating and stirring the mixture until the mixture is uniform and transparent to obtain the adhesive.
Preferably, the volume fraction of the industrial ethanol aqueous solution is 95%.
Preferably, the preparation method of the Dy monatomic permeate comprises the following steps: and weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution.
Preferably, the preparation method of the Dy monatomic permeate, ZIF-8, comprises the following steps:
s1, weighing 0.2-1 part of peptone, 1-5 parts of glucose and 0.2-1 part of yeast powder by weight, adding the peptone, the glucose and the yeast powder into 100 parts of sterile water, fully stirring, and placing the mixture into high-temperature high-pressure sterilization treatment for 15-20 min after the solid is dissolved to obtain a liquid culture medium;
s2, taking 0.002-0.01 part of nano ferroferric oxide particles, sterilizing at high temperature and high pressure, and dispersing in 5-15 parts of sterile water to prepare a suspension of the nano particles; adding the suspension of the nano particles into a liquid culture medium, and fully and uniformly stirring; then inoculating 0.05-1.5 parts of strains to a liquid culture medium, culturing at the temperature of 15-35 ℃ and the rotating speed of 80-200 r/min, filtering after 48-96 h, collecting first filter residue, washing the first filter residue for 1-3 times by using a sodium hydroxide aqueous solution with the mass fraction of 0.5%, then placing the filter residue under flowing sterile water for washing for 2-5 min, and then carrying out freeze drying to obtain a hypha composite material;
s3, soaking 0.02-0.1 part of the hypha composite material obtained in the step S2 into 20-30 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.1-0.5 mol/L, performing ultrasonic oscillation treatment for 20-30 min, standing for 30-40 min, taking the hypha composite material out of the zinc nitrate hexahydrate solution, soaking the hypha composite material into 30-40 parts of 2-methylimidazole solution with the molar concentration of 0.1-0.5 mol/L, performing ultrasonic oscillation for 5-10 min, then placing the hypha composite material in a magnetic field environment, heating to 35-45 ℃, reacting for 30-40 min, and changing the magnetic field direction every 5 min; and after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 2-4 times in sequence, and freeze-drying to obtain the product.
Preferably, in the preparation method of the Dy monatomic permeate, the strain is any one of mucor, aspergillus niger, rhizopus or penicillium.
Preferably, the solvent of the Dy monatomic permeate, the zinc nitrate hexahydrate solution and the 2-methylimidazole solution is absolute methanol.
The invention also provides a using method of the Dy monatomic permeate, which comprises the following steps: mixing the Dy single-atom permeate with an industrial ethanol aqueous solution according to a weight ratio of 1:1 to obtain a permeating solution, coating the permeating solution on the surface of the neodymium iron boron magnet, baking the neodymium iron boron magnet in an oven at 150 ℃ for 40min, taking the neodymium iron boron magnet out of the oven, cooling to room temperature, coating and baking again to obtain the neodymium iron boron magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: the temperature is first maintained for 5h under vacuum at 900 ℃, then the temperature is reduced to 500 ℃ and the temperature is maintained for 5h under vacuum.
Preferably, the Dy single atom permeate is used, and the weight of the neodymium iron boron magnet coated with the permeate is increased by 1.8% compared with that of the starting neodymium iron boron magnet.
