CN112430800B - Preparation method of neodymium iron boron material containing composite coating - Google Patents
Preparation method of neodymium iron boron material containing composite coating Download PDFInfo
- Publication number
- CN112430800B CN112430800B CN202011152396.3A CN202011152396A CN112430800B CN 112430800 B CN112430800 B CN 112430800B CN 202011152396 A CN202011152396 A CN 202011152396A CN 112430800 B CN112430800 B CN 112430800B
- Authority
- CN
- China
- Prior art keywords
- iron boron
- neodymium iron
- base material
- neodymium
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0694—Halides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0572—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
Abstract
The invention relates to the field of magnetic materials, and discloses a preparation method of a neodymium iron boron material containing a composite coating, which comprises the following steps: 1) Carrying out acid washing treatment on the surface of the NdFeB substrate; 2) Plating a layer of Tb, dy and TbF-containing neodymium-iron-boron base material after pickling treatment by adopting a magnetron sputtering method 3 At least one of the inner plating films; then plating an outer coating film of AlCrSiN-Al; 3) And carrying out heat treatment on the coated neodymium iron boron base material under a vacuum condition, then carrying out tempering treatment under the protection of inert gas, and cooling to obtain the neodymium iron boron material. The surface of the neodymium iron boron material is provided with the composite coating, has high coercivity and high temperature stability under the premise of low Dy (Tb) content, is suitable for a magnet base material with the thickness of more than 5mm, and has small residual magnetism reduction amplitude.
Description
Technical Field
The invention relates to the field of magnetic materials, in particular to a preparation method of a neodymium iron boron material containing a composite coating.
Background
Neodymium-iron-boron magnets are widely applied due to excellent magnetic properties such as high saturation magnetic induction, high coercivity, high magnetic energy product and the like, and relate to the fields of computers, intelligent manufacturing, new energy automobiles, motors, variable frequency air conditioners, medical equipment, elevators, acoustic equipment, mineral sorting and the like. But the Curie temperature of the NdFeB alloy is low, and the magnetocrystalline anisotropy field is rapidly reduced along with the temperature rise. Therefore, the coercive force of the neodymium-iron-boron magnet is very fast reduced along with the rise of temperature, and the application requirements of materials with high thermal stability in the fields of motors and the like are difficult to meet. To obtain high thermal stability, the coercivity of the neodymium-iron-boron magnet must be increased.
At present, most of neodymium-iron-boron magnets applied at high temperature are added with relatively large amounts of Dy and Tb so as to improve Nd 2 Fe 14 Magnetocrystalline anisotropy of the B hard magnetic phase. However, in RE 2 Fe 14 In the compound B, the magnetic moment of Dy or Tb is coupled with Fe in antiparallel, and the addition of Dy or Tb can lead to the reduction of the magnetization intensity and magnetic energy product of the material; on the other hand, in the current research of improving neodymium iron boron by a grain boundary diffusion method, a magnet with a thickness of 5mm or less is mainly focused, mainly because the amount of elements in a plating layer entering the neodymium iron boron magnet through a grain boundary during heat treatment is affected by the content of heavy rare earth in the magnet, the content of the plating layer element is gradually reduced inwards along the surface of the magnet, the depth of the same-component magnet entering the magnet through the grain boundary diffusion is constant, and the thicker the magnet is, the smaller the diffusion ratio of the magnet entering is. Therefore, the effect of improving the performance of a magnet of 5mm or more by the grain boundary diffusion material is inferior to that of 5mm or less, and therefore, the effect is not remarkable and less studied for a magnet of 5mm or more. Therefore, development of a neodymium-iron-boron magnet having a high coercivity and high temperature stability with less Dy (Tb) and a low rare earth content, and development of a neodymium-iron-boron magnet having a high coercivity with a substrate thickness of 5mm or more with a slight decrease in remanence, are urgent.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a neodymium iron boron material containing a composite coating. The surface of the neodymium iron boron material is provided with the composite coating, has high coercivity and high temperature stability under the premise of low Dy (Tb) content, is suitable for a magnet base material with the thickness of more than 5mm, and has small residual magnetism reduction amplitude.
