WO2016176974A1 - 复合靶气相沉淀制备晶界扩散稀土永磁材料的方法 - Google Patents

复合靶气相沉淀制备晶界扩散稀土永磁材料的方法 Download PDF

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WO2016176974A1
WO2016176974A1 PCT/CN2015/093951 CN2015093951W WO2016176974A1 WO 2016176974 A1 WO2016176974 A1 WO 2016176974A1 CN 2015093951 W CN2015093951 W CN 2015093951W WO 2016176974 A1 WO2016176974 A1 WO 2016176974A1
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magnet
composite target
ndfeb magnet
rare earth
ndfeb
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PCT/CN2015/093951
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English (en)
French (fr)
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周磊
刘涛
林德
喻晓军
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安泰科技股份有限公司
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Priority to SI201530499T priority Critical patent/SI3121823T1/sl
Priority to KR1020167032336A priority patent/KR101913137B1/ko
Priority to EP15884914.1A priority patent/EP3121823B1/en
Priority to US15/300,683 priority patent/US10385442B2/en
Priority to ES15884914T priority patent/ES2699949T3/es
Publication of WO2016176974A1 publication Critical patent/WO2016176974A1/zh

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    • 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
    • H01F41/02—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 for manufacturing cores, coils, or magnets
    • H01F41/0253—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 for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • 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
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15325—Amorphous metallic alloys, e.g. glassy metals containing rare earths
    • 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
    • H01F41/02—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 for manufacturing cores, coils, or magnets
    • H01F41/0253—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 for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • 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
    • H01F41/02—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 for manufacturing cores, coils, or magnets
    • H01F41/0253—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 for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—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 for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

Definitions

  • the invention belongs to the technical field of rare earth permanent magnet materials, in particular to a method for preparing a grain boundary diffusion rare earth permanent magnet material by vapor phase precipitation of a composite target, which is a method for vapor phase precipitation of a composite metal film on a surface of NdFeB and high temperature treatment. Low temperature aging to improve the performance of the magnet.
  • NdFeB permanent magnet materials in hybrid vehicles and wind power generation are increasing. These fields of application require magnets to operate at high temperatures for extended periods of time, which necessarily requires higher coercivity (Hcj). As the NdFeB magnet becomes thinner with the processing size, the coercive force drops significantly.
  • Substituting heavy rare earth elements such as Dy/Tb for Nd in the main phase of the magnet Nd 2 Fe 14 B to form (Nd, Dy) 2 Fe 14 B, (Nd, Tb) 2 Fe 14 B is more anisotropic than Nd 2 Fe 14 B, which is an effective method for increasing the NdFeB sintered magnet Hcj.
  • the grain boundary diffusion treatment technology mainly applies coating, deposition, plating, sputtering, adhesion, etc., so that metal powder (Dy, Tb or other rare earth elements) or compound adheres to the outer surface of the magnet, and the metal powder or compound is treated by heat treatment.
  • this grain boundary diffusion technique has a significant effect on the composition, microstructure and magnetic properties of the sintered NdFeB magnet.
  • the main techniques are evaporation or sputtering technology and coating. technology.
  • the evaporation or sputtering technique deposits rare earth elements such as Dy and Tb on the surface of the NdFeB sintered magnet, followed by heat treatment and diffusion.
  • the coating technique is to coat a surface of a magnet with a rare earth compound such as a fluoride or oxide powder and heat-spread.
  • the method of attaching Dy/Tb to the surface of NdFeB sintered magnet by sputtering has low productivity, high process cost, easy occurrence of defects such as crater, and a large amount of rare earth metal during evaporation. Dispersed in the furnace chamber, the utilization rate of heavy rare earth metals is low.
  • a method in which a fluoride or an oxide powder of Dy/Tb is adhered to a surface of a magnet and heated, or a method of filling a magnet and heating the mixed powder of the powder and the hydrogenated Ca powder is also as follows, and the number of steps is increased, and the cost is increased. The cost is high.
  • the heat diffusion is limited, and the coercivity is limited and other elements may enter the magnet with the diffusion process.
  • the surface is cleaned by washing or pickling, and then, after being subjected to surface treatment such as nickel plating or aluminum ion plating, after the fluoride or oxide powder is adhered to the surface and heated, Then after heating, it will form on the surface A portion of Dy/Tb is substituted with a surface layer composed of an oxide or fluoride of Nd.
  • surface treatment such as nickel plating or aluminum ion plating
  • the vapor phase precipitation method is a process in which a gaseous reaction raw material is reacted on a surface of a solid substrate and deposited into a solid thin layer or a thin film.
  • composite heavy rare earth elements Dy/Tb and Cu, Nd, Al are obtained by a vapor phase precipitation method using a composite target.
  • the method of evaporating the metal of the element such as Pr to the surface of NdFeB and diffusing the grain boundary to improve the performance of the coercive magnet has not been disclosed.
  • the invention aims at the deficiencies of the prior art, and aims to provide a method for preparing a grain boundary diffusion rare earth permanent magnet material by vapor phase precipitation of a composite target, so as to improve the coercive force of the permanent magnet material, and the residual magnetic and magnetic energy products are not substantially reduced.
  • a method for preparing a grain boundary diffusion rare earth permanent magnet material by vapor phase precipitation of a composite target comprises the following steps:
  • Step two processing the sintered NdFeB magnet into a prescribed shape and size, followed by surface cleaning and drying, thereby obtaining a NdFeB magnet to be processed;
  • Step 3 the composite target and the NdFeB magnet to be processed are alternately stacked in a processing device, and the uppermost layer and the bottommost layer are composite targets, and the composite target is used as an evaporation source under specified conditions.
  • Lower (ie, medium-high temperature) the surface of the NdFeB magnet to be treated is coated with a metal film and grain boundary diffusion occurs, and then cooled with the furnace to obtain a diffused NdFeB magnet;
  • step four the diffused NdFeB magnet is subjected to tempering treatment (ie, low temperature aging treatment), and the grain boundary phase is uniformly wrapped outside the main phase particles, thereby obtaining a magnet with improved performance.
  • tempering treatment ie, low temperature aging treatment
  • the composite target is prepared by weighing the corresponding raw materials according to the atomic percentage of each component of the composite target, After smelting, casting, forging, hot rolling, cold rolling and mechanical processing, a composite target of a predetermined size is formed.