The invention at least comprises the following beneficial effects:
1. the grain size of the penetrating atoms is improved, the grain size is reduced, the obstruction of Dy atoms in the penetrating process is reduced, the penetrating depth is improved along with the refinement of penetrating grains, and the performance is more stable;
ZIF-8 has a thermal cracking temperature of 900 deg.C, i.e., it is thermally cracked at this temperature to form N-doped carbon carriers with a large number of defects, and then thermally cracked at NH3Under the atmosphere, based on strong interaction of Lewis acid and base, NH3And Dy2(CO3)3The Dy atom in the catalyst coordinates to form volatile Dy (NH)3)xDy is emitted out in atomic state and finally in the same NH3In the atmosphere of (1), Dy (NH)3)xThe species are captured by defects in the N-doped carbon carrier to form isolated Dy sites, and then a single atom Dy is formed;
2. the invention also provides a preparation method of the ZIF-8, which comprises the following steps: dispersing the nano ferroferric oxide particles in a culture medium, inoculating a strain to the culture medium to perform hypha culture, and winding hypha growing in the strain on the outer surface of the nano ferroferric oxide particles to prepare magnetic hypha composite nano particles, so that the mechanical strength and the uniform dispersibility of a hypha template agent are improved, the in-situ synthesis of ZIF-8 on the template agent is facilitated, and the effective load rate of ZIF-8 is improved; then taking the hypha composite nano particles as a template agent, uniformly adsorbing zinc ions with strong adsorbability on the surface of hypha, then immersing the hypha composite nano particles into an excessive 2-methylimidazole solution to synthesize ZIF-8 on the surface of the hypha composite nano particles in situ, and replacing a conventional template agent with the hypha composite nano particles, so that byproducts of the ZIF-8 in the synthesis process are reduced, the effective load rate of the ZIF-8 is improved, and the utilization rate of raw materials is further improved;
3. in the in-situ synthesis process of the ZIF-8, due to the existence of hyphae, the external specific surface area of the ZIF-8 can be improved, the hyphae can also be used as a pore canal support body, so that the effect of expanding the pore canal of the ZIF-8 is achieved, the activity of defect sites on the ZIF-8 can be improved due to the increase of the specific surface area of the ZIF-8, Dy atoms can be loaded more quickly on the ZIF-8, and the atom utilization rate is improved; the expansion of the ZIF-8 pore passage can reduce the mass transfer resistance of Dy, when a Dy atom monomer is prepared, Dy atoms can more quickly and smoothly enter the ZIF-8 pore passage and are combined with defect positions on the ZIF-8 pore passage, and when permeation is carried out, the Dy atoms are volatilized under the action of high temperature, and are quickly moved out of the pore passage and permeated into the neodymium iron boron magnet;
4. hyphae grow on the outer surfaces of the nano ferroferric oxide particles, magnetic performance is given to the hyphae, so that in the process of adsorbing zinc ions on the surfaces of the hyphae, in addition to displacement among elements generated by external ultrasonic oscillation, macroscopic displacement among the elements generated by magnetism exists, the zinc ions can be adsorbed on the surfaces of the hyphae more uniformly, and a cushion is laid for the subsequent in-situ synthesis of ZIF-8; further, in the process of synthesizing ZIF-8, the hypha composite nano particles adsorbed with zinc ions are immersed into a 2-methylimidazole solution, a magnetic field interference effect is added, the direction of the magnetic field is changed at intervals, the macroscopic moving speed between elements is accelerated, and the synthesis of ZIF-8 with large external specific surface area and wide pore channel is facilitated;
5. according to the invention, by utilizing the principle that Dy atoms are volatile at high temperature, the permeate is uniformly coated on the outer surface of the neodymium iron boron magnet, the neodymium iron boron magnet coated with the permeate is placed under a vacuum high-temperature condition for tempering treatment, and the Dy atoms volatilize and permeate into the neodymium iron boron magnet in the tempering treatment process, so that the penetration depth is improved due to the advantages of small particle size and strong penetrating power of the Dy atoms, and the method can be used for improving the coercive force of the neodymium iron boron magnet with larger thickness.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1>
The invention provides a preparation method of Dy monatomic permeate, which comprises the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5;
the adhesive is an aqueous solution of polyvinyl alcohol PVA: mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing in a constant-temperature water bath kettle at 60 ℃, heating and stirring until the mixture is uniform and transparent, and obtaining the adhesive; the volume fraction of the industrial ethanol aqueous solution is 95 percent;
the preparation method of the dysprosium carbonate solution comprises the following steps: and weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution. The specific adding sequence is that the industrial ethanol water solution is mixed with the adhesive, and then dysprosium carbonate is added and the mixture is treated under ultrasonic oscillation to be fully stirred.