The specific technical scheme of the invention is as follows: a preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) And carrying out acid washing treatment on the surface of the NdFeB substrate.
2) Plating a layer of Tb, dy and TbF-containing neodymium-iron-boron base material after pickling treatment by adopting a magnetron sputtering method 3 At least one of the inner plating films; then plating an outer plating film containing AlCrSiN-Al.
3) And carrying out heat treatment on the coated neodymium iron boron base material under a vacuum condition, then carrying out tempering treatment under the protection of inert gas, and cooling to obtain the neodymium iron boron material.
In the step 1), the purpose of carrying out acid cleaning treatment on the surface of the NdFeB substrate is as follows: the neodymium iron boron substrate can cause certain damage on the substrate surface in an acidic solution environment, so that the roughness of the substrate surface is increased, the increase of the roughness is favorable for adhesion of coating elements on the substrate surface in a magnetron sputtering process, the utilization rate of a target is greatly improved, and meanwhile, impurities such as greasy dirt, rust and the like on the surface of a magnet can be removed in an acid washing process.
In the step 2), an inner coating film and an outer coating film are sequentially generated on the surface of the neodymium iron boron base material through a magnetron sputtering method. During the heat treatment in the step 3), rare earth elements in the inner coating enter a gap between the main phases through a grain boundary and are distributed along the interface of the main phases, so that the grain boundary phase structure can be improved, the anisotropic field of the surface of the main phase grains can be improved, and the coercive force of the neodymium-iron-boron magnet can be improved. However, in the subsequent heat treatment and tempering treatment, a part of rare earth elements enter the main phase region along the grain boundary through diffusion action in the single rare earth plating film, are distributed along the main phase gap, and the other part of rare earth elements are volatilized and attached on the inner wall of the sintering furnace at high temperature. The volatilization of the coating can cause the reduction of rare earth elements entering the main phase, so that the improvement of the coercive force of the magnet is difficult to achieve the expected result, the aim can be achieved only by increasing the thickness of the coating, and the waste of materials is caused while the production cost is increased. In addition, the volatilization and adhesion of the coating on the inner wall of the sintering furnace can cause pollution problem of the internal environment of the sintering furnace, and unnecessary cost is increased on the cleaning problem.
In order to solve the technical problems, the invention adds a layer of external coating AlCrSiN-Al with high strength and high hardness and high temperature resistance outside the rare earth coating to completely coat the internal coating. The stability of the outer coating film is good in the subsequent heat treatment and tempering treatment, the volatilization phenomenon can not occur outwards, and the outer coating film can not enter the magnet tissue inwards to participate in the reaction so as not to damage the main phase tissue. The blocking of the outer coating to the rare earth element in the inner coating can avoid the volatilization phenomenon of the inner coating at the high temperature of the rare earth element, so that the material can be better utilized to greatly improve the coercive force of the magnet.
In addition, the AlCrSiN and Al are compounded, the addition of Al in the diffusion process of the external coating can reduce the melting point of a diffusion source, simultaneously increase the lubricity of the diffusion source and the surface of a magnet, and rapidly form a continuous grain boundary phase as a diffusion channel to promote Tb, dy or TbF 3 Diffusion of (2); in addition, al enters the magnet to form continuous and uniform grain boundary phase, so that the demagnetizing exchange coupling effect among main phase grains is enhanced, and the performance of the magnet is improved.
In the step 3), during the heat treatment, the Al in the outer coating film is gradually melted along with the rise of the temperature, and after the temperature exceeds the melting point of the Al, the Al in the outer coating film is in a molten state and gradually moves towards the inner coating film along with the progress of the heat treatment, thereby promoting Tb, dy or TbF 3 The molten Al liquid is dispersed and distributed between the inner plating film and the outer plating film, a layer of buffer effect can be achieved between the inner plating film and the outer plating film, the molten Al liquid enters the magnet along with the inner plating film in the heat treatment process, and the outer plating film is uniformly distributed on the surface of the magnet, so that the outer plating film and the surface of the magnet form good combination in the diffusion process.
