CN111235458A - Boron-containing rare earth-containing high-entropy alloy and magnetic field treatment method thereof - Google Patents
Boron-containing rare earth-containing high-entropy alloy and magnetic field treatment method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/04—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering with simultaneous application of supersonic waves, magnetic or electric fields
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
Abstract
The invention provides a boron-containing rare earth-containing high-entropy alloy and a magnetic field treatment method thereof. The pulse magnetic field has high heat treatment energy and high treatment efficiency, and can effectively improve the conversion rate of the hard particle phase. The low-temperature static magnetic field further separates out a grain phase on the basis of inhibiting the growth of grains, simultaneously obviously refines the grains, and can effectively relieve internal stress, so that the mechanical property and the wear resistance of the material are greatly improved, and the material has wide application fields.
Description
Technical Field
The invention belongs to the technical field of rare earth metal materials, belongs to the field of material heat treatment, and relates to a boron-containing rare earth-containing high-entropy alloy and a strengthening and toughening treatment method thereof.
Background
Cryogenic treatment is a new technology developed from common cold treatment (0 ℃ to-100 ℃) in the 60 th century, and people apply the common cold treatment to products such as clock parts, castings and the like as early as one hundred years ago, and find that the strength, the wear resistance, the dimensional stability and the service life of the material can be obviously improved. In 1955, cryogenic treatment (below-130 ℃) appeared for the first time in the united states, and many studies have shown that cryogenic treatment has a better effect than ordinary cold treatment. However, the cryogenic treatment process for the high-entropy alloy is rarely reported.
The high-entropy alloy is a novel multi-component alloy material with a unique design concept proposed at the beginning of the 21 st century, and is a solid solution alloy formed by mixing five or more elements in an equimolar ratio or a nearly equimolar ratio. Researches show that the high-entropy alloy has high strength and hardness, good wear resistance, corrosion resistance and dimensional stability, and can be applied to precision parts such as clock parts, miniature shafts, medical bone nails, optical fiber tail handles and the like in a large scale. Common methods for improving the performance of the high-entropy alloy comprise alloying element adjustment and heat treatment processes, or special preparation methods are adopted, and most of the methods have complex procedures and are difficult to operate, and the performance improvement is limited. Therefore, the magnetic field is applied to the heat treatment and cryogenic treatment process of the boron-containing rare earth-containing high-entropy alloy, the contradiction between the strength and the toughness of the alloy material is overcome by utilizing the special advantages of the magnetic field, the mechanical property and the wear resistance of the boron-containing rare earth-containing high-entropy alloy are improved simultaneously, the operation is simple, the performance improvement is obvious, and the magnetic field has important significance for the future large-scale application of the high-entropy alloy.
Disclosure of Invention
In order to solve the contradiction that the strength and the plasticity of the high-entropy alloy material are improved simultaneously in the prior art, the invention provides a method for improving the mechanical property and the wear resistance of the boron-containing rare earth-containing high-entropy alloy simultaneously by utilizing a mode of coupling a static magnetic field, a pulsed strong magnetic field and a temperature field.
The specific technical scheme of the invention is as follows:
a magnetic field treatment method of boron-containing rare earth-containing high-entropy alloy is characterized by comprising the following steps: after the boron-containing rare earth-containing high-entropy alloy is subjected to pulsed high-intensity magnetic field heat treatment and is reduced to room temperature, the boron-containing rare earth-containing high-entropy alloy is subjected to cryogenic treatment under the condition of a static magnetic field, and is placed in air to be restored to the room temperature after the cryogenic treatment is finished, so that a nanoparticle phase beneficial to simultaneously improving the mechanical property and the wear resistance of the alloy is generated, the internal residual stress is eliminated, and the service life is prolonged.