The invention also provides a use method of the Dy monatomic permeate, which comprises the following steps: the method comprises the following steps: mixing the Dy monatomic permeate with an industrial ethanol aqueous solution according to the weight ratio of 1:1 to obtain a permeate solution, coating the permeate solution on the surface of the NdFeB magnet, baking the NdFeB magnet in an oven at 150 ℃ for 40min, taking the NdFeB magnet out of the oven, cooling to room temperature, coating and baking again to obtain the NdFeB magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: firstly, preserving heat for 5 hours under vacuum at the temperature of 900 ℃, then reducing the temperature to 500 ℃, and continuously preserving heat for 5 hours under vacuum;
the permeate coated ndfeb magnet gained 1.8% weight compared to the starting ndfeb magnet.
< example 2>
The invention provides a preparation method of Dy monatomic permeate, which comprises the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5;
the adhesive is an aqueous solution of polyvinyl alcohol PVA: mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing in a constant-temperature water bath kettle at 60 ℃, heating and stirring until the mixture is uniform and transparent, and obtaining the adhesive; the volume fraction of the industrial ethanol aqueous solution is 95 percent;
the preparation method of the dysprosium carbonate solution comprises the following steps: weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution;
the preparation method of ZIF-8 comprises the following steps:
s1, weighing 0.2 part of peptone, 1 part of glucose and 0.2 part of yeast powder according to parts by weight, adding the peptone, the glucose and the yeast powder into 100 parts of sterile water, fully stirring, and placing the mixture into high-temperature high-pressure sterilization for 15min after the solid is dissolved to obtain a liquid culture medium;
step S2, taking 0.002 part of nano ferroferric oxide particles (the particle size is 100nm), sterilizing at high temperature and high pressure, and dispersing in 5 parts of sterile water to prepare a suspension of the nano particles; adding the suspension of the nano particles into a liquid culture medium, and fully stirring and uniformly mixing; inoculating 0.05 part of strain into a liquid culture medium, culturing at the temperature of 15 ℃ and the rotating speed of 80r/min, filtering after 48 hours, collecting first filter residue, washing the first filter residue for 1 time by using a sodium hydroxide aqueous solution with the mass fraction of 0.5%, then placing the filter residue in flowing sterile water for washing for 2min, and then carrying out freeze drying to obtain a hypha composite material; the strain is Aspergillus niger;
s3, soaking 0.02 part of the hypha composite material obtained in the step S2 into 20 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.1mol/L, standing for 30min after ultrasonic oscillation treatment is carried out for 20min, then taking the hypha composite material out of the zinc nitrate hexahydrate solution, soaking the hypha composite material into 30 parts of 2-methylimidazole solution with the molar concentration of 0.1mol/L, carrying out ultrasonic oscillation for 5min, then placing the hypha composite material in a magnetic field environment, heating to 35 ℃ and reacting for 30min, and changing the direction of the magnetic field every 5 min; after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 2 times in sequence, and then freeze-drying to obtain the compound; the solvents of the zinc nitrate hexahydrate solution and the 2-methylimidazole solution are both anhydrous methanol.
The invention also provides a use method of the Dy monatomic permeate, which comprises the following steps: mixing the Dy monatomic permeate with an industrial ethanol aqueous solution according to a weight ratio of 1:1 to obtain a permeate solution, coating the permeate solution on the surface of the neodymium iron boron magnet, baking the neodymium iron boron magnet in an oven at 150 ℃ for 40min, taking out the neodymium iron boron magnet from the oven, cooling to room temperature, coating and baking again to obtain the neodymium iron boron magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: firstly, preserving heat for 5 hours under vacuum at the temperature of 900 ℃, then reducing the temperature to 500 ℃, and continuously preserving heat for 5 hours under vacuum;
the permeate coated ndfeb magnet gained 1.8% weight compared to the starting ndfeb magnet.
