Disclosure of Invention
The invention aims to provide an NbC particle reinforced CoFeNiMn high-entropy alloy and a preparation method thereof, and the ceramic particle in-situ reinforced high-entropy alloy with excellent comprehensive performance is obtained, so that the problems that in the prior art, the high-entropy alloy material is low in hardness, poor in bonding between a reinforcing phase and a matrix alloy interface, and difficult in matching between strength and plasticity are solved.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:
a ceramic particle in-situ reinforced high-entropy alloy is prepared by mixing Co, Fe, Ni, Mn and (Nb + C) elements in a molar ratio of 1: 1: 1: 1: x is more than or equal to 0.4 and less than or equal to 1.2, the Co, the Fe, the Ni, the Mn and the Nb are all high-purity blocks or sheets, and the C is high-purity graphite.
Further, the molar ratio of the Co, Fe, Ni, Mn, Nb and C elements is 1: 1: 1: 1: 0.5: at 0.5, the alloy has the best strength and plasticity matching, the compressive strength is 1178MPa, and the breaking strain is 31 percent.
The invention also provides a preparation method of the ceramic particle in-situ reinforced high-entropy alloy, which comprises the following steps:
step one, raw material preparation: six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
Step two, polishing and ultrasonic cleaning;
step three: weighing: accurately weighing various raw materials, wherein the molar ratio of Co, Fe, Ni, Mn and (Nb + C) elements is 1: 1: 1: 1: x is more than or equal to 0.4 and less than or equal to 1.2, and the Mn element has volatility, so that the Mn element needs to be added by 5-10 percent in the process of proportioning.
Step four: alloy melting and matching: the alloy melting and matching adopts a non-consumable vacuum arc furnace, firstly, various raw materials weighed in the third step are sequentially placed into a water-cooled copper mold crucible in a hearth according to the sequence of melting points from low to high, oxygen-absorbing titanium is placed in the middle of the crucible, and then a furnace door is closed; then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3Back filling high-purity argon after Pa; finally, the raw material is melted by striking an arc with an arc gun and melted to fill the raw materialThe mixture is homogenized, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for a plurality of times, and the electromagnetic stirring function is turned on in the smelting process.
Step five: after the alloy smelting is finished, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace; then the furnace chamber is opened to take out the alloy.
In the second step, firstly, metallographic abrasive paper with different particle sizes is adopted to polish the surface of the solid raw material, surface oxides, impurities and the like are removed, then the polished raw material is placed in acetone to be subjected to ultrasonic cleaning for 10-30min, and a blower is used for drying after the cleaning.
In the fourth step, the melting current is 300-500A, and the melting time is 40 s.
In the fourth step, the alloy is melted and matched by adopting a non-consumable vacuum arc furnace.
Compared with the prior art, the invention has the advantages that:
(1) the method is based on CoFeNiMn alloy, introduces Nb and C elements, and generates NbC phase through the reaction of the Nb and C elements with alloy liquid;
(2) the size of the prepared NbC particles is 10-40 mu m;
(3) the NbC enhanced phase has good wettability with the alloy liquid, and Nb and C have strong binding force, so that the generated NbC enhanced phase is well bound with a matrix interface, and no other impurity phase is separated out;
(4) the NbC particles generated by the method have high melting point, high hardness and good chemical stability, so that the comprehensive mechanical property of the FCC type high-entropy alloy with better plasticity and lower strength is improved.
(5) The ceramic reinforced high-entropy alloy is prepared by an in-situ autogenous method, the preparation process is simple, the method can reduce the process difficulty and the preparation cost of the alloy, can obtain the alloy without defects and with good interface combination, improves the strength and plasticity of the alloy, and obtains the ceramic particle reinforced high-entropy alloy with good matching of the strength and the plasticity.
Detailed Description
The present invention will be described in more detail with reference to specific examples. The embodiments described herein are exemplary only and are not intended to limit the present invention in any way.
Example 1
CoFeNiMn (NbC)0.4The high-entropy alloy comprises the following components of Co, Fe, Ni, Mn and (Nb + C) in molar ratio of 1: 1: 1: 1: 0.4, specifically prepared by the following method:
step one, raw material preparation. Six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials to be mixed, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
And step two, polishing and ultrasonic cleaning. And (3) adopting metallographic abrasive paper with different particle sizes to polish the surface of the solid raw material, and removing surface oxides, impurities and the like. And then, placing the polished raw materials in acetone for ultrasonic cleaning for 10-30min, and drying by using a blower after cleaning.