In conclusion, the invention can realize the maximum utilization of rare earth elements of the inner plating film, can effectively reduce the thickness of the inner plating film, and ensures that the inner plating film with smaller thickness can achieve the same effect of high-thickness plating film and has low production cost. The invention effectively utilizes the rare earth elements of the inner coating film, so that the performance of the magnetic material with the thickness of the neodymium iron boron matrix being more than 5mm is greatly improved, and the reduction of the remanence accords with the expected standard.
Preferably, in step 1), the composition of the neodymium iron boron base material is RE x B y Ga z Zr v Cu k Al t Co u Fe 1-x-y-z-v-k-t-u Wherein x=31-32.5, y=0.9-1.0, z=0.1-0.2, v=0.1-0.2, k=0.1-0.85, t=0.05-0.09, u=0.5-2.
Preferably, in step 1), the acid washing is performed by using 3 to 5wt% of nitric acid aqueous solution, and the acid washing time is 1 to 3 minutes.
Preferably, in the step 1), after pickling, the neodymium iron boron substrate is subjected to ultrasonic cleaning, then the neodymium iron boron substrate is soaked in absolute ethyl alcohol for 10-30 seconds, taken out, dried and cleaned to remove residual moisture and impurities on the surface of the neodymium iron boron substrate.
Preferably, in the step 2), the composition of the overcoat film is (AlCrSiN) 100-x Al x Where x=5-10.
Preferably, in the step 2), the thickness of the neodymium iron boron base material is 5-8 mm, the thickness of the inner coating film is 4-8 μm, and the thickness of the outer coating film is 2-6 μm.
Preferably, in step 2), the composition of the inner plating film is specifically preferably Tb, dy or TbF 3 。
Preferably, in the step 3), the heat treatment temperature is 870-940 ℃, and the heat treatment time is 4-6h.
Preferably, in the step 3), the tempering treatment temperature is 480-500 ℃ and the tempering treatment time is 4-6 h; the inert gas is argon.
Compared with the prior art, the invention has the following technical effects: the surface of the neodymium-iron-boron substrate is sequentially provided with Tb, dy and TbF 3 The inner coating and the outer coating containing AlCrSiN-Al can realize the maximum utilization of rare earth elements of the inner coating, effectively reduce the thickness of the inner coating, have high coercive force and high temperature stability on the premise of lower Dy (Tb) content, are suitable for magnet base materials with the thickness of more than 5mm, and have small residual magnetism reduction amplitude.
Detailed Description
The invention is further described below with reference to examples.
General examples
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The water solution of 3-5 wt% nitric acid is adopted to make up the NdFeB base material (the composition of the NdFeB base material is RE) x B y Ga z Zr v Cu k Al t Co u Fe 1-x-y-z-v-k-t-u Wherein x=31 to 32.5, y=0.9 to 1.0, z=0.1 to 0.2, v=0.1 to 0.2, k=0.1 to 0.85, t=0.05 to 0.09, u=0.5 to 2) is subjected to acid cleaning treatment for 1 to 3 minutes. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 10-30 s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer of Tb, dy and TbF-containing neodymium-iron-boron base material after pickling treatment by adopting a magnetron sputtering method 3 At least one of the inner plating films; then plating an outer coating film containing AlCrSiN-Al (the specific component is (AlCrSiN) 100-x Al x Where x=5-10). Wherein the thickness of the NdFeB substrate is 5-8 mm, the thickness of the inner coating is 4-8 mu m, and the thickness of the outer coating is 2-6 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 4-6 hours under vacuum condition at 870-940 ℃, then tempering for 4-6 hours under the protection of inert gas (preferably argon) at 480-500 ℃, and cooling to obtain the neodymium iron boron material.