  • the forging, hot rolling, and cold rolling processes will increase the density of the composite target, thereby affecting the life of the target and the degree of evaporation.
  • the thickness of the composite target will affect the strength of the target and the subsequent osmotic treatment effect. Under the same treatment conditions, the larger the surface area, the thinner the thickness, the more obvious the penetration effect of the composite target of the same weight.
  • the composite target The specified dimensions are: thickness of 0.5-3 mm, length of 180-300 mm, and width of 100-240 mm; preferably, the smelting is performed by vacuum medium frequency induction furnace, and the degree of vacuum is not higher than 10 -2 Pa (such as 0.05 Pa, 0.1 Pa, 0.5 Pa, 1 Pa, 2 Pa, 3 Pa), more preferably a vacuum of 10 -2 -1 Pa.
  • the The process of surface cleaning is as follows: firstly, the NdFeB magnet is placed in a degreasing tank for 10-15 minutes to remove the oil stain on the surface of the magnet, and then subjected to the first water washing, pickling, the second washing and ultrasonic treatment, and finally the air drying station.
  • the surface of the NdFeB magnet Preferably, the pickling time is 20-45 s (such as 22 s, 28 s, 35 s, 39 s, 44 s), and the ultrasonic treatment time is 20-45 s (such as 22 s, 28 s, 35 s, 39 s, 44 s).
  • the size of the NdFeB magnet to be processed is not strictly required.
  • the orientation direction of the NdFeB magnet to be processed is controlled to a thickness of 1-8 mm (for example, 2 mm, 4 mm, 6 mm, 7 mm).
  • the method of the present invention can process NdFeB magnets of a simple planar shape such as square or circular.
  • a piece of the NdFeB magnet to be processed is sandwiched between two of the composite targets, and the surface area of the composite target is larger than the The surface area of the NdFeB magnet to be treated.
  • the predetermined condition is as follows: the degree of vacuum is not more than 10 -3 Pa (for example, 5 ⁇ 10 -4 Pa, 1 ⁇ 10 -4 Pa, 8) ⁇ 10 -5 Pa, 5 ⁇ 10 -5 Pa, 1 ⁇ 10 -6 Pa), holding temperature is 650-900 ° C (such as 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C), insulation
  • the time is 5-50 h (6 h, 10 h, 20 h, 30 h, 40 h, 48 h); the furnace is cooled to not higher than 50 ° C (25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C). More preferably, in the third step, the holding temperature is 700-850 ° C, and the holding time is 5-35 h.
  • the tempering treatment condition is: tempering temperature is 420-640 ° C (such as 420 ° C, 460 ° C, 500 ° C, 550 ° C, 600 ° C 630 ° C), tempering time is 2-10h (such as 3h, 4h, 6h, 8h, 9h), then cooled to room temperature by natural cooling.
  • the processing device in the third step may be a vacuum heat treatment furnace.
  • the technical key of the third step is to overcome the disadvantage that a large amount of rare earth metal is dispersed in the furnace chamber in the evaporation method, and the utilization rate of the heavy rare earth metal is low, and the superposition performance can be generated by effectively utilizing the rare earth.
  • the amount of evaporation reduces excess adhesion to improve material utilization.
  • a composite metal target is used as a high-temperature evaporation source to form a metal film containing a heavy rare earth element and an auxiliary metal element on the surface of the sintered NdFeB magnet under medium and high temperature conditions. Evaporation, adhesion and grain boundary diffusion are carried out simultaneously, and the temperature is kept for a certain time under this temperature condition, so that the heavy rare earth element and the auxiliary metal diffuse through the grain boundary to the inside of the magnet, and the heavy rare earth element and the Nd in the main phase edge Nd 2 Fe 14 B A substitution reaction occurs to form a (Nd,H) 2 Fe 14 B phase with higher anisotropy, and a distinct network-like transition zone can be observed in the microstructure.
  • this transition zone allows the magnet to During the demagnetization process, the growth of the demagnetization domain nucleus is suppressed, so that the coercive force of the magnet is increased by 4000 to 13000 Oe, and the residual magnetization is reduced by less than 4.5%.
  • the present invention can reduce the amount of heavy rare earth used compared with the conventional method (that is, depositing rare earth elements such as Dy and Tb on the surface of the NdFeB magnet by evaporation technology). 20% while maintaining a very low remanence reduction rate.
  • the method of the present invention belongs to a method of condensing and attaching an auxiliary metal rich in heavy rare earth elements and having good wettability on the surface of NdFeB and treating it at a medium temperature.
  • the evaporation source material used in the present invention is a composite target material, and the target material is made of a substance having a different melting point. Due to the difference in the force between the internal particles of the material, the internal alloy target material can be increased, resulting in a decrease in the melting point. This allows the composite target to have a lower evaporation temperature, ie a lower processing temperature, than a pure metal target.
  • the invention has the beneficial effects that the preparation of the composite target is relatively simple, the vapor deposition precipitation temperature of the composite target is lower than other grain boundary diffusion techniques, and the heavy rare earth element can be enriched in the boundary region between the main phase and the rich phase, thereby making the NdFeB magnet
  • the coercivity has been significantly improved.
  • the invention opens up a novel route for improving the performance of the rare earth permanent magnet material NdFeB.
  • the invention is used to improve the performance of the magnet, on the one hand, the efficiency is high; on the other hand, the amount of heavy rare earth used is greatly reduced, the cost of the product is lowered, the cost performance of the product is more advantageous, and the melting pit caused by long-time high-temperature treatment can be eliminated.
  • the corrosion resistance is significantly improved.
  • the method of preparing grain boundary diffusion NdFeB rare earth permanent magnet by composite target vapor phase precipitation can effectively reduce the grain boundary diffusion treatment temperature and achieve grain boundary diffusion at a lower temperature. On the one hand, it can effectively control the evaporation amount and improve the utilization rate of the evaporation material; on the other hand, the low-temperature grain boundary diffusion treatment can avoid the defects such as the ablation pit and the abnormal growth of the crystal grains, and improve the yield of the grain boundary diffusion treatment magnet.
  • the composite addition of non-heavy rare earth elements has a significant improvement in the corrosion resistance and mechanical properties of the magnet.
  • Figure 1 is a process flow diagram of the present invention
  • Embodiment 2 is a micro-structure diagram of a magnet finally obtained in Embodiment 1 of the present invention.