Further, the magnetic field treatment method of the boron-containing rare earth-containing high-entropy alloy comprises the following steps:
step (1): loading the boron-containing rare earth-containing high-entropy alloy product after being processed and formed into an alumina crucible, then placing the boron-containing rare earth-containing high-entropy alloy product into a tubular furnace, setting the heating rate, the heat preservation temperature and the heat preservation time, vacuumizing and introducing protective gas after setting, and operating the program to carry out heat treatment;
step (2): after the temperature is raised to the treatment temperature, introducing a magnetic field, wherein the pulse frequency of the magnetic field is 0.1-1000 Hz, and the magnetic field intensity is 0.1-10T;
and (3): closing the magnetic field after the heat treatment is finished, taking out the boron-containing rare earth-containing high-entropy alloy product, cooling the boron-containing rare earth-containing high-entropy alloy product in air to room temperature, and performing cleaning, finishing, grinding and polishing treatment on the surface of the boron-containing rare earth-containing high-entropy alloy product;
and (4): placing a boron-containing rare earth-containing high-entropy alloy product into a clamp, clamping strong magnets at two ends of the clamp, wrapping the whole static magnetic field device by using a heat-preservation fiber felt, and immersing the product into liquid nitrogen at the temperature of-180 to-190 ℃ for cryogenic treatment, wherein the cryogenic heat preservation time is 1 to 120 hours;
and (5): and taking the boron-containing rare earth-containing high-entropy alloy product out of the clamp, and restoring the boron-containing rare earth-containing high-entropy alloy product to room temperature in the air.
Further, in the step 1), the initial heating rate of the tube furnace is 5 ℃/min, and the heating rate is 2 ℃/min when the temperature is raised to 400 ℃; when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, the heat treatment temperature is 400-450 ℃, and the treatment time is 0.1-2 h; when the boron-containing rare earth-containing high-entropy alloy is thicker than 10mm and belongs to a heavy part, the heat treatment temperature is 450-550 ℃, and the treatment time is 2-5 h. Although the precipitated phase conversion rate can be improved due to the overlong heat treatment time or overhigh temperature of the product, the mechanical property of the product is influenced due to the coarseness of the structure grains, and for the condition that light and thin parts even have high-temperature deformation, the low precipitated phase conversion rate is caused due to the overlong heat treatment temperature or shorter heat treatment time, so that the service performance of the product is influenced.
Further, in the step 4), when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, a strong magnet of 0.1-1T is selected; when the boron-containing rare earth-containing high-entropy alloy is thicker than 10mm and belongs to a heavy part, a strong magnet with the magnetic field intensity larger than 1T needs to be selected. Because when the intensity of the strong magnetic field selected by the heavy piece is smaller, the internal tissue can not be driven and converted due to insufficient magnetic field energy, and the cryogenic magnetic field effect is weakened.
Further, in the step 4), when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin part, the deep cooling heat preservation time is 1-60 h. When the thickness of the boron-containing rare earth-containing high-entropy alloy is larger than 10mm and belongs to a heavy part, the deep cooling heat preservation time needs to be prolonged to 60-120 h. This is because the performance of the light thin parts is not improved significantly after the cryogenic insulation time exceeds a certain time. For heavy and thick parts, if the heat preservation time of the subzero treatment is too short, the conditions of low grain refinement degree and low precipitated phase conversion rate can occur, so that the treatment effect is not obvious.
Further, the main components of the boron-containing high-entropy alloy comprise Fe, Co, Ni, Cu, B and Y, and the atomic ratio expression of the alloy components is FeCoNi1.5CuBnYmWherein 0 is<n<1.2；0<m<0.5. But is not limited to this component, and other hardening and tempering elements may be added. The rare earth element is not limited to yttrium, but other rare earth elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), and the like may be used.
Further, yttrium, which is a rare earth element, is replaced with lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), or erbium (Er).
Further, the boron-containing rare earth-containing high-entropy alloy also comprises a quenching and tempering element.
Further, the preparation method of the high-entropy alloy is one of microwave sintering, a copper mold suction casting method, magnetron sputtering coating and a powder metallurgy method.