Example 1
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 4wt% nitric acid aqueous solution 31.35 Dy 0.7 B 0.9 4 Ga 0.17 Zr 0.15 Cu 0.13 Al 0.07 Co 0.7 Fe 65.79 ) The surface is subjected to pickling treatment for 2min. Ultrasonic cleaning is carried out on the NdFeB substrate after pickling, and thenSoaking the NdFeB substrate in absolute ethyl alcohol for 20s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer of Tb inner coating on the neodymium-iron-boron base material subjected to acid washing treatment by adopting a magnetron sputtering method; then further plating a layer (AlCrSiN) 95 Al 5 And (5) coating a film. Wherein the thickness of the NdFeB substrate is 5mm, the thickness of the inner coating is 4 mu m, and the thickness of the outer coating is 3 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 6 hours under vacuum condition at 900 ℃, then carrying out tempering treatment under the protection of argon at 480 ℃ for 4 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in example 1 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Example 2
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is treated by 5wt% of nitric acid aqueous solution 31.45 Dy 0.7 B 0.9 2 Ga 0.15 Zr 0.16 Cu 0.2 Al 0.08 Co 0.9 Fe 65.44 ) The surface is subjected to pickling treatment for 1min. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 30s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer of Tb inner coating on the neodymium-iron-boron base material subjected to acid washing treatment by adopting a magnetron sputtering method; then further plating a layer (AlCrSiN) 94 Al 6 And (5) coating a film. Wherein the thickness of the NdFeB substrate is 6mm, the thickness of the inner coating is 6 mu m, and the thickness of the outer coating is 4 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 6 hours under vacuum condition at 900 ℃, then carrying out tempering treatment under the protection of argon at 480 ℃ for 5 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in example 2 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Example 3
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 3wt% of nitric acid aqueous solution 31.35 Dy 0.8 B 0.9 6 Ga 0.17 Zr 0.15 Cu 0.25 Al 0.07 Co 1.1 Fe 65.15 ) The surface is subjected to pickling treatment for 3min. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 10s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer of Tb inner coating on the neodymium-iron-boron base material subjected to acid washing treatment by adopting a magnetron sputtering method; then further plating a layer (AlCrSiN) 92 Al 8 And (5) coating a film. Wherein the thickness of the NdFeB substrate is 7mm, the thickness of the inner coating is 8 mu m, and the thickness of the outer coating is 6 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 5 hours under vacuum condition at 920 ℃, then carrying out tempering treatment under the protection of inert gas (preferably argon) at 500 ℃ for 5 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in example 3 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Example 4
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 4wt% nitric acid aqueous solution 31.2 Dy 0.8 B 0.94 Ga 0.18 Zr 0.17 Cu 0.15 Al 0.06 Co 1.2 Fe 65.3 ) The surface is subjected to pickling treatment for 2min. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 15s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Neodymium-iron-boron base after pickling treatment by magnetron sputtering methodPlating a layer of Tb inner coating film; then further plating a layer (AlCrSiN) 90 Al 10 And (5) coating a film. Wherein the thickness of the NdFeB substrate is 8mm, the thickness of the inner coating is 8 mu m, and the thickness of the outer coating is 6 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 4 hours under vacuum condition at 940 ℃, then carrying out tempering treatment under argon protection at 500 ℃ for 6 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in example 4 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Comparative example 1
The preparation method of the neodymium iron boron material comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 4wt% nitric acid aqueous solution 31.2 Dy 0.8 B 0.94 Ga 0.18 Zr 0.17 Cu 0.15 Al 0.06 Co 1.2 Fe 65.3 ) The surface is subjected to pickling treatment for 2min. And (3) carrying out ultrasonic cleaning on the neodymium-iron-boron substrate after pickling, soaking the neodymium-iron-boron substrate in absolute ethyl alcohol for 20s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the neodymium-iron-boron substrate, thereby obtaining the neodymium-iron-boron material with the thickness of 8mm.