  • Fig. 3 is a graph showing changes in performance of magnets before and after treatment in Example 1 of the present invention.
  • the NdFeB magnets to be treated used in the following methods were all sintered NdFeB magnets, and the same batches of sintered NdFeB magnets of the same grade were used in the respective examples.
  • Figure 1 shows the process flow of the process of the present invention comprising the steps of processing a sintered magnet into a sheet, cleaning the surface of the magnet, treating the medium and high temperatures, and treating the low temperature aging. Specific embodiments are given below.
  • the composite target having a thickness of 2 mm and a length and a width of 240 and 160 mm is respectively formed by forging, hot rolling, cold rolling and machining; then the scale of the surface of the composite target is removed to maintain the surface flatness of the target.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace, and the composite target is used as an evaporation source, and the degree of vacuum is 10 - Under 4 Pa conditions, heat at 700 ° C for 24 hours; then cool with the furnace to about 50 ° C;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 500 ° C for 5 hours, and then naturally cooled to room temperature to obtain a magnet having improved performance.
  • the microstructure of the magnet obtained in the present embodiment is compared with the conventional preparation method (such as the method described in the patent document of the publication No. CN101404195).
  • the microstructure of the magnet prepared by the conventional method (see the publication number CN101404195) Figure 1) of the patent document does not show a complete network-like structure; while the magnet microstructure of the present invention exhibits a distinct network-like structure, which shows that a continuous layer of rare earth-rich layer is coated on the surface of the main phase particles.
  • this thin layer can prevent the demagnetized domain core from nucleating and growing under the action of a lower external field, and on the other hand can perform a good demagnetization coupling effect on the main phase particles, thereby significantly increasing the coercive force.
  • the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the performance of the magnets before and after treatment by the method of the present embodiment is tested.
  • the test method is carried out according to the GB/T3217-1992 standard, and the tempered finished magnet is cut into a cylinder having a diameter of 10 mm, and tested, before high temperature and low temperature aging treatment.
  • the coercive force of the magnet is increased by 10990 Oe, the remanence is slightly reduced, the 330 Gs is reduced, and the remanence reduction rate is 2.3%, as shown in Fig. 3; the performance of the NdFeB magnet before and after the treatment of steps 3) and 4)
  • the change is shown in Table 1, that is, the comparative example described in FIG. 3 before the treatment, and the treatment is obtained after the treatment.
  • the performance of the improved magnet is shown in Table 1, that is, the comparative example described in FIG. 3 before the treatment, and the treatment is obtained after the treatment. The performance of the improved magnet.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace under the condition of a vacuum of 10 -4 Pa at 690. Incubate at °C for 30 hours; then cool to about 45 °C with the furnace;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 510 ° C for 5 hours, and then naturally cooled to room temperature to obtain a magnet having improved performance.
  • the microstructure of the magnet obtained in this embodiment is substantially the same as that of Fig. 2 and will not be repeated here. It can be seen from the figure that the microstructure of the magnet of the present invention exhibits a distinct network-like structure, which shows that a layer of continuous rare earth-rich layer is coated on the surface of the main phase particles, and this thin layer can prevent the demagnetization domain core from being
  • the nucleation and growth under the action of the lower external field on the other hand, can achieve a good demagnetization coupling effect on the main phase particles, so the coercivity can be significantly improved.
  • the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the performance of the magnet obtained in this example was tested according to the method of Example 1.
  • the test results showed that the coercive force of the magnet was increased by 8510 Oe, the remanence was slightly decreased, the 280 Gs was decreased, and the remanence reduction rate was 2%.
  • the NdFeB magnet was subjected to the step. 3) and 4) Performance changes before and after processing are shown in Table 1.
  • Tb 97 Nd 1 Al 2 (subscript of which is the atomic percentage of the corresponding element) composite target: the raw material Tb element (purity of 99.95%) and Nd element are weighed according to the chemical formula ratio of the above composite target ( The purity is 99.95%), Cu powder (purity is 99.95%), and it is smelted in a vacuum medium frequency induction furnace, wherein the smelting vacuum is 10 -2 Pa, the smelting temperature is 1040 ° C, and the smelting time is 15 minutes.
  • the molten alloy liquid is cast into a cast slab, and then subjected to forging, hot rolling, cold rolling and mechanical processing to form a composite target having a thickness of 3.0 mm and a length and a width of 200 and 110 mm, respectively; and then removing the oxidation of the surface of the target. Leather, etc., to maintain the surface flatness of the target.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace under the condition of a vacuum degree of 5 ⁇ 10 ⁇ 4 Pa. Incubate at 820 ° C for 35 hours; then cool to about 40 ° C with the furnace;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 470 ° C for 5 hours, and then naturally cooled to room temperature.
  • the microstructure of the magnet obtained in this embodiment is substantially the same as that of Fig. 2 and will not be repeated here. It can be seen from the figure that the microstructure of the magnet of the present invention exhibits a distinct network-like structure, which shows that a layer of continuous rare earth-rich layer is coated on the surface of the main phase particles, and this thin layer can prevent the demagnetization domain core from being
  • the nucleation and growth under the action of the lower external field on the other hand, can achieve a good demagnetization coupling effect on the main phase particles, so the coercivity can be significantly improved.
  • the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the performance of the magnet obtained in this example was tested according to the method of Example 1.
  • the test results showed that the coercive force of the magnet was increased by 7640 Oe, the remanence of the magnet was slightly decreased, the 40 Gs was decreased, and the remanence reduction rate was 0.3%.
  • the NdFeB magnet was subjected to the step. 3) and 4) Performance changes before and after processing are shown in Table 1.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace under the condition of a vacuum of 10 -4 Pa at 790. Incubate at °C for 30 hours; then cool to 50 °C with the furnace;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 460 ° C for 5 hours, and then naturally cooled to room temperature.
  • the microstructure of the magnet obtained in this embodiment is substantially the same as that of Fig. 2 and will not be repeated here. It can be seen from the figure that the microstructure of the magnet of the present invention exhibits a distinct network-like structure, which shows that a layer of continuous rare earth-rich layer is coated on the surface of the main phase particles, and this thin layer can prevent the demagnetization domain core from being
  • the nucleation and growth under the action of the lower external field on the other hand, can achieve a good demagnetization coupling effect on the main phase particles, so the coercivity can be significantly improved.
  • the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the performance of the magnet obtained in this example was tested according to the method of Example 1.