< example 3>
The invention provides a preparation method of Dy monatomic permeate, which comprises the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5;
the adhesive is an aqueous solution of polyvinyl alcohol PVA: mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing in a constant-temperature water bath kettle at 60 ℃, heating and stirring until the mixture is uniform and transparent, and obtaining the adhesive; the volume fraction of the industrial ethanol aqueous solution is 95 percent;
the preparation method of the dysprosium carbonate solution comprises the following steps: weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution;
the preparation method of ZIF-8 comprises the following steps:
s1, weighing 1 part of peptone, 5 parts of glucose and 1 part of yeast powder according to parts by weight, adding the mixture into 100 parts of sterile water, fully stirring, and placing the mixture under high temperature and high pressure for sterilization treatment for 20min after the solid is dissolved to obtain a liquid culture medium;
s2, taking 0.01 part of nano ferroferric oxide particles (the particle size is 120nm), sterilizing at high temperature and high pressure, and dispersing in 15 parts of sterile water to prepare a suspension of the nano particles; adding the suspension of the nano particles into a liquid culture medium, and fully stirring and uniformly mixing; then inoculating 1.5 parts of strains on a liquid culture medium, culturing at the temperature of 35 ℃ and the rotating speed of 200r/min, filtering after 96h, collecting first filter residue, washing the first filter residue for 3 times by using a sodium hydroxide aqueous solution with the mass fraction of 0.5%, then placing in flowing sterile water for washing for 5min, and then carrying out freeze-drying to obtain a hypha composite material; the strain is Aspergillus niger;
s3, soaking 0.1 part of the hypha composite material obtained in the step S2 into 30 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.5mol/L, standing for 40min after ultrasonic oscillation treatment is carried out for 30min, then taking the hypha composite material out of the zinc nitrate hexahydrate solution, soaking the hypha composite material into 40 parts of 2-methylimidazole solution with the molar concentration of 0.5mol/L, carrying out ultrasonic oscillation for 10min, then placing the hypha composite material in a magnetic field environment, heating to 45 ℃ and reacting for 40min, and changing the direction of the magnetic field every 5 min; after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 4 times in sequence, and then freeze-drying to obtain the compound; the solvents of the zinc nitrate hexahydrate solution and the 2-methylimidazole solution are both anhydrous methanol.
The invention also provides a use method of the Dy monatomic permeate, which comprises the following steps: mixing the Dy monatomic permeate with an industrial ethanol aqueous solution according to a weight ratio of 1:1 to obtain a permeate solution, coating the permeate solution on the surface of the neodymium iron boron magnet, baking the neodymium iron boron magnet in an oven at 150 ℃ for 40min, taking out the neodymium iron boron magnet from the oven, cooling to room temperature, coating and baking again to obtain the neodymium iron boron magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: firstly, preserving heat for 5 hours under vacuum at the temperature of 900 ℃, then reducing the temperature to 500 ℃, and continuously preserving heat for 5 hours under vacuum;
the permeate coated ndfeb magnet gained 1.8% weight compared to the starting ndfeb magnet.