The boron-containing and rare-earth-containing high-entropy alloy is obtained by the magnetic field treatment method of the boron-containing and rare-earth-containing high-entropy alloy.
The principle of the invention is that the phase change driving force generated by the magnetic field is utilized to promote the soft phase rare earth-rich phase in the boron-containing rare earth-containing high-entropy alloy to generate hard particle phase, and the generation of the particle phase can improve the strength of the rare earth-rich phase, thereby improving the mechanical property and the wear resistance of the whole alloy. The heat treatment energy of the pulsed magnetic field is high, the treatment efficiency is high, but the boride grains can grow rapidly, and the coarse boride can make the alloy become brittle and the toughness is reduced. Therefore, the efficiency is improved by adopting a pulsed magnetic field heat treatment mode in the early stage of treatment, and the structure is further optimized by adopting a static magnetic field deep cooling mode in the later stage. The coupling effect of the deep cooling field and the static magnetic field can also promote the generation of hard particle phase, and simultaneously has good effects of grain refinement and internal residual stress relief, but also has the problems of low conversion efficiency and excessive consumption. Therefore, the combination of pulsed magnetic field heat treatment and static magnetic field cryogenic treatment can exert the high-quality effect of respective treatment to the maximum extent and avoid adverse reaction, is an effective post-treatment method, and provides a wide prospect for future development of high-entropy alloy.
Compared with the prior art, the invention has the following remarkable advantages and effects:
(1) the method is suitable for carrying out strengthening and toughening treatment on the boron-containing rare earth-containing high-entropy alloy product after precision machining, does not influence metal components, does not damage the surface layer and the structure of the product, and has outstanding advantages compared with the existing chemical plating, deposition and mechanical machining deformation strengthening.
(2) The liquid nitrogen and the static magnetic field adopted in the treatment process do not pollute the environment, do not influence the health of operators, and have controllable operation process, better safety and low cost. Therefore, the invention belongs to a novel green and environment-friendly material processing method.
(3) The treatment method adopted by the invention can play a role in obviously regulating the structure of the boron-containing rare earth-containing high-entropy alloy, thereby improving the obdurability of the boron-containing rare earth-containing high-entropy alloy and obviously improving the wear resistance of the alloy. The experimental result shows that under the same condition, the improvement of the conversion rate of the beneficial phase hard particle phase by the pulse magnetic field can averagely reach 18%, the static magnetic field effect is 8.7%, and the temperature field effect is the lowest and is 4.3%. The single heat treatment can not produce obvious effect under the condition of not adding a magnetic field, the performance of the material can not be obviously improved by the single magnetic field treatment, and the generation and the growth of the hard particle phase can be realized only by combining the temperature field and the magnetic field, so that the comprehensive mechanical property and the wear resistance of the alloy are greatly improved.
In conclusion, the method greatly expands the application range of the high-entropy alloy, further excavates the performance potential of the existing high-entropy alloy, reduces the production cost and has higher market economic benefit.
Drawings
Fig. 1 is a schematic diagram of a magnetic field apparatus employed in the present invention.
FIG. 2 shows FeCoNi after a 400 ℃ pulsed magnetic field annealing treatment for 0.5h and a 0.2T magnetostatic field intensity cryogenic treatment for 5h1.5CuB0.5Y0.2Scanning electron microscopy electron diffraction pattern of (2).
FIG. 3 shows FeCoNi after a 0.5h annealing treatment at 400 ℃ in a pulsed magnetic field and a 5h deep cooling treatment at a static magnetic field intensity of 0.2T1.5CuB0.5Y0.2Scanning electron microscope images after the frictional wear test.
FIG. 4 shows FeCoNi after 30h of deep cooling treatment at 400 ℃ and a pulsed magnetic field annealing treatment at a static magnetic field intensity of 0.2T for 2h1.5CuB0.5Y0.2Scanning electron microscopy electron diffraction pattern of (2).