  • the test results showed that the coercive force of the magnet was increased by 4100 Oe, the remanence was slightly decreased, the reduction of 240 Gs, and the remanence reduction rate was 1.7%; the NdFeB magnet was subjected to steps. 3) and 4)
  • the performance changes of the magnets before and after treatment are shown in Table 1.
  • Tb 98 Al 2 (subscript of which is the atomic percentage of the corresponding element) composite target: the raw material Tb element (purity: 99.95%) and Al powder (purity is calculated according to the chemical formula ratio of the above composite target) 99.95%), it is smelted in a vacuum medium frequency induction furnace, wherein the smelting vacuum is 10 -2 Pa, the smelting temperature is 1039 ° C, the smelting time is 15 minutes, and then the molten alloy liquid is cast into a slab.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace under the condition of a vacuum of 10 -4 Pa at 835. Incubate at °C for 35 hours; then cool to 50 °C with the furnace;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 450 ° C for 5 hours, and then naturally cooled to room temperature.
  • the microstructure of the magnet obtained in this embodiment is substantially the same as that of Fig. 2. It can be seen from the figure that the microstructure of the magnet of the present invention exhibits a distinct network structure, which shows that a layer of continuous rare earth-rich thin film is coated on the surface of the main phase particles. Layer, this thin layer can prevent the demagnetization domain nucleation from nucleation and growth under the action of a lower external field on the one hand, and can perform good demagnetization coupling on the main phase particles on the other hand, thus significantly improving the coercivity force. At the same time, the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the molten alloy liquid is cast into a cast slab, and then subjected to forging, hot rolling, cold rolling, and machining to obtain a target having a thickness of 1.5 mm and a length and a width of 200 and 150 mm, respectively; then removing the scale on the surface of the target, etc. , to maintain the surface flatness of the target.
  • the piece of the NdFeB magnet to be treated obtained in the step 2) is sandwiched between the two composite targets obtained in the step 1) and placed in a vacuum heat treatment furnace under the condition of a vacuum of 10 -4 Pa at 800. Incubate at °C for 35 hours; then cool to 50 °C with the furnace;
  • the NdFeB magnet treated in the step 3) was placed in a tempering furnace, tempered at 490 ° C for 5 hours, and then naturally cooled to room temperature.
  • the microstructure of the magnet obtained in this embodiment is substantially the same as that of Fig. 2. It can be seen from the figure that the microstructure of the magnet of the present invention exhibits a distinct network structure, which shows that a layer of continuous rare earth-rich thin film is coated on the surface of the main phase particles. Layer, this thin layer can prevent the demagnetization domain nucleation from nucleation and growth under the action of a lower external field on the one hand, and can perform good demagnetization coupling on the main phase particles on the other hand, thus significantly improving the coercivity force. At the same time, the heavy rare earth elements Dy and Tb are less, and the degree of reduction of remanence is greatly reduced.
