CN111136268A - High-throughput alloy preparation and Ho-Fe-B phase diagram test method - Google Patents
High-throughput alloy preparation and Ho-Fe-B phase diagram test method Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 238000010587 phase diagram Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 18
- 238000010998 test method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000009792 diffusion process Methods 0.000 claims abstract description 30
- 238000012360 testing method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 7
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- 239000000203 mixture Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 5
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- 229910052786 argon Inorganic materials 0.000 claims description 4
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- 239000005457 ice water Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
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- 229910052771 Terbium Inorganic materials 0.000 description 2
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 2
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
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- 241000282414 Homo sapiens Species 0.000 description 1
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Abstract
The invention provides a method for preparing a high-flux alloy and testing a Ho-Fe-B phase diagram, which comprises the following steps: weighing and proportioning the FeB according to design requirements; smelting the proportioned Fe and B to form a FeB alloy compound; carrying out homogenization heat treatment on the smelted FeB cast ingot in a vacuum state; cutting the processed sample, and then carrying out metallographic treatment on the sample; the FeB alloy and the Ho cylinder which are subjected to metallographic treatment are combined in a stacking mode in a vacuum sintering furnace burning mode; placing the FeB-Ho prepared by high flux in a vacuum sealed tube, and preserving heat for 480h at 800 ℃; after the diffusion is finished, cutting the sample and observing a phase structure formed by the diffusion layer; and (3) acquiring the metallographic structure distribution of the diffusion layers by adopting a high-throughput test, and analyzing the phase structure relationship among the diffusion layers. The invention shortens the experimental period of phase diagram drawing, saves manpower and material resources and obtains a clear and accurate Ho-Fe-B correlation system.
Description
Technical Field
The invention belongs to the field of permanent magnet materials, and particularly relates to a high-flux alloy preparation and Ho-Fe-B phase diagram test method.
Background
The development, production and application degree of the rare earth permanent magnet material is a material basis for national high and new technology and social development; widely applied to computer technology, information technology, aerospace technology, automation technology, medical appliances and household appliances; the rare earth permanent magnet material is not available, so that the industrial modernization is not available, and the civilization progress of human beings is not more available. China contains abundant rare earth resources, and is also a large country for rare earth production. According to the statistics of the China rare earth industry Association, the rare earth permanent magnet blank produced in 2016 China reaches 14 ten thousand t, wherein 2.69 ten thousand t is exported, and the high-speed growth is continuously kept; the total rare earth reserves of 1.2 hundred million tons in the world in 2018, 4400 ten thousand tons in China, accounting for 38 percent. However, in the process of rapid development and application of the rare earth permanent magnet, a large amount of rare earth elements such as Pr, Nd, Dy, Tb and the like are consumed, so that rare earth resources such as Gd, Ho, Ce and the like which are short in resource and low in price are greatly accumulated; meanwhile, serious ecological environment pollution is caused in the process of separating and purifying the rare earth. In order to realize the balanced utilization of rare earth resources and reduce the production cost, the search and development of new rare earth materials for replacing neodymium iron boron strong magnetic rare earth permanent magnetic materials becomes one of the research directions of current researchers.
In the rare earth elements, except Eu and Pm, the rare earth elements can form RE with Fe and B2Fe14B structure, RE2Fe14B belongs to a hard magnetic main phase in the rare earth permanent magnetic material, and the magnetism of the rare earth permanent magnetic material is separated from the component. Wherein Nd2Fe14B has high coercive force and high remanence and is called "magnetic king", and Pr, Nd, Sm, Tb, Dy and Ho all have high anisotropy field Ha。Ho2Fe14B has high anisotropy field, and can improve the coercive force of the material. The balance of Nd rare earth resources is realized while improving the performance of the neodymium iron boron by replacing part of Nd by Ho. Therefore, the determination of the phase forming rule and the solidification characteristic of the Ho-Fe-B phase diagram is very important for sintering the double-main-phase Ho-Nd-Fe-B permanent magnet.