The magnetic properties of the neodymium-iron-boron magnet prepared in comparative example 1 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Comparative example 2
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 4wt% nitric acid aqueous solution 31.2 Dy 0.8 B 0.94 Ga 0.18 Zr 0.17 Cu 0.15 Al 0.06 Co 1.2 Fe 65.3 ) The surface is subjected to pickling treatment for 2min. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 25 seconds, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer of Tb inner coating on the neodymium-iron-boron base material subjected to acid washing treatment by adopting a magnetron sputtering method; then an AlCrSiN outer coating film is coated. Wherein the thickness of the NdFeB substrate is 8mm, the thickness of the inner coating is 8 mu m, and the thickness of the outer coating is 6 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 4 hours under vacuum condition at 940 ℃, then carrying out tempering treatment under argon protection at 500 ℃ for 6 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in comparative example 2 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Comparative example 3
The preparation method of the neodymium iron boron material comprises the following steps:
1) The NdFeB substrate (the composition of the NdFeB substrate is PrNd) is subjected to 4wt% nitric acid aqueous solution 31.2 Dy 0.8 B 0.94 Ga 0.18 Zr 0.17 Cu 0.15 Al 0.06 Co 1.2 Fe 65.3 ) The surface is subjected to pickling treatment for 2min. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 20s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) And plating a layer of Tb 8 mu m coating film on the NdFeB substrate subjected to acid washing treatment by adopting a magnetron sputtering method. Wherein, the thickness of neodymium iron boron substrate is 8mm.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 4 hours under vacuum condition at 940 ℃, then carrying out tempering treatment under argon protection at 500 ℃ for 6 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet prepared in comparative example 3 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Comparative example 4
A preparation method of a neodymium iron boron material containing a composite coating comprises the following steps:
1) The water solution of 3-5 wt% nitric acid is adopted to make up the NdFeB base material (the composition of the NdFeB base material is PrNd 31.2 Dy 0. 8 B 0.94 Ga 0.18 Zr 0.17 Cu 0.15 Al 0.06 Co 1.2 Fe 65.3 ) The surface is subjected to acid washing treatment for 1 to 3 minutes. And (3) carrying out ultrasonic cleaning on the NdFeB substrate after pickling, soaking the NdFeB substrate in absolute ethyl alcohol for 10-30 s, taking out, drying, and cleaning the surface to remove residual moisture and impurities on the surface of the NdFeB substrate.
2) Plating a layer (AlCrSiN) on the NdFeB substrate after pickling by adopting a magnetron sputtering method 90 Al 10 And (5) coating. Wherein the thickness of the NdFeB substrate is 8mm, and the thickness of the coating film is 6 mu m.
3) And carrying out heat treatment on the neodymium iron boron base material subjected to film coating for 4 hours under vacuum condition at 940 ℃, then carrying out tempering treatment under argon protection at 500 ℃ for 6 hours, and cooling to obtain the neodymium iron boron material.
The magnetic properties of the neodymium-iron-boron magnet obtained in comparative example 4 were measured by using a test apparatus, and the magnetic properties data are shown in table 1.
Table 1 results of magnetic performance test of neodymium-iron-boron magnet
| Residual magnetism Br (kGs) | Intrinsic coercivity Hcj (kOe) | Magnetic energy product (BH) max (KGs) | |
| Example 1 | 13.91 | 26.4 | 47.9 |
| Example 2 | 13.94 | 25.6 | 48.2 |
| Example 3 | 13.93 | 24.4 | 48.3 |
| Example 4 | 13.94 | 23.3 | 48.7 |
| Comparative example 1 | 14.02 | 17.5 | 48.7 |
| Comparative example 2 | 13.98 | 22.6 | 48.2 |
| Comparative example 3 | 13.98 | 21.1 | 48.7 |
| Comparative example 4 | 13.98 | 17.4 | 48.3 |