  • the performance of the magnet obtained in this example was tested according to the method of Example 1.
  • the test results showed that the coercive force of the magnet was increased by 9060 Oe, the remanence was slightly decreased, the 60 Gs was decreased, and the remanence reduction rate was 0.5%.
  • the NdFeB magnet was subjected to the step. 3) and 4) performance changes before and after processing As shown in Table 1.
  • Examples 7-15 and Comparative Example 1 are listed below.
  • the chemical formulas of the respective composite targets are shown in Table 2, each The preparation methods of the magnets of the examples and the comparative examples were the same as those of the first embodiment.
  • the specifications of the magnets of the respective examples and comparative examples were the same as those of the first embodiment, and the specifications of the composite target were also the same as those of the examples 1, the examples and the comparative examples.
  • the performance test is the same as in Embodiment 1, and the test results are shown in Table 2.
  • examples 16-23 are listed below, except in step 16-23, except for step 3).
  • the insulation temperature and the tempering temperature of the step 4) are different from those of the first embodiment, and other parameters are the same as those of the first embodiment.
  • the performance test of the magnet obtained in each example is the same as that of the first embodiment, and the test results are shown in Table 3.
  • Comparative Example 2-3 was also set. In Comparative Example 2-3, except that the holding temperature of the step 3) and the tempering temperature of the step 4) were different from those of the first embodiment, the other parameters were the same as those of the first embodiment, and the test was performed. See Table 3 for the results.
  • the holding temperature and the tempering temperature have an important influence on the coercive force and the remanence of the magnet.

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Abstract

一种复合靶气相沉淀制备晶界扩散稀土永磁材料的方法，该方法是采用复合靶材蒸发附着于NdFeB磁体表面，通过中高温处理以及低温时效处理，磁体矫顽力明显提高，剩磁和磁能积基本不降低。有益效果是提高了磁体的矫顽力，同时消除了长时间高温处理导致的融坑和晶粒长大等缺陷，使得重稀土的使用量大幅降低，降低了产品的成本。

Description

复合靶气相沉淀制备晶界扩散稀土永磁材料的方法 技术领域
本发明属于稀土永磁材料技术领域，特别涉及一种复合靶气相沉淀制备晶界扩散稀土永磁材料的方法，该方法是在钕铁硼(NdFeB)表面气相沉淀复合金属膜并中高温处理、低温时效以提高磁体性能的方法。
背景技术
钕铁硼(NdFeB)永磁材料在混合动力汽车、风力发电等领域中的应用与日俱增。这些应用领域要求磁体长时间高温工作，这必然要求磁体具有更高矫顽力(Hcj)。而NdFeB磁体随加工尺寸的变薄，矫顽力会明显下降。采用重稀土元素如Dy/Tb取代磁体主相Nd2Fe14B中的Nd，形成(Nd、Dy)2Fe14B，(Nd、Tb)2Fe14B的各向异性强于Nd2Fe14B，这是一种提高NdFeB烧结磁体Hcj的有效方法。但Dy/Tb这些重稀土元素资源稀缺且价格昂贵；另一方面，Nd和铁的磁矩是平行排列，而Dy/Tb与铁则是反平行排列，这导致磁体剩磁Br和最大磁能积(BH)max都会降低。因此，寻找一种有效提高矫顽力，而剩磁和磁能积的相应牺牲很少的制备和处理方法，已成为钕铁硼磁体研究和生产领域的共识，并有很多团队致力于这方面的研究。
近期，诸多研究团队或个人报道了多种将稀土元素从磁体表面扩散到基体内部的晶界扩散处理技术。晶界扩散处理技术主要采用涂覆、沉积、镀覆、溅射、粘覆等方式，使金属粉末(Dy、Tb或其它稀土元素)或化合物附着在磁体外表面，通过热处理使金属粉末或化合物经晶界扩散到烧结磁体主相内，这种晶界扩散技术对烧结NdFeB磁体的成分、微观组织和磁性能都有显著的影响，其中，主要的技术有蒸渡或溅射技术以及涂覆技术。蒸镀或溅射技术是将Dy、Tb等稀土元素沉积在NdFeB烧结磁体表面，随后进行热处理和扩散。涂覆技术是在磁体表面涂覆稀土化合物如氟化物或氧化物粉末并加热扩散。通过上述方法能使渗透的稀土元素沿着晶界以及主相晶粒表面区域，使得稀土元素能择优分布，不仅提高了矫顽力，还节约了贵重稀土的使用量，使剩磁及磁能积没有明显降低。然而，仍有一些问题亟待解决：(1)利用溅射将Dy/Tb附着在NdFeB烧结磁铁的表面的方法生产率低，工序费用过高，容易出现融坑等缺陷，蒸镀过程中大量稀土金属散布在加热炉腔室内，重稀土金属利用率较低。(2)将Dy/Tb的氟化物或氧化物粉末附着在磁铁表面并加热的方法或向这些粉末和氢化Ca粉末的混合粉末中填充磁铁并加热的方法也是如下所述，工序数增多，成本费用高，另外，在表面涂覆稀土氧化物或氟化物加热扩散则存在矫顽力提高受限和其他元素会随扩散过程进入磁体内等问题。在将NdFeB磁铁进行机械加工，利用清洗、酸洗等使表面洁净，然后作为能够进行镀镍或铝的离子电镀等表面处理的状态后，将氟化物或氧化物粉末附着于表面并加热时，则加热后就会在表面形成由 Dy/Tb的一部分置换了Nd的氧化物或氟化物构成的表面层。虽然附着氟化物或氧化物粉末的操作本身是廉价的，然而去除此种表面层工序，也会提升磁体的价格。(3)另外由于Dy/Tb昂贵，最有效地利用Dy/Tb的资源，也是该类技术中的关键问题。