FIG. 5 shows FeCoNi after 30h of deep cooling treatment at 400 ℃ and a pulsed magnetic field annealing treatment at a static magnetic field intensity of 0.2T for 2h1.5CuB0.5Y0.2Scanning electron microscope images after the frictional wear test.
FIG. 6 shows FeCoNi after cryogenic treatment for 30h at 450 ℃ and 1T in the intensity of static magnetic field for 2h in the annealing treatment of a pulsed magnetic field1.5CuB0.5Y0.2Scanning electron microscopy electron diffraction pattern of (2).
FIG. 7 shows FeCoNi after cryogenic treatment for 30h at 450 ℃ and 1T in the intensity of static magnetic field for 2h in the annealing treatment of a pulsed magnetic field1.5CuB0.5Y0.2Scanning electron microscope images after the frictional wear test.
In the figure: 1. the first strong magnet, 2, the clamp, 3, the second strong magnet, 4, the goods.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
The magnetic field treatment method of the boron-containing and rare-earth-containing high-entropy alloy promotes the soft phase rare earth-rich phase in the boron-containing and rare-earth-containing high-entropy alloy to generate a hard particle phase by utilizing the phase change driving force generated by the magnetic field, and the generation of the particle phase can improve the strength of the rare earth-rich phase, thereby improving the mechanical property and the wear resistance of the whole alloy. Can simultaneously improve the mechanical property and the wear resistance of the boron-containing rare earth-containing high-entropy alloy. The magnetic field treatment method comprises the steps of firstly, conducting cryogenic treatment on the boron-containing rare earth-containing high-entropy alloy under the condition of a static magnetic field after the boron-containing rare earth-containing high-entropy alloy is cooled to room temperature through pulsed high-intensity magnetic field heat treatment, placing the boron-containing rare earth-containing high-entropy alloy in air to recover to the room temperature after the cryogenic treatment is finished, generating a nanoparticle phase which is beneficial to simultaneously improving the mechanical property and the wear resistance of the alloy, eliminating internal residual stress and prolonging the service life. The magnetic field device used is shown in fig. 1. Comprises two opposite strong magnets, namely a first strong magnet 1 and a second strong magnet 2, and a clamp 2 for clamping a product 4.
The heat treatment energy of the pulsed magnetic field is high, the treatment efficiency is high, but the boride grains can grow rapidly, and the coarse boride can make the alloy become brittle and the toughness is reduced. Therefore, the efficiency is improved by adopting a pulsed magnetic field heat treatment mode in the early stage of treatment, and the structure is further optimized by adopting a static magnetic field deep cooling mode in the later stage. The coupling effect of the deep cooling field and the static magnetic field can also promote the generation of hard particle phase, and simultaneously has good effects of grain refinement and internal residual stress relief, but also has the problems of low conversion efficiency and excessive consumption. Therefore, the combination of the pulsed magnetic field heat treatment and the static magnetic field cryogenic treatment can exert the good quality effect of the respective treatment to the maximum extent and avoid the adverse reaction, and the method is a very effective post-treatment method.
The boron-containing rare earth-containing high-entropy alloy and the magnetic field treatment method thereof specifically comprise the following steps:
(1) and (3) filling the boron-containing rare earth-containing high-entropy alloy product after being processed and formed into an alumina crucible, then putting the boron-containing rare earth-containing high-entropy alloy product into a tubular furnace, setting heat treatment process parameters such as heating rate, heat preservation temperature, heat preservation time and the like, vacuumizing after setting, introducing protective gas, and operating a program to perform heat treatment. The initial heating rate of the tube furnace is 5 ℃/min, and the heating rate is 2 ℃/min when the temperature is raised to 400 ℃. Although the precipitated phase conversion rate can be improved due to the overlong heat treatment time or overhigh temperature of the product, the mechanical property of the product is influenced due to the coarseness of the structure grains, and for the condition that light and thin parts even have high-temperature deformation, the low precipitated phase conversion rate is caused due to the overlong heat treatment temperature or shorter heat treatment time, so that the service performance of the product is influenced. Therefore, when the thickness of the boron-containing rare earth-containing high-entropy alloy to be treated is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, the heat treatment temperature is 400-450 ℃, and the treatment time is 0.1-2 h; when the thickness of the boron-containing rare earth-containing high-entropy alloy to be treated is more than 10mm and belongs to a heavy part, the heat treatment temperature is 450-550 ℃, and the treatment time is 2-5 h.