The conventional method for determining the phase diagram is to use an alloy method, however, the method for determining the phase diagram by using the alloy method is inefficient and easily ignores certain phase components, thereby causing the loss of the phase diagram.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for drawing a phase system and a phase forming rule of a Ho-Fe-B system based on a technology for obtaining a Ho-Fe-B phase diagram of a rare earth alloy by high-throughput preparation and test. Compared with the traditional alloy method for drawing a phase diagram, the technology for preparing and testing the rare earth alloy Ho-Fe-B phase diagram with high throughput shortens the experimental period, greatly saves manpower and material resources, and can obtain a clear and accurate Ho-Fe-B phase system.
The method for drawing the 800 ℃ isothermal section phase diagram of the Ho-Fe-B system comprises the following main steps:
(1) in the application, the purity of initial raw materials of Ho, Fe and B is more than or equal to 99.99%, and according to the high-throughput preparation and test technology, the FeB is weighed and proportioned according to the design requirement;
(2) smelting the proportioned Fe and B to form a FeB alloy compound, then preparing a Ho ingot under the same condition, and taking inert gas argon as protective gas in the whole process;
(3) in the smelting process of the FeB alloy, because of different cooling speeds, the smelted FeB ingot needs to be subjected to homogenization heat treatment in a vacuum state;
(4) cutting the processed sample into a cylinder with the size of phi 10 multiplied by 3 mm; then carrying out metallographic treatment on the mixture;
(5) combining the FeB alloy subjected to metallographic treatment with the Ho cylinder in a vacuum sintering furnace (SPS) sintering mode;
(6) placing the FeB-Ho prepared by high flux in a vacuum sealed tube, and preserving heat for 480h at 800 ℃ to carry out mutual diffusion and stress relief treatment;
(7) taking out the prepared sample after the diffusion is finished, forming a diffusion layer, and cutting the sample to observe a phase structure formed by the diffusion layer;
(8) after the process is finished, the metallographic structure distribution of the diffusion layers is obtained by adopting a high-throughput test, and the phase structure relation among the diffusion layers is analyzed, so that a phase diagram of the Ho-Fe-B ternary system at 800 ℃ is obtained.
The smelting is carried out in a non-consumable vacuum electric arc furnace, and in order to obtain a qualified sample, a heating mode needs to be controlled and the sample needs to be turned over.
The heat treatment is carried out by quenching after heat preservation for 120 hours. The heat treatment temperature is preferably 1000 ℃, and the heat preservation time is preferably 120 hours.
The metallographic treatment is performed by grinding and polishing with 400#, 600#, 800#, 1000#, 1200#, 1500#, 2000#, 3600# and 5400 #.
And in the vacuum sintering step, samples of the FeB alloy and the Ho cylinder which are subjected to metallographic treatment are placed into corresponding dies for sintering. And a pressure of 30Mp is applied to the mixture, and the mixture is kept at the sintering temperature of 600 ℃ for 20 minutes.
The key technical detection indexes of the rare earth alloy Ho-Fe-B phase diagram technology are obtained through high-throughput preparation and test:
ensuring that the smooth and flat sample surface can be obtained when the FeB alloy and Ho are subjected to metallographic treatment, and the mutual diffusion cannot be completed to form a diffusion layer when the sample surface is not flat enough; when vacuum sintering is carried out, the heating temperature, the holding time and the pressure applied to the sample are controlled well, and the solid diffusion and liquid infiltration can be ensured to be carried out on the sample; and testing the formed diffusion layer through an electronic probe and a field emission scanning electron microscope to clearly determine the relationship among all tissue phases in detail, thereby completing the phase diagram of Ho-Fe-B at 800 ℃.
The technology for preparing and testing the rare earth alloy Ho-Fe-B phase diagram with high flux has the advantages that:
because a plurality of three-phase and two-phase equilibrium relations can be obtained on one sample by high flux, and repeated preparation and test of a plurality of samples are avoided, the invention adopts high flux preparation and test, and can completely avoid the defects of low efficiency of determining a phase diagram by an alloy method and easy omission of certain phase components, thereby causing the loss of the phase diagram. Therefore, the method adopts the high-throughput preparation and test to obtain the Ho-Fe-B phase diagram technology of the rare earth alloy to clarify the Ho-Fe-B phase system and the phase forming rule, and establishes a database of the components, the organization structure and the performance of the Ho-Fe-B rare earth permanent magnetic material, thereby realizing the high-efficiency, balanced and high-value utilization of rare earth resources.