气相沉淀法是用气态反应原料在固态基体表面反应并淀积成固体薄层或薄膜的工艺过程，目前，利用复合靶材通过气相沉淀方法将复合重稀土元素Dy/Tb和Cu、Nd、Al、Pr等元素的金属蒸发到NdFeB表面，并晶界扩散来提高矫顽力磁体性能的方法还未见公开报道。
发明内容
本发明针对现有技术的不足，目的在于提供一种复合靶气相沉淀制备晶界扩散稀土永磁材料的方法，以提高永磁材料矫顽力，同时剩磁和磁能积基本不降低。
为了实现上述目的，本发明采用了以下技术方案：
一种复合靶气相沉淀制备晶界扩散稀土永磁材料的方法，包括如下操作步骤：
步骤一，复合靶材的制备，所述复合靶材具有如下化学式H100-x-yMxQy，其中，H为Dy或/和Tb，M为Nd或/和Pr，Q为Cu、Al、Zn和Sn中的一种或多种，x、y为所述复合靶材中各成分的原子百分含量，x＝0-20、y＝0-40且x和y不同时为零；
步骤二，将烧结NdFeB磁体加工成规定形状和尺寸，随后进行表面清理及干燥，从而得到待处理NdFeB磁体；
步骤三，将所述复合靶材和所述待处理NdFeB磁体依次交替叠置于处理设备中，且最上层和最底层均为复合靶材，以所述复合靶材作为蒸发源，在规定条件下(即中高温)使所述待处理NdFeB磁体表面包覆金属膜并发生晶界扩散，之后随炉冷却，从而得到扩散后的NdFeB磁体；
步骤四，将所述扩散后的NdFeB磁体进行回火处理(即低温时效处理)，使晶界相均匀包裹在主相粒子外，从而得到性能提高的磁体。
在上述方法中，作为一种优选实施方式，在所述步骤一中，所述复合靶材H100-x-yMxQy中x＝0-5、y＝1-10；更优选地，所述复合靶材为Tb95Cu5、Tb98Al2或Tb95.9Dy0.4Nd0.7Zn2Sn1。
在上述方法中，作为一种优选实施方式，在所述步骤一中，所述复合靶材是通过如下方法制备的：按照所述复合靶材各成分的原子百分含量称取相应原料，依次经冶炼、浇铸、锻造、热轧、冷轧以及机械加工，形成规定尺寸的复合靶材。锻造、热轧、冷轧过程将提高复合靶材致密度，从而影响靶材的使用寿命以及蒸发度。复合靶材厚度不同将影响靶材强度以及后续渗透处理效果，相同重量的复合靶材，在相同处理条件下，表面积越大即厚度越薄其渗透效果越明显，优选地，所述复合靶材的规定尺寸为：厚度为0.5-3mm、长度为180-300mm和宽度为100-240mm；优选地，所述冶炼采用真空中频感应炉冶炼，真空度不高于10-2Pa(比如0.05Pa、0.1Pa、0.5Pa、1Pa、2Pa、3Pa)，更优选真空度为10-2-1Pa。
在上述方法中，作为一种优选实施方式，在所述步骤二中，所述 表面清理的过程如下：首先将所述NdFeB磁体放入除油槽中浸泡10-15min以去除磁体表面的油污，然后依次经第一次水洗、酸洗、第二次水洗及超声波处理，最后风干所述NdFeB磁体表面。优选地，所述酸洗的时间为20-45s(比如22s、28s、35s、39s、44s)，所述超声波处理的时间为20-45s(比如22s、28s、35s、39s、44s)。
在上述方法中，所述待处理NdFeB磁体的尺寸没有严格要求，作为一种优选实施方式，所述待处理NdFeB磁体的取向方向控制在1-8mm厚度(比如2mm、4mm、6mm、7mm)。本发明方法可以处理比如方形、圆形等简单平面形状的NdFeB磁体。
在上述方法中，作为一种优选实施方式，在所述步骤三中，一块所述待处理NdFeB磁体夹置于两块所述复合靶材之间，且所述复合靶材的表面积大于所述待处理NdFeB磁体的表面积。
在上述方法中，作为一种优选实施方式，在所述步骤三中，所述规定条件如下：真空度不大于10-3Pa(比如5×10-4Pa、1×10-4Pa、8×10-5Pa、5×10-5Pa、1×10-6Pa)，保温温度为650-900℃(比如650℃、700℃、750℃、800℃、850℃、900℃)，保温时间为5-50h(6h、10h、20h、30h、40h、48h)；所述随炉冷却至不高于50℃(25℃、30℃、35℃、40℃、45℃)。更优选地，在所述步骤三中，所述保温温度为700-850℃，保温时间为5-35h。
在上述方法中，作为一种优选实施方式，所述步骤四中，所述回火处理条件为：回火温度为420-640℃(比如420℃、460℃、500℃、550℃、600℃、630℃)，回火时间为2-10h(比如3h、4h、6h、8h、 9h)，之后采用自然冷却的方式冷却至室温。
在上述方法中，所述步骤三中的处理设备可以为真空热处理炉。
在上述方法中，所述步骤三的技术关键是克服了蒸镀法中大量稀土金属散布在加热炉腔室内，重稀土金属利用率较低的缺点，并且能够产生叠加的性能，通过有效利用稀土的蒸发量，降低多余的附着以提高材料利用率。
在本发明中，将复合金属靶材作为高温蒸发源，在中高温度条件下在烧结NdFeB磁体表面形成一种包含重稀土元素和辅助金属元素的金属膜。蒸发、附着和晶界扩散同步进行，在该温度条件下保温一定时间，使重稀土元素和辅助金属通过晶界向磁体内部进行扩散，重稀土元素和主相边缘Nd2Fe14B中的Nd发生取代反应，形成具有较高各向异性的(Nd，H)2Fe14B相，在微观结构中可以观察到明显的网络状过渡带，参见附图2，这种过渡带可以使磁体在反磁化过程中抑制反磁化畴核的长大，从而使磁体矫顽力提高4000～13000Oe，剩磁降低小于4.5％。在提高相同磁体矫顽力的情况下，与采用传统方法(即采用蒸镀技术将Dy、Tb等稀土元素沉积在NdFeB磁体表面)改善磁体性能相比，本发明可降低重稀土使用量10-20％，同时保持很低的剩磁降低率。
本发明的方法属于在NdFeB表面冷凝附着富含重稀土元素和具有良好浸润性的辅助金属并经中高温处理的方法。本发明所使用的蒸发源材料为复合靶材，靶材由熔点不同的物质制成，由于其物质内部微粒间作用力的大小不同，整体合金靶材内能增大，导致熔点降低， 这使得复合靶材和纯金属靶材相比具有较低的蒸发温度即较低的处理温度。
本发明的有益效果：复合靶材制备较为简单，复合靶材气相沉淀扩散温度低于其他晶界扩散技术，并能保证重稀土元素在主相和富钕相交界区域富集，从而使NdFeB磁体的矫顽力有显著提高。本发明为稀土永磁材料NdFeB性能的改善开辟了一条新颖的路线。采用本发明来改善磁体性能，一方面效率高；另一方面使用的重稀土量大幅降低，降低了产品的成本，使产品的性价比更具优势，此外还能消除长时间高温处理导致的融坑和晶粒长大等缺陷；采用的辅助金属元素都是在高温下容易融于液态富钕相，有助于提高高温富钕相的流动性和浸润性，更利于晶界扩散；还对磁体的耐蚀性有明显的改善。采用复合靶气相沉淀制备晶界扩散NdFeB稀土永磁体的方法，可有效地降低晶界扩散处理温度，在较低的温度下实现晶界扩散。一方面可以有效控制蒸发量，提高蒸发材料的利用率；另一方面低温进行晶界扩散处理可以避免磁体出现融蚀坑和晶粒异常长大等缺陷，提高晶界扩散处理磁体的成品率。此外，复合添加的非重稀土元素对磁体的耐蚀性和机械性能有显著改善。
附图说明
图1为本发明的工艺流程图；
图2为本发明实施例1最终得到的磁体的微结构图；
图3为本发明的实施例1中处理前后磁体的性能变化图。
具体实施方式
以下将结合实例对本发明进行进一步说明，本发明的实施例仅用于说明本发明，并非限定本发明。
以下方法中使用的待处理的NdFeB磁体均为烧结NdFeB磁体，各实施例中使用的均为同一批次、同一牌号的烧结NdFeB磁体。
图1给出了本发明方法的工艺流程，包括如下步骤：烧结磁体加工成薄片、磁体表面清理、中高温处理以及低温时效处理。下面给出具体实施例。
实施例1