(2) After the temperature is raised to the treatment temperature, introducing a magnetic field, wherein the pulse frequency of the magnetic field is 0.1-1000 Hz, and the magnetic field intensity is 0.1-10T;
(3) after the heat treatment is finished, closing the magnetic field, taking out the product, cooling the product in the air to room temperature, and performing cleaning, finishing, grinding and polishing treatment on the surface of the product so as to improve the efficiency of the magnetic field treatment;
(4) putting a sample into a clamp, clamping strong magnets at two ends of the clamp, wrapping the whole static magnetic field device by using a heat-preservation fiber felt with the surface magnetic field intensity of 0.1-2T, and immersing the sample into liquid nitrogen at the temperature of-180 to-190 ℃ for cryogenic treatment, wherein the cryogenic heat preservation time is 1-120 h. Because when the intensity of the strong magnetic field selected by the heavy piece is smaller, the internal tissue can not be driven and converted due to insufficient magnetic field energy, and the cryogenic magnetic field effect is weakened. For light thin parts, the performance of the light thin parts is not obviously improved after the deep cooling heat preservation time exceeds a certain time. For heavy and thick parts, if the heat preservation time of the subzero treatment is too short, the conditions of low grain refinement degree and low precipitated phase conversion rate can occur, so that the treatment effect is not obvious. Therefore, when the thickness of the boron-containing rare earth-containing high-entropy alloy to be treated is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, a strong magnet of 0.1-1T is selected, and the deep cooling heat preservation time is 1-60 hours; when the thickness of the boron-containing rare earth-containing high-entropy alloy to be treated is larger than 10mm and belongs to a heavy part, a strong magnet with the magnetic field intensity larger than 1T needs to be selected, and the deep cooling heat preservation time is prolonged to 60-120 h.
(5) And taking the boron-containing rare earth-containing high-entropy alloy product out of the clamp, and restoring the boron-containing rare earth-containing high-entropy alloy product to room temperature in the air.
The boron-containing high-entropy alloy used by the magnetic field treatment method mainly comprises Fe, Co, Ni, Cu, B and Y, and the atomic ratio expression of the alloy components is FeCoNi1.5CuBnYmWherein 0 is<n<1.2；0<m<0.5. But is not limited to this component, and other hardening and tempering elements may be added. The rare earth element is not limited to yttrium, and other rare earth elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), and the like may be used. The preparation method of the high-entropy alloy is one of microwave sintering, copper mold suction casting, magnetron sputtering coating and powder metallurgy.
FeCoNi used in the following examples1.5CuB0.5Y0.2The high-entropy alloy is boron-containing rare earth-containing high-entropy alloy, the thickness of a sample is 6mm, and the high-entropy alloy belongs to a light thin piece and is matched with a style clamp with the same thickness. The strong magnet is N52 type Nd-Fe-B strong magnet. FeCoNi subjected to cryogenic treatment1.5CuB0.5Y0.2The high-entropy alloy is processed into a cylindrical pattern of phi 6 x 9mm by adopting a linear cutting mode for a compression experiment. The invention uses CET-I type friction wear tester to test the wear resistance of the alloy, the sample size is 7 × 2.5mm, and the diameter of the grinding ball is 4mm3N4The abrasion time of the ball is 30 minutes, the load is 100N, the rotating speed is 220t/m, and the sliding distance is 5 mm.