< example 4>
The invention provides a preparation method of Dy monatomic permeate, which comprises the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5;
the adhesive is an aqueous solution of polyvinyl alcohol PVA: mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing in a constant-temperature water bath kettle at 60 ℃, heating and stirring until the mixture is uniform and transparent, and obtaining the adhesive; the volume fraction of the industrial ethanol aqueous solution is 95 percent;
the preparation method of the dysprosium carbonate solution comprises the following steps: weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution;
the preparation method of ZIF-8 comprises the following steps:
s1, weighing 0.6 part of peptone, 3 parts of glucose and 0.6 part of yeast powder according to parts by weight, adding the peptone, the glucose and the yeast powder into 100 parts of sterile water, fully stirring, and placing the mixture into a high-temperature high-pressure sterilization treatment room for 18min after the solid is dissolved to obtain a liquid culture medium;
step S2, taking 0.006 part of nano ferroferric oxide particles (the particle size is 110nm), and dispersing the nano ferroferric oxide particles into 10 parts of sterile water after high-temperature and high-pressure sterilization to prepare a suspension of the nano particles; adding the suspension of the nano particles into a liquid culture medium, and fully stirring and uniformly mixing; then inoculating 0.05-1.5 parts of strains to a liquid culture medium, culturing at the temperature of 25 ℃ and the rotating speed of 140r/min, filtering after 72 hours, collecting first filter residue, washing the first filter residue for 2 times by using a sodium hydroxide aqueous solution with the mass fraction of 0.5%, then placing the filter residue in flowing sterile water for washing for 3min, and then carrying out freeze drying to obtain a hypha composite material; the strain is Aspergillus niger;
s3, soaking 0.06 part of the hypha composite material obtained in the step S2 into 25 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.3mol/L, carrying out ultrasonic oscillation treatment for 25min, standing for 35min, taking the hypha composite material out of the zinc nitrate hexahydrate solution, soaking the hypha composite material into 35 parts of 2-methylimidazole solution with the molar concentration of 0.3mol/L, carrying out ultrasonic oscillation for 8min, then placing the hypha composite material in a magnetic field environment, heating to 40 ℃, reacting for 35min, and changing the direction of the magnetic field every 5 min; after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 3 times in sequence, and then freeze-drying to obtain the compound; the solvents of the zinc nitrate hexahydrate solution and the 2-methylimidazole solution are both anhydrous methanol.
The invention also provides a use method of the Dy monatomic permeate, which comprises the following steps: mixing the Dy monatomic permeate with an industrial ethanol aqueous solution according to a weight ratio of 1:1 to obtain a permeate solution, coating the permeate solution on the surface of the neodymium iron boron magnet, baking the neodymium iron boron magnet in an oven at 150 ℃ for 40min, taking out the neodymium iron boron magnet from the oven, cooling to room temperature, coating and baking again to obtain the neodymium iron boron magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: firstly, preserving heat for 5 hours under vacuum at the temperature of 900 ℃, then reducing the temperature to 500 ℃, and continuously preserving heat for 5 hours under vacuum;
the permeate coated ndfeb magnet gained 1.8% weight compared to the starting ndfeb magnet.
< comparative example 1>
A Dy single atom permeate was prepared, which is different from example 4 in that, in step S2, a suspension of nanoparticles was not added to the liquid medium, and the remaining conditions and parameters were the same as those of example 4.
The method for using Dy monatomic permeate was the same as in example 4.
< comparative example 2>
A method for preparing a Dy single atom permeate, which is different from example 4 in that 0.06 part of nano ferroferric oxide particles are directly immersed in a zinc nitrate hexahydrate solution without the steps of S1 and S2, and the rest of conditions and parameters are the same as those of example 4.
The method for using Dy monatomic permeate was the same as in example 4.
< comparative example 3>
A Dy monatomic permeate production method, which is different from example 4 in that the magnetic field direction is not changed in the magnetic field environment in step S3, and the other conditions and parameters are the same as those of example 4.
The method for using Dy monatomic permeate was the same as in example 4.
< comparative example 4>
The preparation method of the Dy monatomic permeate is different from that in embodiment 4, in the step S3, 0.02-0.1 part of the hypha composite material obtained in the step S2 is soaked in 20-30 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.1-0.5 mol/L, the mixture is subjected to ultrasonic oscillation treatment for 20-30 min and then is kept stand for 30-40 min, then the hypha composite material is taken out of the zinc nitrate hexahydrate solution and is soaked in 30-40 parts of 2-methylimidazole solution with the molar concentration of 0.1-0.5 mol/L, the mixture is subjected to ultrasonic oscillation for 5-10 min, and the mixture is heated to 35-45 ℃ to react for 30-40 min; and after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 2-4 times in sequence, and freeze-drying to obtain ZIF-8. The remaining conditions and parameters were the same as in example 4.