1)制备Tb98Cu2(其下标为相应元素的原子百分含量)复合靶材：按照复合靶材的化学式配比称取原料Tb单质(纯度为99.95％)、Cu粉(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，其中冶炼的真空度为10-2Pa，冶炼温度为1040℃，在该温度保持15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为2mm，长度和宽度分别为240和160mm的复合靶材；然后去除复合靶材表面的氧化皮等，保持靶材表面平整度。
2)采用机械加工方式将大块烧结NdFeB磁体加工成表1所示的烧结磁体规格，之后将其放入除油槽中浸泡10min以去除磁体表面的油污，然后用清水洗净表面后用稀硝酸(浓度为0.5wt％)洗约40s，再经过水洗，之后超声波处理35s后，最后采用强风快速干燥，即得 到待处理NdFeB磁体。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到的两块复合靶材之间并放置于真空热处理炉内，以复合靶材作为蒸发源，在真空度为10-4Pa的条件下，于700℃保温24小时；之后随炉冷却至50℃左右；
4)将步骤3)处理后的NdFeB磁体放置于回火炉内，在500℃下回火处理5小时，之后自然冷却至室温，从而获得性能提高的磁体。
参见图2，为本实施例得到的磁体的微观结构图，与传统制备方法(比如公开号为CN101404195的专利文献中记载的方法)相比较，传统方式制备的磁体微结构(参见公开号为CN101404195的专利文献中的图1)不能看到完整的网络状结构；而本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
对采用本实施例方法处理前后的磁体进行性能测试，测试方法按照GB/T3217-1992标准进行，将回火处理完的磁体切割成直径为10mm的圆柱，经测试，中高温以及低温时效处理前和处理后相比，磁体矫顽力提高了10990Oe，剩磁稍有降低，降低了330Gs，剩磁降低率为2.3％，如图3所示；NdFeB磁体经步骤3)和4)处理前后性能变化如表1所示，即处理前即为图3所述比较例，处理后即为本发明得到 的性能提高的磁体。
实施例2
1)制备Tb95Cu5(其下标为相应元素的原子百分含量)复合靶材，按照复合靶材的化学式配比称取原料Tb单质(纯度为99.95％)、Cu粉(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，其中冶炼的真空度为10-2Pa，冶炼温度为1042℃，冶炼时间为15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为2.2mm，长度和宽度分别为220和140mm的靶材。然后去除靶材表面的氧化皮等，保持靶材表面平整度。
2)采用烧结磁体机将烧结NdFeB磁体机械加工成表1中所示规格，之后进行表面清理和风干，具体步骤同实施例1步骤2)。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到的两块复合靶材之间并放置于真空热处理炉内，在真空度为10-4Pa的条件下，于690℃保温30小时；之后随炉冷却至45℃左右；
4)将步骤3)处理后的NdFeB磁体放置于回火炉，在510℃条件下回火处理5小时，之后自然冷却至室温，从而获得性能提高的磁体。
该实施例得到磁体的微观结构与图2基本相同，此处不再重复给出。从图中可以看出本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。 同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
按照实施例1的方法对本实施例得到的磁体进行性能测试，测试结果表明，磁体矫顽力提高了8510Oe，剩磁稍有降低，降低了280Gs，剩磁降低率为2％；NdFeB磁体经步骤3)和4)处理前后性能变化如表1所示。
实施例3
1)制备Tb97Nd1Al2(其下标为相应元素的原子百分含量)复合靶材：按照上述复合靶材的化学式配比称取原料Tb单质(纯度为99.95％)、Nd单质(纯度为99.95％)、Cu粉(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，其中冶炼的真空度为10-2Pa，冶炼温度为1040℃，冶炼时间为15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为3.0mm，长度和宽度分别为200和110mm的复合靶材；之后去除靶材表面的氧化皮等，保持靶材表面平整度。
2)采用烧结磁体机将烧结NdFeB磁体机械加工成表1中所示规格，之后进行表面清理和风干，具体步骤同实施例1步骤2)。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到的两块复合靶材之间并放置于真空热处理炉内，在真空度为5×10-4Pa的条件下，于820℃保温35小时；之后随炉冷却至40℃左右；
4)将步骤3)处理后的NdFeB磁体放置于回火炉内，在经470℃回火处理5小时，之后自然冷却至室温。
该实施例得到磁体的微观结构与图2基本相同，此处不再重复给出。从图中可以看出本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
按照实施例1的方法对本实施例得到的磁体进行性能测试，测试结果表明，磁体矫顽力提高了7640Oe，剩磁稍有降低，降低了40Gs，剩磁降低率为0.3％；NdFeB磁体经步骤3)和4)处理前后性能变化如表1所示。
实施例4
1)制备Dy98Al2(其下标为相应元素的原子百分含量)复合靶材：按照上述复合靶材的化学式配比称取原料Dy单质(纯度为99.95％)、Al粉(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，冶炼温度为1048℃，冶炼时间为15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为2.0mm，长度和宽度分别为190mm和110mm的复合靶材；之后去除靶材表面的氧化皮等，保持靶材表面平整度。
2)采用烧结磁体机将烧结NdFeB磁体机械加工成表1中所示规格，之后进行表面清理和风干，具体步骤同实施例1步骤2)。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到 的两块复合靶材之间并放置于真空热处理炉内，在真空度为10-4Pa的条件下，于790℃保温30小时；之后随炉冷却至50℃；
4)将步骤3)处理后的NdFeB磁体放置于回火炉，在460℃条件下回火处理5小时，之后自然冷却至室温。
该实施例得到磁体的微观结构与图2基本相同，此处不再重复给出。从图中可以看出本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
按照实施例1的方法对本实施例得到的磁体进行性能测试，测试结果表明，磁体矫顽力提高了4100Oe，剩磁稍有降低，降低了240Gs，剩磁降低率为1.7％；NdFeB磁体经步骤3)和4)处理前后磁体性能变化如表1所示。
实施例5
1)制备Tb98Al2(其下标为相应元素的原子百分含量)复合靶材：按照上述复合靶材的化学式配比称取原料Tb单质(纯度为99.95％)、Al粉(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，其中冶炼的真空度为10-2Pa，冶炼温度为1039℃，冶炼时间为15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为1.5mm，长度和宽度分别为200和140mm的靶材；之后去 除靶材表面的氧化皮等，保持靶材表面平整度。
2)采用烧结磁体机将烧结NdFeB磁体机械加工成表1中所示规格，之后进行表面清理和风干，具体步骤同实施例1步骤2)。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到的两块复合靶材之间并放置于真空热处理炉内，在真空度为10-4Pa的条件下，于835℃保温35小时；之后随炉冷却至50℃；