Example 1
And (2) putting the processed and formed boron-containing rare earth-containing high-entropy alloy product into an alumina crucible, then putting the product into a tubular furnace, setting the heat preservation temperature and the heat preservation time to be 400 ℃, annealing for 0.5h, vacuumizing and introducing protective gas after the setting is finished, operating the program to carry out heat treatment, and introducing a magnetic field after the temperature is raised to the treatment temperature. After the heat treatment is finished, closing the magnetic field, taking out the product, cooling the product in the air to room temperature, and performing cleaning, finishing, grinding and polishing treatment on the surface of the product so as to improve the efficiency of the magnetic field treatment; putting a sample into a clamp, clamping strong magnets at two ends of the clamp, wrapping the whole static magnetic field device by using a heat-preservation fiber felt with the surface magnetic field intensity of 0.2T, and immersing the sample into liquid nitrogen at the temperature of minus 180 to minus 190 ℃ for cryogenic treatment, wherein the cryogenic heat preservation time is 5 hours. And taking the boron-containing rare earth-containing high-entropy alloy product out of the clamp, and restoring the boron-containing rare earth-containing high-entropy alloy product to room temperature in the air.
FIG. 2 shows FeCoNi after annealing at 400 deg.C for 0.5h and cryogenic treatment at 0.2T static magnetic field strength for 5h1.5CuB0.5Y0.2The scanning electron microscope image shows that the cryogenic treatment and the annealing treatment are short, and the appearance of a precipitated phase is not obvious, so that only a rare earth-rich phase (soft phase) and a boride phase and a high-entropy alloy base phase can be seen in the scanning image, and the mechanical property and the wear resistance of the boron-containing rare earth-containing high-entropy alloy are greatly limited by the soft phase. The compressive strength of the alloy is 1228MPa, which is improved by 2.25% compared with the untreated parent metal (1201MPa), the maximum compression ratio is 28.72%, which is improved by 1.81% compared with the untreated parent metal (28.21%), and the mechanical property is not obviously improved at this time.
FIG. 3 shows FeCoNi after a 0.5h annealing treatment at 400 ℃ in a pulsed magnetic field and a 5h deep cooling treatment at a static magnetic field intensity of 0.2T1.5CuB0.5Y0.2In a scanning electron microscope image after a frictional wear test, the wear types mainly include abrasive wear, adhesive wear and stripping wear, a left side grinding mark has a large-range adhesive trace, the surface of the left side grinding mark is covered with more new abrasive grains, a right side of the left side grinding mark has a large stripping pit, the edge of the stripping pit has more irregular cracks, and the left side grinding mark is likely to be evolved into a new stripping area under the action of a load perpendicular to the wear surface to cause more wear loss. At the moment, the abrasion performance of the alloy is not obviously improved, and the abrasion resistance is poor.
Example 2
After the surface treatment of the boron-containing rare earth-containing high-entropy alloy product after the processing and forming, the cryogenic magnetic field treatment is performed on the alloy according to the operation flow of the embodiment 1, it should be noted that in order to improve the treatment effect, the pulsed magnetic field annealing treatment time and the static magnetic field cryogenic treatment time are respectively prolonged to 2h and 30h, the prolongation of the cryogenic treatment time is beneficial to the generation of a precipitated phase, and the prolongation of the annealing treatment time is beneficial to the alleviation of the internal residual stress generated under the coupling effect of the cryogenic field and the magnetic field.
FIG. 4 shows FeCoNi after 30h of deep cooling treatment at 0.2T and annealing treatment at 400 deg.C for 2h with pulsed magnetic field1.5CuB0.5Y0.2The scanning electron micrograph of (1) shows that the crystal grains are refined compared with those in example 1, a submicron-order hard particle phase is generated in the rare earth-rich phase, and the generation of the hard particle phase contributes to the improvement of the strength of the rare earth-rich phase, thereby improving the strength of the entire alloy. The compressive strength of the alloy is 1314Mpa, the maximum compression ratio is 31.25 percent compared with 9.5 percent of that of the untreated parent metal, and the mechanical property is obviously improved compared with 10.78 percent of that of the untreated parent metal.