The method for using Dy monatomic permeate was the same as in example 4.
The performance of the magnets obtained by the permeation treatment method in the embodiments 1 to 4 and the comparative examples 1 to 4 of the invention is tested, meanwhile, the original shape of the non-permeated neodymium-iron-boron magnet with the same specification is used as a comparison group 1, a conventional technical means is adopted, the surface of the neodymium-iron-boron magnet is coated with nano dysprosium oxide as a permeant in a weight ratio as equal to that in the embodiments 1 to 4 of the invention, and the permeation treatment is used as a comparison group 2; the neodymium iron boron magnet was selected from 7cm x 3cm, 7cm x 5cm, 7cm x 7cm and 7cm x 10cm, and the detection results are shown in table 1:
TABLE 1 residual magnetism and intrinsic coercivity measurements of NdFeB magnets
Figure BDA0002345441270000101
As can be seen from the data in table 1, when Dy atoms are used for infiltration, the remanence and coercivity of a magnet with a large thickness can be greatly improved, i.e., the Dy atom infiltration technology is not affected by the thickness of the magnet compared with the prior art; (comparison of controls 1-2 with example 1);
ZIF-8 is synthesized in situ on the hypha composite nano material and is used in the technology for preparing Dy atoms, so that the permeability of a Dy atom penetrating agent can be improved, and the aims of improving the residual magnetism and coercive force performance of a magnet are fulfilled; (comparison of example 1 with examples 2 to 4);
hyphae are cultured on the nano ferroferric oxide particles, the formed hypha composite nano material is used as a substrate for synthesizing ZIF-8, and the permeability of the permeate can be further improved through magnetic field treatment during preparation, so that the aim of further improving the residual magnetism and coercive force performance of the magnet is fulfilled (comparison between example 4 and comparative examples 1-4).
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, whereby the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (9)

  1. A preparation method of Dy monatomic permeate is characterized by comprising the following steps: adding ZIF-8 powder into dysprosium carbonate solution, and placing into NH at 900 deg.C3Preserving heat for 1h in the environment to obtain solid powder, namely Dy monatomic permeate;
    wherein the dysprosium carbonate solution comprises an industrial ethanol aqueous solution, a binder and dysprosium carbonate in a weight ratio of 10:1.8: 5.
  2. 2. The method of claim 1, wherein the binder is an aqueous solution of polyvinyl alcohol (PVA): mixing polyvinyl propanol PVA powder and water according to a weight ratio of 1:10, placing the mixture in a constant-temperature water bath kettle at the temperature of 60 ℃, and heating and stirring the mixture until the mixture is uniform and transparent to obtain the adhesive.
  3. 3. The method of claim 2, wherein the industrial ethanol aqueous solution has a volume fraction of 95%.
  4. 4. The method for preparing Dy monatomic permeate according to claim 3, wherein the method for preparing the dysprosium carbonate solution comprises: and weighing the industrial ethanol aqueous solution, the adhesive and the dysprosium carbonate in sequence according to the weight ratio, mixing, and fully stirring to obtain a homogeneous solution.