4)将步骤3)处理后的NdFeB磁体放置于回火炉内，在450℃条件下回火处理5小时，之后自然冷却至室温。
该实施例得到磁体的微观结构与图2基本相同，从图中可以看出本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
按照实施例1的方法对本实施例得到的磁体进行性能测试，测试结果表明，磁体矫顽力提高了7180Oe，剩磁稍有降低，降低了220Gs，剩磁降低率为1.7％；NdFeB磁体经步骤3)和4)处理前后性能变化如表1所示。
实施例6
1))制备Tb95.9Dy0.4Nd0.7Zn2Sn1的靶材，按照上述复合靶材的化学式配比称取原料Tb单质(纯度为99.95％)、Dy单质(纯度为99.95％)、 Nd单质(纯度为99.95％)、Zn单质(纯度为99.95％)、Sn单质(纯度为99.95％)，将其置于真空中频感应炉中进行冶炼，冶炼温度为1041℃，冶炼时间为15分钟，之后将熔融的合金液浇铸成铸坯，再经锻压、热轧、冷轧及机械加工制成厚度为1.5mm，长度和宽度分别为200和150mm的靶材；之后去除靶材表面的氧化皮等，保持靶材表面平整度。
2)采用烧结磁体机将烧结NdFeB磁体机械加工成表1中所示规格，之后进行表面清理和风干，具体步骤同实施例1步骤2)。
3)将步骤2)得到的一块待处理NdFeB磁体夹置于步骤1)得到的两块复合靶材之间并放置于真空热处理炉内，在真空度为10-4Pa的条件下，于800℃保温35小时；之后随炉冷却至50℃；
4)将步骤3)处理后的NdFeB磁体放置于回火炉，在490℃条件下回火处理5小时，之后自然冷却至室温。
该实施例得到磁体的微观结构与图2基本相同，从图中可以看出本发明例的磁体微结构出现明显的网络状结构，这显示在主相粒子表面包裹了一层连续的富稀土薄层，这个薄层一方面可以阻止反磁化畴核在较低的外场作用下成核和长大，另一方面可以对主相粒子起到很好的去磁耦合作用，因此可以显著提高矫顽力。同时所含的重稀土元素Dy、Tb较少，对剩磁的降低程度将大大降低。
按照实施例1的方法对本实施例得到的磁体进行性能测试，测试结果表明，磁体矫顽力提高了9060Oe，剩磁稍有降低，降低了60Gs，剩磁降低率为0.5％；NdFeB磁体经步骤3)和4)处理前后性能变化 如表1所示。
表1 六个实施例得到的磁体性能检测结果
Figure PCTCN2015093951-appb-000001
表1中实施例所取得的结果：矫顽力提高了4100Oe-10990Oe，而剩磁仅降低0.3％-2.3％，均是基于优选条件下取得的结果。
实施例7-15
为了更好地说明本发明中不同复合靶材对磁体性能的影响，下面列举了实施例7-15和对比例1，在实施例7-15中，各复合靶材的化学式参见表2，各实施例和对比例的磁体制备方法同实施例1，各实施例和对比例处理前磁体的规格同实施例1，复合靶材的规格也同实施例1，各实施例和对比例得到的磁体的性能测试同实施例1，测试结果参见表2。
表2 实施例7-15和对比例1得到的磁体性能测试结果
Figure PCTCN2015093951-appb-000002
实施例16-23
为了更好地说明本发明中步骤3)的保温温度和步骤4)的回火温度对磁体性能的影响，下面列举了实施例16-23，在实施例16-23中，除步骤3)的保温温度和步骤4)的回火温度不同于实施例1以外，其他参数均与实施例1相同，各实施例得到的磁体的性能测试同实施例1，测试结果参见表3。同时还设置了对比例2-3，在对比例2-3中，除步骤3)的保温温度和步骤4)的回火温度不同于实施例1以外，其他参数均与实施例1相同，测试结果参见表3。
从表3中可知，保温温度以及回火温度对磁体矫顽力和剩磁具有重要影响。
表3 实施例16-23得到的磁体性能测试结果
Figure PCTCN2015093951-appb-000003

Claims (10)

  1. 一种复合靶气相沉淀制备晶界扩散稀土永磁材料的方法，其特征在于，包括如下操作步骤：
    步骤一，复合靶材的制备，所述复合靶材具有如下化学式H100-x-yMxQy，其中，H为Dy或/和Tb，M为Nd或/和Pr，Q为Cu、Al、Zn和Sn中的一种或多种，x、y为所述复合靶材中各成分的原子百分含量，x＝0-20、y＝0-40且x和y不同时为零；
    步骤二，将烧结NdFeB磁体加工成规定形状和尺寸，随后进行表面清理及干燥，从而得到待处理NdFeB磁体；
    步骤三，将所述复合靶材和所述待处理NdFeB磁体依次交替叠置于处理设备中，且最上层和最底层均为所述复合靶材，以所述复合靶材作为蒸发源，在规定条件下使所述待处理NdFeB磁体表面包覆金属膜并发生晶界扩散，之后随炉冷却，从而得到扩散后的NdFeB磁体；
    步骤四，将所述扩散后的NdFeB磁体进行回火处理，使晶界相均匀包裹在主相粒子外，从而得到性能提高的磁体。
  2. 根据权利要求1所述的方法，其特征在于，在所述步骤一中，所述复合靶材H100-x-yMxQy中x＝0-5、y＝1-10。
  3. 根据权利要求2所述的方法，其特征在于，所述复合靶材为Tb95Cu5、Tb98Al2或Tb95.9Dy0.4Nd0.7Zn2Sn1。
  4. 根据权利要求1所述的方法，其特征在于，在所述步骤一中，所述复合靶材是通过如下方法制备的：按照所述复合靶材各成分的原子百分含量称取相应原料，依次经冶炼、浇铸、锻造、热轧、冷轧以及机械加工，形成规定尺寸的复合靶材；优选地，所述冶炼采用真空中频感应炉冶炼，真空度不高于10-2Pa。
  5. 根据权利要求4所述的方法，其特征在于，所述复合靶材的规定尺寸为：厚度为0.5-3mm、长度为180-300mm和宽度为100-240mm。
  6. 根据权利要求1所述的方法，其特征在于，在所述步骤二中，所述表面清理的过程如下：首先将所述NdFeB磁体放入除油槽中浸泡10-15min以去除磁体表面的油污，然后依次经第一次水洗、酸洗、第二次水洗及超声波处理，最后风干所述NdFeB磁体表面；优选地，所述酸洗的时间为20-45s，所述超声波处理的时间为20-45s。
  7. 根据权利要求1所述的方法，其特征在于，所述待处理NdFeB磁体的取向方向控制在1-8mm厚度。
  8. 根据权利要求1所述的方法，其特征在于，在所述步骤三中，一块所述待处理NdFeB磁体夹置于两块所述复合靶材之间，且所述复合靶材的表面积大于所述待处理NdFeB磁体的表面积。
  9. 根据权利要求1所述的方法，其特征在于，在所述步骤三中，所述规定条件如下：真空度不大于10-3Pa，保温温度为650-900℃，保温时间为5-50h；所述随炉冷却至不高于50℃；优选地，在所述步骤三中，所述保温温度为700-850℃，保温时间为5-35h。
  10. 根据权利要求1所述的方法，其特征在于，在所述步骤四中，所述回火处理条件为：回火温度为420-640℃，回火时间为2-10h，之后采用自然冷却的方式冷却至室温。
PCT/CN2015/093951 2015-05-07 2015-11-06 复合靶气相沉淀制备晶界扩散稀土永磁材料的方法 WO2016176974A1 (zh)

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ES15884914T ES2699949T3 (es) 2015-05-07 2015-11-06 Procedimiento para preparar un material magnético permanente de tierras raras con una difusión intercristalina utilizando una diana compuesta mediante deposición en fase vapor

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