FIG. 5 shows FeCoNi after 30h of subzero treatment at 400 deg.C and 0.2T for 2h of pulsed magnetic field annealing1.5CuB0.5Y0.2In a scanning electron microscope image after a frictional wear test, the wear types mainly include abrasive wear and stripping wear, irregular stripping occurs in a plurality of areas, a fresh matrix is exposed, a plurality of abrasive grains are gathered in a stripping pit and may cause new grinding marks on the surface, the wear condition is obviously improved compared with that of the embodiment 1, and the generation of the submicron particle phase is also greatly improved for the wear resistance of the alloy.
Example 3
After the surface treatment of the boron-containing rare earth-containing high-entropy alloy product after the processing and forming, the cryogenic magnetic field treatment is performed on the alloy according to the operation flow of the embodiment 2, it should be noted that, in order to further improve the treatment effect, the annealing temperature and the static magnetic field strength are respectively increased to 450 ℃ and 1T, the increase of the magnetic field strength is helpful for the generation of a precipitated phase, and the increase of the annealing temperature is helpful for further effectively relieving the internal stress residue generated under the coupling effect of the cryogenic field and the magnetic field.
FIG. 6 shows FeCoNi after cryogenic treatment for 30h at 450 ℃ and 1T in the intensity of static magnetic field for 2h in the annealing treatment of a pulsed magnetic field1.5CuB0.5Y0.2Scanning electron micrograph (c). The further precipitation of the submicron particle phase can be seen from the figureAnd are uniformly distributed in the rare earth-rich phase. The compressive strength of the alloy is 1421Mpa, which is 18.32% higher than that of the untreated parent metal, the maximum compression ratio is 32.71%, which is 15.95% higher than that of the untreated parent metal, and the mechanical property is obviously improved.
FIG. 7 shows FeCoNi after cryogenic treatment for 30h at 450 ℃ and 1T in the intensity of static magnetic field for 2h in the annealing treatment of a pulsed magnetic field1.5CuB0.5Y0.2Scanning electron microscope images after the frictional wear test. The abrasion type is abrasive particle abrasion, the abrasive particle has a shallow and fine furrow-shaped appearance parallel to an abrasion direction, a small amount of abrasive particles are remained on the surface, the abrasion condition is good, and the abrasion condition is greatly improved compared with that of the embodiment 1 and the embodiment 2, because the second phase strengthening is generated due to the precipitation of the submicron hard particle phase.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A magnetic field treatment method of boron-containing rare earth-containing high-entropy alloy is characterized by comprising the following steps: after the boron-containing rare earth-containing high-entropy alloy is subjected to pulsed high-intensity magnetic field heat treatment and is reduced to room temperature, the boron-containing rare earth-containing high-entropy alloy is subjected to cryogenic treatment under the condition of a static magnetic field, and is placed in air to be restored to the room temperature after the cryogenic treatment is finished, so that a nanoparticle phase beneficial to simultaneously improving the mechanical property and the wear resistance of the alloy is generated, the internal residual stress is eliminated, and the service life is prolonged.
2. The magnetic field treatment method of the boron-containing rare earth-containing high entropy alloy of claim 1, characterized in that: the method comprises the following steps:
step (1): loading the boron-containing rare earth-containing high-entropy alloy product after being processed and formed into an alumina crucible, then placing the boron-containing rare earth-containing high-entropy alloy product into a tubular furnace, setting the heating rate, the heat preservation temperature and the heat preservation time, vacuumizing and introducing protective gas after setting, and operating the program to carry out heat treatment;
step (2): after the temperature is raised to the treatment temperature, introducing a magnetic field, wherein the pulse frequency of the magnetic field is 0.1-1000 Hz, and the magnetic field intensity is 0.1-10T;
and (3): closing the magnetic field after the heat treatment is finished, taking out the boron-containing rare earth-containing high-entropy alloy product, cooling the boron-containing rare earth-containing high-entropy alloy product in air to room temperature, and performing cleaning, finishing, grinding and polishing treatment on the surface of the boron-containing rare earth-containing high-entropy alloy product;
and (4): placing a boron-containing rare earth-containing high-entropy alloy product into a clamp, clamping strong magnets at two ends of the clamp, wrapping the whole static magnetic field device by using a heat-preservation fiber felt, and immersing the product into liquid nitrogen at the temperature of-180 to-190 ℃ for cryogenic treatment, wherein the cryogenic heat preservation time is 1 to 120 hours;
and (5): and taking the boron-containing rare earth-containing high-entropy alloy product out of the clamp, and restoring the boron-containing rare earth-containing high-entropy alloy product to room temperature in the air.