  5. 5. The method of preparing a Dy single atom permeate according to claim 4, wherein the method of preparing ZIF-8 comprises the steps of:
    s1, weighing 0.2-1 part of peptone, 1-5 parts of glucose and 0.2-1 part of yeast powder by weight, adding into 100 parts of sterile water, fully stirring, and placing in high-temperature high-pressure sterilization for 15-20 min after the solid is dissolved to obtain a liquid culture medium;
    s2, taking 0.002-0.01 part of nano ferroferric oxide particles, sterilizing at high temperature and high pressure, and dispersing in 5-15 parts of sterile water to prepare a suspension of the nano particles; adding the suspension of the nano particles into a liquid culture medium, and fully stirring and uniformly mixing; then inoculating 0.05-1.5 parts of strains to a liquid culture medium, culturing at the temperature of 15-35 ℃ and the rotating speed of 80-200 r/min, filtering after 48-96 h, collecting first filter residue, washing the first filter residue for 1-3 times by using a sodium hydroxide aqueous solution with the mass fraction of 0.5%, then placing the filter residue under flowing sterile water for washing for 2-5 min, and then carrying out freeze drying to obtain a hypha composite material;
    s3, soaking 0.02-0.1 part of the hypha composite material obtained in the step S2 into 20-30 parts of zinc nitrate hexahydrate solution with the molar concentration of 0.1-0.5 mol/L, performing ultrasonic oscillation treatment for 20-30 min, standing for 30-40 min, taking the hypha composite material out of the zinc nitrate hexahydrate solution, soaking the hypha composite material into 30-40 parts of 2-methylimidazole solution with the molar concentration of 0.1-0.5 mol/L, performing ultrasonic oscillation for 5-10 min, then placing the hypha composite material in a magnetic field environment, heating to 35-45 ℃, reacting for 30-40 min, and changing the magnetic field direction every 5 min; and after the reaction is finished, filtering and collecting second filter residue, washing the second filter residue with ethanol and water for 2-4 times in sequence, and freeze-drying to obtain the product.
  6. 6. The method of claim 5, wherein the Dy monatomic permeate is produced by any one of Mucor, Aspergillus niger, Rhizopus, and Penicillium.
  7. 7. The method of claim 6, wherein the solvent for the zinc nitrate hexahydrate solution and the 2-methylimidazole solution is absolute methanol.
  8. 8. The use method of the Dy monatomic permeate according to any one of claims 1 to 7, which is specifically characterized by comprising the following steps: mixing the Dy monatomic permeate with an industrial ethanol aqueous solution according to a weight ratio of 1:1 to obtain a permeate solution, coating the permeate solution on the surface of the neodymium iron boron magnet, baking the neodymium iron boron magnet in an oven at 150 ℃ for 40min, taking out the neodymium iron boron magnet from the oven, cooling to room temperature, coating and baking again to obtain the neodymium iron boron magnet coated with the permeate; placing the neodymium iron boron magnet coated with the permeant in a tempering furnace, vacuumizing until the internal pressure of the tempering furnace is 0.5Pa, and then tempering; the tempering treatment comprises two steps: the temperature is first maintained for 5h under vacuum at 900 ℃, then the temperature is reduced to 500 ℃ and the temperature is maintained for 5h under vacuum.
  9. 9. The method of using Dy single atom permeate of claim 8, wherein the permeate coated ndfeb magnet is weighted 1.8% compared to the starting ndfeb magnet.
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JPH02106009A (en) * 1988-10-14 1990-04-18 Murata Mfg Co Ltd Manufacture of ferrite core
US20150031908A1 (en) * 2013-07-23 2015-01-29 Northwestern University Metallated metal-organic frameworks
WO2017210874A1 (en) * 2016-06-08 2017-12-14 Xia, Ling Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation
CN108929684A (en) * 2018-08-29 2018-12-04 济南大学 A kind of coconut palm monofilament is the preparation method of carbon source dysprosium doped carbon quantum dot composite material
CN109821576A (en) * 2019-02-18 2019-05-31 河海大学 A kind of dysprosium Base Metal organic framework material Dy-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02106009A (en) * 1988-10-14 1990-04-18 Murata Mfg Co Ltd Manufacture of ferrite core
US20150031908A1 (en) * 2013-07-23 2015-01-29 Northwestern University Metallated metal-organic frameworks
WO2017210874A1 (en) * 2016-06-08 2017-12-14 Xia, Ling Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation
CN108929684A (en) * 2018-08-29 2018-12-04 济南大学 A kind of coconut palm monofilament is the preparation method of carbon source dysprosium doped carbon quantum dot composite material
CN109821576A (en) * 2019-02-18 2019-05-31 河海大学 A kind of dysprosium Base Metal organic framework material Dy-MOF and preparation method thereof, methylene blue dye photocatalytic degradation method

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