The technology for obtaining the phase diagram of the rare earth alloy through high-throughput preparation and test is to sinter two samples, form diffusion layers through heating treatment, measure the structure according to the fact that each diffusion layer represents a phase structure to obtain a compound or solid solubility, and draw Ho-Fe-B according to measured data. The technology for preparing and testing the rare earth alloy phase diagram with high flux greatly reduces the workload, obtains a clear and complete phase system and accelerates the determination of the rare earth alloy phase diagram. The method for measuring the phase diagram of the Ho-Fe-B system at 800 ℃ by the high-throughput preparation and test acquisition rare earth alloy Ho-Fe-B phase diagram technology provided by the invention has the advantages of low cost, high efficiency and short research period compared with the traditional alloy method.
Because the phases can reach dynamic balance in the high-temperature box, and quenching can be carried out quickly, the invention uses ice-water mixture for quenching after homogenization heat treatment, thereby keeping the balance state of the phases at high temperature.
When the invention adopts the vacuum sintering furnace for sintering, the heat preservation is carried out for 8 minutes at 600 ℃, and the diffusion balance can be achieved at the temperature.
Drawings
FIG. 1 is a technical flow chart of the high-throughput preparation and test of rare earth alloy Ho-Fe-B phase diagram according to the present invention;
FIG. 2 is a schematic representation of the stacking pattern used during sintering;
FIG. 3 is Fe25B75-a back-scattered map of the Ho diffusion layer;
FIG. 4 is Fe85B15-a back-scattered map of the Ho diffusion layer;
FIG. 5 is a graph of phase equilibrium relationship at 800 ℃ for Ho-Fe-B obtained by high throughput preparation and testing.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIG. 1, the specific implementation steps for determining the 800 ℃ isothermal phase diagram of the Ho-Fe-B ternary system in this example include:
(1) in the application, the purity of initial raw materials of Ho, Fe and B is more than or equal to 99.99%, and according to the high-throughput preparation and test technology, the FeB is weighed and proportioned according to the design requirement;
(2) smelting the proportioned Fe and B to form Fe25B75And Fe85B15Alloy compounds, then preparing a Ho ingot under the same conditions, taking inert gas argon as protective gas in the whole process, manufacturing three ingot alloys in order to ensure the effectiveness of the experiment, and repeatedly smelting for 3-4 times;
(3) fe to be smelted25B75And Fe85B15Firstly, feasibility determination is carried out, if the alloy composition does not meet the preset alloy composition, the alloy needs to be prepared again, and if the alloy ingot meets the requirements, the alloy ingot needs to be placed under a vacuum condition, heat preservation is carried out for 120 hours at the temperature of 1000 ℃, homogenization heat treatment is carried out, and then quenching is carried out by using an ice-water mixture;
(4) keeping the temperature of the Fe at 1000 ℃ for 120h25B75And Fe85B15And carrying out electric spark cutting on the cast ingot Ho to cut a cylinder with the size of phi 10 multiplied by 3 mm; then grinding and polishing with 400#, 600#, 800#, 1000#, 1200#, 1500#, 2000#, 3600# and 5400# to obtain a clean and flat mirror surface;
(5) grinding and polishing the Fe25B75、Fe85B15Sintering with ingot Ho cylinder in vacuum sintering furnace (SPS), stacking up and down to obtain Fe25B75And Ho, Fe85B15Completing connection with Ho to form Fe25B75-Ho and Fe85B15-Ho。
The sintering time of the embodiment is set as 20 minutes, the temperature is increased to 600 ℃ at 10 ℃/min, the temperature is kept for 8 minutes at the temperature, then the temperature is reduced to the room temperature at 10 ℃/min, and the pressure is kept at 30Mp in the sintering process;
(6) sintering the Fe25B75-Ho and Fe85B15After vacuum sealing of Ho, putting the tube into a muffle furnace, and annealing at 800 ℃ for 480 h;
(7) fe prepared by high flux25B75-Ho and Fe85B15-Ho is cut along the axial position and then ground and polished, and the diffusion layer metallographic structure distribution is observed using an Electron Probe (EPMA); the scattering patterns are shown in fig. 3 and 4. As can be seen from fig. 3 and 4, a plurality of phase equilibrium relationships can be determined for one sample. Such as: ho + HoB2+HoFe2、HoFeB3+HoB2+HoFe2、HoFeB3+HoB2+HoB4、HoFeB3+FeB+HoB4、FeB+HoB6+HoB4、Ho5Fe17B17+HoFe2+HoFeB3、Ho5Fe17B17+HoFe2+HoFe3、Ho5Fe17B17+Ho6Fe23+HoFe3、Ho5Fe17B17+Ho2Fe14B+Ho6Fe23、Ho5Fe17B17+Ho2Fe14B+Fe、Ho5Fe17B17+Fe2B + Fe, and the like.