3. The magnetic field treatment method of the boron-containing rare earth-containing high-entropy alloy according to claim 2, wherein in the step 1), the initial temperature rise rate of the tube furnace is 5 ℃/min, and the temperature rise rate is 2 ℃/min when the temperature rises to 400 ℃; when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, the heat treatment temperature is 400-450 ℃, and the treatment time is 0.1-2 h; when the boron-containing rare earth-containing high-entropy alloy is thicker than 10mm and belongs to a heavy part, the heat treatment temperature is 450-550 ℃, and the treatment time is 2-5 h.
4. The magnetic field treatment method of the boron-containing rare earth-containing high-entropy alloy as claimed in claim 2, wherein in the step 4), when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin piece, a strong magnet of 0.1-1T is selected; when the boron-containing rare earth-containing high-entropy alloy is thicker than 10mm and belongs to a heavy part, a strong magnet with the magnetic field intensity larger than 1T needs to be selected.
5. The magnetic field treatment method for the boron-containing rare earth-containing high-entropy alloy as claimed in claim 2, wherein in the step 4), when the thickness of the boron-containing rare earth-containing high-entropy alloy is less than or equal to 10mm, namely the boron-containing rare earth-containing high-entropy alloy belongs to a light thin part, the deep cooling heat preservation time is 1-60 h. When the thickness of the boron-containing rare earth-containing high-entropy alloy is larger than 10mm and belongs to a heavy part, the deep cooling heat preservation time needs to be prolonged to 60-120 h.
6. The magnetic field treatment method for the boron-containing rare earth-containing high-entropy alloy as claimed in claim 2, wherein the boron-containing high-entropy alloy mainly comprises Fe, Co, Ni, Cu, B and Y, and the atomic ratio expression of the alloy components is FeCoNi1.5CuBnYmWherein 0 is<n<1.2；0<m<0.5。
7. The magnetic field treatment method for the boron-containing rare earth-containing high entropy alloy of claim 6, wherein the rare earth element yttrium is replaced by lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho) or erbium (Er).
8. The magnetic field treatment method for the boron-containing rare earth-containing high entropy alloy as claimed in claim 6, wherein the boron-containing rare earth-containing high entropy alloy further comprises a quenching and tempering element.
9. The magnetic field treatment method for the boron-containing rare earth-containing high-entropy alloy as claimed in claim 6, wherein the preparation method for the boron-containing rare earth-containing high-entropy alloy is one of microwave sintering, copper mold suction casting, magnetron sputtering coating and powder metallurgy.
10. The boron-containing and rare-earth-containing high-entropy alloy obtained by the magnetic field treatment method of the boron-containing and rare-earth-containing high-entropy alloy according to any one of claims 1 to 9.
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| GB2212502.5A GB2606330B (en) | 2020-02-28 | 2021-02-24 | Boron-containing and rare earth-containing high-entropy alloy and magnetic field treatment method therefor |
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| WO2021169985A1 (en) * | 2020-02-28 | 2021-09-02 | 江苏大学 | High-entropy alloy containing boron and rare earth and magnetic field treatment method therefor |
| CN115354126A (en) * | 2022-08-15 | 2022-11-18 | 武汉理工大学 | Method and device for improving toughness of metal material by using cryogenic electromagnetic composite field |
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