As can be seen from the test data in Table 1, examples 1 to 4 are data of the same substrate having different thicknesses after diffusion treatment, and comparative example 1 is the property of the original substrateThe data can be analyzed from the table, and the coercivity of the base materials with different thicknesses is greatly improved after diffusion treatment, and the coercivity improving effect of the material is reduced along with the increase of the thickness of the base materials; example 4 differs from comparative example 2 in that the overcoat film in comparative example 2 has no Al component, and the addition of Al can lower the melting point of the diffusion source while increasing the lubricity of the diffusion source and the magnet surface, and rapidly forms a continuous grain boundary phase as a diffusion channel, promoting Tb, dy or TbF 3 Diffusion of (2); in addition, al enters the magnet to form a continuous and uniform grain boundary phase, so that the demagnetizing exchange coupling effect among main phase grains is enhanced, and the performance of the magnet is improved, therefore, the coercivity improving effect of the material in the embodiment 4 is more remarkable than that in the comparative example 2, but the addition of Al also reduces the remanence of the material to a certain extent, so that the remanence in the embodiment 4 is lower than that in the comparative example 2; example 4 differs from comparative example 3 in that comparative example 3 has only one layer of Tb film on the surface of the substrate, and in the diffusion process, there is no layer of high temperature resistant AlCrSiN-Al on the surface of the Tb plating layer, tb volatilizes to cause decrease of Tb diffused into the magnet interior while no Al helps Tb diffuse insufficiently in the magnet interior, so that the coercivity boosting effect in comparative example 3 is lower than that in example 4; comparative example 4 only had a single AlCrSiN-Al coating on the substrate surface, and since AlCrSiN in the coating had high strength, high hardness and high temperature resistance, it did not enter the inside of the magnet during diffusion, and therefore the coercive force of the material was not improved, and Al in the coating could enter the inside of the magnet by diffusion, resulting in a decrease in remanence.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the neodymium iron boron material containing the composite coating film is characterized by comprising the following steps of:
1) Carrying out acid washing treatment on the surface of the NdFeB substrate;
2) Plating a layer of Tb, dy and TbF-containing neodymium-iron-boron base material after pickling treatment by adopting a magnetron sputtering method 3 At least one of the inner plating films; then plating a layer composed of AlCrSiN and Al (AlCrSiN) 100-x Al x An overcoat film, wherein x=5 to 10;
3) And carrying out heat treatment on the coated neodymium iron boron base material under a vacuum condition, then carrying out tempering treatment under the protection of inert gas, and cooling to obtain the neodymium iron boron material.
2. The method of manufacturing according to claim 1, wherein: in the step 1), 3-5wt% of nitric acid aqueous solution is adopted for pickling, and the pickling time is 1-3 min.
3. The preparation method according to claim 1 or 2, characterized in that: in the step 1), ultrasonic cleaning is carried out on the neodymium iron boron base material after pickling, then the neodymium iron boron base material is soaked in absolute ethyl alcohol for 10-30 s, taken out, dried and cleaned to remove residual moisture and impurities on the surface of the neodymium iron boron base material.
4. The method of manufacturing according to claim 1, wherein: in the step 2), the components of the inner coating film are Tb, dy or TbF 3 。
5. The method of claim 1 or 4, wherein: in the step 2), the thickness of the neodymium iron boron base material is 5-8 mm, the thickness of the inner coating film is 4-8 mu m, and the thickness of the outer coating film is 2-6 mu m.
6. The method of manufacturing according to claim 1, wherein: in the step 3), the heat treatment temperature is 870-940 ℃ and the heat treatment time is 4-6h.
7. The method of claim 1 or 6, wherein: in the step 3), the tempering treatment temperature is 480-500 ℃ and the tempering treatment time is 4-6h.
8. The method of manufacturing according to claim 1, wherein: in the step 3), the inert gas is argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011152396.3A CN112430800B (en) | 2020-10-23 | 2020-10-23 | Preparation method of neodymium iron boron material containing composite coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011152396.3A CN112430800B (en) | 2020-10-23 | 2020-10-23 | Preparation method of neodymium iron boron material containing composite coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112430800A CN112430800A (en) | 2021-03-02 |
| CN112430800B true CN112430800B (en) | 2023-04-28 |
Family
ID=74696028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011152396.3A Active CN112430800B (en) | 2020-10-23 | 2020-10-23 | Preparation method of neodymium iron boron material containing composite coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112430800B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61150201A (en) * | 1984-12-24 | 1986-07-08 | Sumitomo Special Metals Co Ltd | Permanent magnet with excellent anticorrosion property |