(8) The phase structure relationship of the diffusion layer is analyzed, and a 800 ℃ phase diagram of the Ho-Fe-B system is drawn, as shown in FIG. 5. Compared with the traditional alloy method for drawing a phase diagram, the method for obtaining the rare earth alloy Ho-Fe-B phase diagram based on the high-throughput preparation and test shortens the experimental period, greatly saves manpower and material resources, and can obtain a clear and accurate Ho-Fe-B phase relationship. The method mainly utilizes high-throughput preparation and test to obtain a rare earth alloy Ho-Fe-B system, and an isothermal section phase diagram at 800 ℃. In Fe25B75In the diffusion layer of-Ho, FeB and HoB are present4And HoFeB3Node of, and HoB2、HoFe2And HoFeB3A node of (2); and in Fe85B15HoFe is present in the diffusion layer of-Ho3、Fe23Ho6And Ho5Fe17B17And Ho2Fe14B and HoFe2Through the nodes and the key alloy, a phase equilibrium diagram of the ternary system Ho-Fe-B at 800 ℃ is determined.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A high-throughput alloy preparation and Ho-Fe-B phase diagram testing method is characterized by comprising the following steps of:
(1) the purity of initial raw materials of Ho, Fe and B is more than or equal to 99.99 percent, and according to the technology of high-throughput preparation and test, the FeB is weighed and proportioned according to the design requirement;
(2) smelting the proportioned Fe and B to form a FeB alloy compound, then preparing a Ho ingot under the same condition, and taking inert gas argon as protective gas in the whole process;
(3) in the smelting process of the FeB alloy, because of different cooling speeds, the smelted FeB ingot needs to be subjected to homogenization heat treatment in a vacuum state;
(4) cutting the processed sample into a cylinder with the size of phi 10 multiplied by 3 mm; then carrying out metallographic treatment on the sample to obtain a smooth and flat sample surface;
(5) the FeB alloy and the Ho cylinder which are processed by metallographic phase are combined in a stacking mode by adopting a vacuum sintering furnace burning mode;
(6) placing the FeB-Ho prepared by high flux in a vacuum sealed tube, and preserving heat for 480h at 800 ℃ to carry out mutual diffusion and stress relief treatment;
(7) taking out the prepared sample after the diffusion is finished, forming a diffusion layer, and cutting the sample to observe a phase structure formed by the diffusion layer;
(8) after the process is finished, the metallographic structure distribution of the diffusion layers is obtained by adopting a high-throughput test, and the phase structure relation among the diffusion layers is analyzed, so that a phase diagram of the Ho-Fe-B ternary system at 800 ℃ is obtained.
2. The method of claim 1, wherein the smelting in step (2) is carried out in a non-consumable vacuum arc furnace to a vacuum of 3.0 x 10-3During the process, argon is filled into the furnace body, and the smelted sample needs to be turned over for 3-4 times.
3. The method according to claim 1, wherein said homogenizing heat treatment in step (3) is carried out at 1000 ℃ for 120 hours.
4. A process according to claim 3, characterized in that quenching with an ice-water mixture is carried out after the homogenization heat treatment.
5. The method of claim 1, wherein the metallographic treatment in the step (4) comprises buff polishing using 400#, 600#, 800#, 1000#, 1200#, 1500#, 2000#, 3600#, and 5400#, to obtain a clean and flat sample surface.
6. The method of claim 1, wherein the step (5) sintering uses a vacuum sintering furnace to sinter to form the solid state diffusion; the sintering time is set to 20 minutes, the temperature is increased to 600 ℃ at 10 ℃/min, the temperature is kept for 8 minutes, then the temperature is reduced to the room temperature at 10 ℃/min, and the pressure is kept at 30Mp during the sintering process.
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