Step three: and (4) weighing the materials. Converting into mass percent according to atomic percent, and accurately weighing various raw materials according to mass percent for alloy smelting; because Mn element has volatility, 5-10% more is needed when the material is prepared.
Step four: and (4) alloy melting and matching. The alloy melting and matching adopts a non-consumable vacuum arc furnace. Weighing the third stepThe raw materials are sequentially put into a water-cooled copper mold crucible in a hearth according to the sequence of melting points from low to high, oxygen-absorbing titanium is placed in the middle of the crucible, and then a furnace door is closed. Then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3And back filling high-purity argon after Pa. Thirdly, the arc gun is ignited to melt the raw materials, the melting current is 300-500A, and the melting time is about 40 seconds. In order to fully mix the raw materials to achieve homogenization, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for 5 times, and the electromagnetic stirring function is turned on in the smelting process. And after the alloy is smelted, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace. Preparation to obtain CoFeNiMn (NbC)0.4High entropy alloy.
FIG. 1 shows CoFeNiMn (NbC) prepared in example 10.4X-ray diffraction pattern of high entropy alloy. As can be seen from the figure, the alloy mainly consists of an FCC phase and an NbC phase, wherein the main diffraction peak of the FCC phase has the highest diffraction intensity and the sharpest peak type, which indicates that the crystal structure of the FCC phase has the highest crystallization degree and the FCC phase occupies the largest volume fraction. FIG. 2(a) is a photograph of the microstructure of example 1. The alloy matrix is an FCC phase; the white particles are NbC particles, about 40 μm in size, uniformly distributed in the matrix. FIG. 3 shows CoFeNiMn (NbC)0.4The high-entropy alloy has a compression stress-strain curve, excellent plasticity, a breaking strain of more than 50 percent and a yield strength of 234 MPa. FIG. 4 shows CoFeNiMn (NbC)0.4The microhardness of the high-entropy alloy is 214 HV.
Example 2
CoFeNiMn (NbC)0.6The high-entropy alloy comprises the following components of Co, Fe, Ni, Mn and (Nb + C) in molar ratio of 1: 1: 1: 1: 0.6, specifically prepared by the following method:
step one, raw material preparation. Six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials to be mixed, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
And step two, polishing and ultrasonic cleaning. And (3) adopting metallographic abrasive paper with different particle sizes to polish the surface of the solid raw material, and removing surface oxides, impurities and the like. And then, placing the polished raw materials in acetone for ultrasonic cleaning for 10-30min, and drying by using a blower after cleaning.
Step three: and (4) weighing the materials. Converting into mass percent according to atomic percent, and accurately weighing various raw materials according to mass percent for alloy smelting; because Mn element has volatility, 5-10% more is needed when the material is prepared.
Step four: and (4) alloy melting and matching. The alloy melting and matching adopts a non-consumable vacuum arc furnace. And (3) sequentially putting the raw materials weighed in the step three into a water-cooled copper mold crucible in the hearth according to the sequence of melting points from low to high, placing oxygen-absorbing titanium in the middle of the crucible, and then closing the furnace door. Then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3And back filling high-purity argon after Pa. Thirdly, the arc gun is ignited to melt the raw materials, the melting current is 300-500A, and the melting time is about 40 seconds. In order to fully mix the raw materials to achieve homogenization, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for 5 times, and the electromagnetic stirring function is turned on in the smelting process. And after the alloy is smelted, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace. Preparation to obtain CoFeNiMn (NbC)0.6High entropy alloy.
FIG. 1 shows CoFeNiMn (NbC) prepared in example 20.6X-ray diffraction pattern of high entropy alloy. As can be seen from the figure, the alloy is composed mainly of FCC phase and NbC phase. FIG. 2(b) is a photograph of the microstructure of example 2, in which the white particles are NbC particles having an average size of about 40 μm and are uniformly distributed in the matrix. FIG. 3 shows CoFeNiMn (NbC)0.6The high-entropy alloy has a compression stress-strain curve, excellent plasticity, a breaking strain of more than 50 percent and a yield strength of 287 MPa. FIG. 4 shows CoFeNiMn (NbC)0.6The microhardness of the high-entropy alloy is 229 HV.
Example 3
CoFeNiMn (NbC)0.8The high-entropy alloy comprises the following components of Co, Fe, Ni, Mn and (Nb + C) in molar ratio of 1: 1: 1: 1: 0.8, specifically prepared by the following method:
step one, raw material preparation. Six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials to be mixed, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
And step two, polishing and ultrasonic cleaning. And (3) adopting metallographic abrasive paper with different particle sizes to polish the surface of the solid raw material, and removing surface oxides, impurities and the like. And then, placing the polished raw materials in acetone for ultrasonic cleaning for 10-30min, and drying by using a blower after cleaning.
Step three: and (4) weighing the materials. Converting into mass percent according to atomic percent, and accurately weighing various raw materials according to mass percent for alloy smelting; because Mn element has volatility, 5-10% more is needed when the material is prepared.
Step four: and (4) alloy melting and matching. The alloy melting and matching adopts a non-consumable vacuum arc furnace. And (3) sequentially putting the raw materials weighed in the step three into a water-cooled copper mold crucible in the hearth according to the sequence of melting points from low to high, placing oxygen-absorbing titanium in the middle of the crucible, and then closing the furnace door. Then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3And back filling high-purity argon after Pa. Thirdly, the arc gun is ignited to melt the raw materials, the melting current is 300-500A, and the melting time is about 40 seconds. In order to fully mix the raw materials to achieve homogenization, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for 5 times, and the electromagnetic stirring function is turned on in the smelting process. And after the alloy is smelted, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace. Preparation to obtain CoFeNiMn (NbC)0.8High entropy alloy.
FIG. 1 shows CoFeNiMn (NbC) prepared in example 30.8X-ray diffraction pattern of high entropy alloy. As can be seen from the figure, the alloy is composed mainly of FCC phase and NbC phase. FIG. 2(c) is a photograph of the microstructure of example 3, in which the white particles are NbC particles whose content is gradually increased, and whose average size is about 30 μm, and which are uniformly distributed in the matrix. FIG. 3 shows CoFeNiMn (NbC)0.8Compressive stress-strain curve of high entropy alloy, the alloy has excellent plasticity, and the fracture shouldThe yield strength becomes more than 50% and 346 MPa. FIG. 4 shows CoFeNiMn (NbC)0.8The microhardness of the high-entropy alloy is 241 HV.
Example 4
CoFeNiMn (NbC)1.0The high-entropy alloy comprises the following components of Co, Fe, Ni, Mn and (Nb + C) in molar ratio of 1: 1: 1: 1: the preparation method specifically comprises the following steps:
step one, raw material preparation. Six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials to be mixed, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
And step two, polishing and ultrasonic cleaning. And (3) adopting metallographic abrasive paper with different particle sizes to polish the surface of the solid raw material, and removing surface oxides, impurities and the like. And then, placing the polished raw materials in acetone for ultrasonic cleaning for 10-30min, and drying by using a blower after cleaning.
Step three: and (4) weighing the materials. Converting into mass percent according to atomic percent, and accurately weighing various raw materials according to mass percent for alloy smelting; because Mn element has volatility, 5-10% more is needed when the material is prepared.
Step four: and (4) alloy melting and matching. The alloy melting and matching adopts a non-consumable vacuum arc furnace. And (3) sequentially putting the raw materials weighed in the step three into a water-cooled copper mold crucible in the hearth according to the sequence of melting points from low to high, placing oxygen-absorbing titanium in the middle of the crucible, and then closing the furnace door. Then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3And back filling high-purity argon after Pa. Thirdly, the arc gun is ignited to melt the raw materials, the melting current is 300-500A, and the melting time is about 40 seconds. In order to fully mix the raw materials to achieve homogenization, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for 5 times, and the electromagnetic stirring function is turned on in the smelting process. And after the alloy is smelted, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace. Preparation to obtain CoFeNiMn (NbC)1.0High entropy alloy.
FIG. 1 shows Co prepared in example 4FeNiMn(NbC)1.0X-ray diffraction pattern of a high entropy alloy consisting essentially of FCC phase and NbC phase. FIG. 2(d) is a photograph of the microstructure of example 4. As can be seen from the figure, the alloy matrix is composed of a solid solution having an FCC structure; the white particles are NbC particles, the average size is 30 mu m, and the white particles are uniformly distributed in the alloy matrix. FIG. 3 shows CoFeNiMn (NbC)1.0According to the compressive stress-strain curve of the high-entropy alloy, the fracture strain of the alloy is 31%, the yield strength is 401MPa, the compressive strength is 1178MPa, and the high-entropy alloy has the best matching of strength and plasticity. FIG. 4 shows CoFeNiMn (NbC)1.0The microhardness of the high-entropy alloy is 263 HV.
Example 5
CoFeNiMn (NbC)1.2The high-entropy alloy comprises the following components of Co, Fe, Ni, Mn and (Nb + C) in molar ratio of 1: 1: 1: 1: 1.2, the preparation method specifically comprises the following steps:
step one, raw material preparation. Six elements of Co, Fe, Ni, Mn, Nb and C are selected as raw materials to be mixed, wherein the purity of the Co, Fe, Ni, Mn and Nb is higher than 99.9 percent, and the purity of the C is 99.9 percent of graphite.
And step two, polishing and ultrasonic cleaning. And (3) adopting metallographic abrasive paper with different particle sizes to polish the surface of the solid raw material, and removing surface oxides, impurities and the like. And then, placing the polished raw materials in acetone for ultrasonic cleaning for 10-30min, and drying by using a blower after cleaning.
Step three: and (4) weighing the materials. Converting into mass percent according to atomic percent, and accurately weighing various raw materials according to mass percent for alloy smelting; because Mn element has volatility, 5-10% more is needed when the material is prepared.
Step four: and (4) alloy melting and matching. The alloy melting and matching adopts a non-consumable vacuum arc furnace. And (3) sequentially putting the raw materials weighed in the step three into a water-cooled copper mold crucible in the hearth according to the sequence of melting points from low to high, placing oxygen-absorbing titanium in the middle of the crucible, and then closing the furnace door. Then, the electric arc furnace is vacuumized, and when the vacuum degree in the vacuum cavity reaches 5 multiplied by 10-3And back filling high-purity argon after Pa. In the third place, the first place is,the arc gun is ignited to melt the raw materials, the melting current is 300-500A, and the melting time is about 40 seconds. In order to fully mix the raw materials to achieve homogenization, the alloy ingot is turned over and then smelted again after the alloy is melted, the smelting is repeated for 5 times, and the electromagnetic stirring function is turned on in the smelting process. And after the alloy is smelted, the power supply is turned off, and the alloy ingot is statically placed on a water-cooling copper mold and cooled along with the furnace. Preparation to obtain CoFeNiMn (NbC)1.2High entropy alloy.
FIG. 1 shows CoFeNiMn (NbC) prepared in example 51.2X-ray diffraction pattern of a high entropy alloy consisting essentially of FCC phase and NbC phase. FIG. 2(e) is a photograph of the microstructure of example 5. As can be seen from the figure, the alloy matrix is composed of a solid solution having an FCC structure; in the figure, the white particles are NbC particles with the average size of 25 μm and are uniformly distributed in the alloy matrix. FIG. 3 shows CoFeNiMn (NbC)1.2According to the compressive stress-strain curve of the high-entropy alloy, the fracture strain of the alloy is 25%, the yield strength is 570MPa, and the compressive strength is 1045 MPa. FIG. 4 shows CoFeNiMn (NbC)1.2The microhardness of the high-entropy alloy is 280 HV.
The ratio of Nb to C is adjusted mainly to control the size and volume fraction of NbC particles in the structure (see fig. 2), because the properties of the alloy (such as strength and plasticity) are closely related to the size and volume fraction of NbC particles. The (Nb + C) content is low, the alloy plasticity is excellent, but the strength is low; the content of (Nb + C) is further increased, the plasticity of the alloy is reduced, the compressive strength is increased rapidly, the hardness of the alloy is continuously enhanced, and the alloy with both strength and plasticity is favorably obtained.
TABLE 1 CoFeNiMn (NbC)x(x ═ 0.4,0.6,0.8,1.0,1.2) compressibility of high entropy alloys
Although the embodiments of the present invention have been disclosed above, they are merely preferred examples of the present invention, and are not intended to limit the present invention in any way, and they can be applied to various fields suitable for the present invention. The invention is not limited to the specific details and illustrations shown and described, and indeed any simple modification, equivalent replacement or improvement made to the above embodiments in accordance with the teachings of the invention is within the scope of the invention.