| CN104681225A (en) * | 2013-12-03 | 2015-06-03 | 湖南稀土金属材料研究院 | Treating method for improving performance of sintered NdFeB (neodymium iron boron) materials |
| CN105755441A (en) * | 2016-04-20 | 2016-07-13 | 中国科学院宁波材料技术与工程研究所 | Method for diffusing permeation of heavy rare earth through magnetron sputtering method to improve coercivity of sintered neodymium iron boron |
| CN111524670A (en) * | 2019-02-01 | 2020-08-11 | 天津三环乐喜新材料有限公司 | Method for producing rare earth diffusion magnet and rare earth diffusion magnet |
-
2020
- 2020-10-23 CN CN202011152396.3A patent/CN112430800B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61150201A (en) * | 1984-12-24 | 1986-07-08 | Sumitomo Special Metals Co Ltd | Permanent magnet with excellent anticorrosion property |
| CN104681225A (en) * | 2013-12-03 | 2015-06-03 | 湖南稀土金属材料研究院 | Treating method for improving performance of sintered NdFeB (neodymium iron boron) materials |
| CN105755441A (en) * | 2016-04-20 | 2016-07-13 | 中国科学院宁波材料技术与工程研究所 | Method for diffusing permeation of heavy rare earth through magnetron sputtering method to improve coercivity of sintered neodymium iron boron |
| CN111524670A (en) * | 2019-02-01 | 2020-08-11 | 天津三环乐喜新材料有限公司 | Method for producing rare earth diffusion magnet and rare earth diffusion magnet |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced magnetic properties and improving thermal stability for sintered Nd-Fe-B magnets prepared by two-step grain boundary diffusion processes;X.T.Yan et al.;《Journal of Magnetism and Magnetic Materials》;20190708;第491卷;Abstract、第3页右栏第2段、第5页左栏第2段、图1-6以及4.Conclusion * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112430800A (en) | 2021-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101534717B1 (en) | Process for preparing rare earth magnets | |
| CN106409497B (en) | A kind of method of neodymium iron boron magnetic body grain boundary decision | |
| RU2367045C2 (en) | Production of material of rare earth permanent magnet | |
| KR101624245B1 (en) | Rare Earth Permanent Magnet and Method Thereof | |
| EP3182423B1 (en) | Neodymium iron boron magnet and preparation method thereof | |
| CN107026003B (en) | Preparation method of sintered neodymium-iron-boron magnet | |
| RU2417139C2 (en) | Method of producing rare-earth permanent magnet material | |
| EP2808877A1 (en) | Method for preparing R-Fe-B based sintered magnet | |
| KR20060057540A (en) | Rare earth-iron-boron based magnet and method for production thereof | |
| JP2018082146A (en) | Method for manufacturing rare earth-iron-boron based sintered magnet | |
| CN109360728B (en) | Method for enhancing coercive force of neodymium iron boron magnet by evaporation crystal boundary diffusion | |
| KR101906069B1 (en) | Method For Preparing R-Fe-B Based Sintered Magnet | |
| US20190027306A1 (en) | Method of improving the coercivity of nd-fe-b magnets | |
| KR101932551B1 (en) | RE-Fe-B BASED RARE EARTH MAGNET BY GRAIN BOUNDARY DIFFUSION OF HAEVY RARE EARTH AND MANUFACTURING METHODS THEREOF | |
| WO2014034854A1 (en) | Production method for rare earth permanent magnet | |
| JP6107545B2 (en) | Rare earth permanent magnet manufacturing method | |
| CN106920669B (en) | Preparation method of R-Fe-B sintered magnet | |
| JP2015154051A (en) | Method for manufacturing rare earth permanent magnet | |
| KR20180025193A (en) | Method For Preparing R-Fe-B Based Sintered Magnet | |
| EP3667685A1 (en) | Heat-resistant neodymium iron boron magnet and preparation method therefor | |
| CN112489914A (en) | Method for preparing high-coercivity neodymium-iron-boron magnet through composite diffusion | |
| KR101995536B1 (en) | Manufacturing method of high performance rare earth magnet | |
| CN112430800B (en) | Preparation method of neodymium iron boron material containing composite coating | |
| CN110993307B (en) | Method for improving coercive force and thermal stability of sintered neodymium-iron-boron magnet | |
| KR20170045184A (en) | Method for manufacturing rare earth sintered magnet using low melting point elements |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230320 Address after: 310000 Qianjiang Farm 1st Branch, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant after: HANGZHOU PERMANENT MAGNET GROUP ZHENZE MAGNETIC INDUSTRY CO.,LTD. Address before: 311201 permanent magnet Industrial Park, No.1 Branch of Qianjiang farm, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: HANGZHOU PERMANENT MAGNET GROUP Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |