CN112725678B - Non-equal atomic ratio medium/high entropy alloy containing NiCoCr and preparation method thereof - Google Patents

Non-equal atomic ratio medium/high entropy alloy containing NiCoCr and preparation method thereof Download PDF

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CN112725678B
CN112725678B CN202011468310.8A CN202011468310A CN112725678B CN 112725678 B CN112725678 B CN 112725678B CN 202011468310 A CN202011468310 A CN 202011468310A CN 112725678 B CN112725678 B CN 112725678B
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李松
黄学玲
黄兰萍
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Central South University
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Abstract

The invention belongs to the field of medium/high entropy alloys, and particularly relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr and a preparation method thereof. The medium/high entropy alloy comprises Ni, Co, Cr and M, wherein the atomic percentages of the elements in the medium/high entropy alloy are respectively as follows: 30 to 50 percent of Ni, 20 to 40 percent of Co, 10 to 30 percent of Cr and 0 to 12 percent of M; m is selected from 0-2 of Al and Ti. The preparation method comprises the following steps: putting the high-purity metal block raw material into a water-cooling copper mold crucible of an electric arc melting furnace according to a certain proportion, and melting under the protection of argon atmosphere to obtain an as-cast product. The invention has reasonable component design, simple and controllable preparation process and excellent product performance.

Description

Non-equal atomic ratio medium/high entropy alloy containing NiCoCr and preparation method thereof
Technical Field
The invention belongs to the field of medium/high entropy alloys, and particularly relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr and a preparation method thereof, wherein the alloy has excellent room temperature mechanical properties.
Background
Medium-entropy alloys (MEAs) or High-entropy alloys (HEAs) are used as structural materials with great potential in the future, and the alloys are required to have better strength and toughness in engineering application. In a plurality of high-entropy alloy systems pursuing both obdurability, alloying elements Al and Ti are added, and the plasticity can be greatly reserved on the basis of greatly improving the strength by precipitating in a high-plasticity medium/high-entropy alloy matrix or directly introducing second-phase particles. The precipitation-strengthened high-entropy alloy matrix component is generally in a single-phase face-centered cubic (FCC) structure and is mainly selected from a 3d transition metal system mainly comprising three to five elements such as Co, Cr, Fe, Ni, Mn and the like, such as FeCoCrNiMn, FeCoCrNi, FeCoNi, NiCoCr and the like. At room temperature, the plasticity of a NiCoCr ternary alloy system is better than that of other ternary systems and even quaternary and quinary alloy systems, but at present, most of researches are conducted on NiCoCr ternary medium entropy alloys with equal atomic ratio or NiCoCr-based high entropy alloys with equal atomic ratio, and few reports about high-performance NiCoCr ternary medium entropy alloys with unequal atomic ratio or NiCoCr-based high entropy alloys with unequal atomic ratio exist, so that the current high-performance NiCoCr-based medium/high entropy alloys with unequal atomic ratio are to be developed.
Disclosure of Invention
The invention aims to prepare a non-equiatomic ratio NiCoCr medium/high-entropy alloy with excellent room-temperature mechanical property, obtains excellent room-temperature initial plasticity by adjusting the mixture ratio of three components in NiCoCr, and then introduces alloying elements Al and/or Ti to further obtain a high-volume-fraction nano precipitated phase to improve the alloy strength, thereby preparing the non-equiatomic ratio NiCoCr-based high-entropy alloy with excellent room-temperature mechanical property.
According to the invention, the Ni-and Co-rich non-equal atomic ratio NiCoCr medium entropy alloy is tried for the first time, and the non-equal atomic ratio NiCoCr-based high entropy alloy with Al added separately and Al and Ti added simultaneously is tried for the first time; the obtained product has excellent room-temperature mechanical property and industrial application value. Meanwhile, the design idea adopted by the invention has certain foresight.
The technical scheme adopted by the invention is as follows:
a non-equiatomic ratio medium/high entropy alloy containing NiCoCr; the medium/high entropy alloy comprises the following components in atomic percentage: 30 to 50 percent of Ni, 20 to 40 percent of Co, 10 to 30 percent of Cr and 0 to 12 percent of M; m is selected from 0-2 of Al and Ti.
As one of the preferred embodiments; the invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; in the alloy, the atomic percent content of nickel is greater than the atomic percent content of cobalt, and the atomic percent content of cobalt is greater than the atomic percent content of Cr.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; as one of optimization schemes, in the medium-entropy alloy, in atomic percentage: 40-45% of Ni, 35-40% of Co and 15-20% of Cr.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; preferably, in the medium entropy alloy, in terms of atomic ratio: co, Cr 3.5:3: 1.5.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; the current medium entropy alloy is Ni3.5Co3Cr1.5In the case of the medium entropy alloy, the room temperature tensile yield strength of the as-cast sample is 147MPa, the tensile strength is 445MPa, the elongation at break is 78.8%, the Vickers hardness is 149HV, the microhardness is 2.81GPa, and the elastic modulus is 246 GPa.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; as a further optimization scheme, the M element is composed of Al, and the atomic percentages of the elements are respectively as follows: 35-45% of Ni, 30-40% of Co, 10-20% of Cr and 5-12% of Al.
The invention isThe medium/high entropy alloy with non-equal atomic ratio containing NiCoCr; preferably, when the high-entropy alloy is (Ni)3.5Co3Cr1.5)90Al10In the case of the high-entropy alloy, the tensile yield strength at room temperature of an as-cast sample is 406MPa, the tensile strength is 646MPa, the elongation at break is 100.2%, the Vickers hardness is 269HV, the microhardness is 4.35GPa, and the elastic modulus is 220 GPa.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; as a further optimized scheme, the M element is composed of Al and Ti, and the atomic percentages of the elements are respectively: 35-45% of Ni, 30-40% of Co, 10-20% of Cr, 0-10% of Al and 0-10% of Ti; when Al and Ti are contained together, (Al + Ti) is 12% or less.
The invention relates to a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; preferably, when the high-entropy alloy is (Ni)3.5Co3Cr1.5)90Al5Ti5In the case of the high-entropy alloy, the as-cast sample has a tensile yield strength of 792MPa at room temperature, a tensile strength of 1004MPa, an elongation at break of 38.2%, a Vickers hardness of 429HV, a microhardness of 6.43GPa, and an elastic modulus of 268 GPa.
The invention relates to a preparation method of a non-equal atomic ratio medium/high entropy alloy containing NiCoCr; the method comprises the following specific steps:
(1) removing an oxide layer on the surface of a metal raw material of Ni, Co, Cr and M (Al and Ti) with the purity of more than 99.99 wt.% by using SiC sand paper, then putting the metal raw material into an ultrasonic cleaner, cleaning the metal raw material by using alcohol, taking the metal raw material out, and naturally drying the metal raw material in the air;
(2) weighing and proportioning by using an electronic precision balance according to the designed atomic percentage;
(3) sequentially putting the raw materials into a copper mold crucible of a vacuum arc melting furnace from low to high of the melting point of the metal raw materials in sequence, wherein the vacuum degree is at least 3 multiplied by 10-3Introducing high-purity argon in a Pa environment;
(4) firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then, smelting the alloy, and keeping the arc for 10-20 seconds when the sample is completely molten; after the alloy is cooled, turning over the alloy, and repeating the process for more than 5 times; and (5) obtaining a product.
In general, compared with the NiCoCr-based medium/high entropy alloy with equal atomic ratio, the technical scheme of the invention has the following advantages and positive effects:
(1) the invention prepares the non-equiatomic ratio NiCoCr intermediate entropy alloy, obtains the non-equiatomic ratio NiCoCr intermediate entropy alloy with a single-phase FCC structure by utilizing the characteristic matching dosage of each element, and the cast alloy without subsequent treatment shows excellent room temperature elongation (about 78.8 percent) which is higher than the room temperature elongation (about 60 percent) of the equiatomic ratio NiCoCr intermediate entropy alloy after homogenizing annealing, cold rolling and recrystallization annealing.
(2) Al (2.7 g/cm) for use in the present invention3)、Ti(4.5g/cm3) The low-density element can reduce the overall density of an alloy system, meet the trend of light weight development of future materials, and simultaneously Ni and Al can form Ni3Al intermetallic compound, L1, which is in coherent relationship with NiCoCr matrix2The (ordered FCC) tough phase is obtained by controlling the Al content to be less than or equal to 12 percent to precipitate a large amount of L12Without the formation of dendritic structures or hard brittle phases. Meanwhile, the invention also contains proper amount of Co, Cr and Ti which can promote the formation of (Ni, Co, Cr)3The (Al, Ti) multi-component intermetallic compound has better strengthening effect, which provides necessary conditions for obtaining the quinary high-entropy alloy with high strength, high hardness and high elongation.
(3) According to the invention, the medium entropy alloy of the NiCoCr with unequal atomic ratio is taken as a matrix, after a proper amount of alloying elements Al and Ti are introduced, because Ni/Al is more than 3, and the use amount of Co is more than that of Cr, the high entropy alloy of the NiCoCr with unequal atomic ratio can form a multi-component L1 with high volume fraction in an as-cast state2The strengthening phase, and thus the preferred embodiment, increases both strength and plasticity with the addition of 10 at.% Al, and increases strength by a large factor (-5 times) with the addition of 5 at.% Al and 5 at.% Ti, while still retaining some plasticity.
Drawings
FIG. 1 is a metallographic microstructure of a non-equiatomic ratio NiCoCr medium/high entropy alloy obtained in examples and comparative examples of the present invention.
FIG. 2 shows the morphology of the precipitated phase of the NiCoCr-based high-entropy alloy with unequal atomic ratio, which is added with Al and Ti and is obtained in example 3 of the invention, by a transmission electron microscope.
FIG. 3 is a three-dimensional plot of tensile yield strength, tensile strength and elongation at break of as-cast, anisometric NiCoCr medium/high entropy alloys obtained in examples and comparative examples of the present invention.
FIG. 4 is a room temperature nanoindentation load-displacement curve of as-cast non-equiatomic ratio NiCoCr medium/high entropy alloy obtained in the example of the present invention.
FIG. 5 is a graph showing the results of Vickers hardness testing of as-cast non-equiatomic ratio NiCoCr medium/high entropy alloy obtained in accordance with the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments, and it should be noted that the embodiments described herein are only for explaining the present invention and are not limited to the present invention. Further modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention.
In the following examples and comparative examples:
a vacuum arc melting furnace: a WK series vacuum arc melting furnace manufactured by beijing physic-electric limited company.
Metallographic structure: and observing the microstructure of the medium/high entropy alloy prepared by the invention by using an LEICA DM 2007M metallographic microscope.
Appearance of precipitated phase: the appearance of the precipitated phase of the unequal atom NiCoCr-based high-entropy alloy added with Al and Ti is observed by adopting a Tecnai G2F 20 field emission transmission electron microscope, and the radius and the proportion of the nano particles are statistically analyzed by ImageJ software.
Vickers hardness test: vickers hardness test was performed using HV-50 type durometer of the Vinan peak tester, Inc., with a load of 300g (2.942N) and a retention time of 15s, and the average and standard deviation were calculated for 10 measurements of each sample in different areas, and the standard deviation was expressed as an error bar.
Testing the tensile mechanical property at room temperature: using an American MTS landmark testerThe strain rate of the room temperature tensile test is 3 multiplied by 10-3s-1The dimensions of the tensile samples are as follows: the gauge length is 8mm, the width is 3.4mm, and the thickness is 1 mm.
And (3) nano indentation testing: the microhardness and the elastic modulus of the medium/high entropy alloy prepared by the invention are measured by an indentation tester (UNHT + MCT), and the test parameters are as follows: the loading load is 30mN, the loading rate is 1mN/s, the load retention time is 10s, and each sample is tested for 5 times, namely 5 impressions are made.
The examples and comparative examples of the non-equiatomic NiCoCr medium/high entropy alloys proposed by the present invention are detailed as follows:
example 1
The method comprises the following steps: removing oxide layers on the surfaces of Ni, Co and Cr metal raw materials with the purity of more than 99.99% by using SiC sand paper, then putting the materials into an ultrasonic cleaning instrument, cleaning the materials by using alcohol, taking the materials out, and naturally drying the materials in the air;
step two: calculating and weighing pure metal raw materials with the total mass of (50 +/-0.1) g according to the atomic ratio of Ni, Co and Cr being 3.5:3: 1.5;
step three: sequentially putting the raw materials into a copper mold crucible of a vacuum arc melting furnace from low to high of the melting point of the metal raw materials in sequence, wherein the vacuum degree is at least 3 multiplied by 10-3Introducing high-purity argon in a Pa environment;
step four: firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then, smelting the alloy, and keeping the arc for 10-20 seconds when the sample is completely molten; and (3) overturning the alloy after the alloy is cooled, and repeating the process for more than 5 times to obtain the NiCoCr medium entropy alloy with unequal atomic ratio.
As can be seen from the metallographic structure diagram of FIG. 1, Ni3.5Co3Cr1.5The medium entropy alloy is a coarse isometric crystal structure, and the grain size range is between 100 and 500 mu m. As is clear from FIGS. 3, 4 and 5, the as-cast sample had a room-temperature tensile yield strength of 147MPa, a tensile strength of 445MPa, an elongation at break of 78.8%, a Vickers hardness of 149HV, a microhardness of 2.81GPa and an elastic modulus of 246 GPa.
Example 2
The method comprises the following steps: removing oxide layers on the surfaces of Ni, Co, Cr and Al metal raw materials with the purity of more than 99.99% by using SiC sand paper, then putting the materials into an ultrasonic cleaner, cleaning the materials by using alcohol, taking the materials out, and naturally drying the materials in the air;
step two: according to (Ni)3.5Co3Cr1.5)90Al10Calculating the components and weighing pure metal raw materials with the total mass of (50 +/-0.1) g;
step three: sequentially putting the raw materials into a copper mold crucible of a vacuum arc melting furnace from low to high of the melting point of the metal raw materials in sequence, wherein the vacuum degree is at least 3 multiplied by 10-3Introducing high-purity argon in a Pa environment;
step four: firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then, smelting the alloy, and keeping the arc for 10-20 seconds when the sample is completely molten; cooling the alloy, turning over, repeating the process for more than 5 times to obtain the component (Ni)3.5Co3Cr1.5)90Al10Is higher entropy than NiCoCr.
As can be seen from the metallographic microstructure of FIG. 1, (Ni)3.5Co3Cr1.5)90Al10The high-entropy alloy is of an equiaxed crystal or columnar crystal structure, and the grain size range is 100-400 mu m. As can be seen from FIGS. 3, 4 and 5, the as-cast sample had a tensile yield strength of 406MPa at room temperature, a tensile strength of 646MPa, an elongation at break of 100.2%, a Vickers hardness of 269HV, a microhardness of 4.35GPa and an elastic modulus of 220 GPa. The grain boundary is a small-angle grain boundary, so that the grain boundary sliding is facilitated, the plasticity is improved, and the addition of Al promotes the generation of a precipitated phase, so that the strength is improved.
Example 3
The method comprises the following steps: removing oxide layers on the surfaces of Ni, Co, Cr, Al and Ti metal raw materials with the purity of more than 99.99% by using SiC sand paper, then putting the materials into an ultrasonic cleaner, cleaning the materials by using alcohol, taking the materials out, and naturally drying the materials in the air;
step two: according to the composition (Ni)3.5Co3Cr1.5)90Al5Ti5Calculating and weighing pure metal raw materials with the total mass of (50 +/-0.1) g;
step three: from low to low in melting point of the metal raw materialSequentially placing the raw materials into a copper mold crucible of a vacuum arc melting furnace in a vacuum degree of less than 3 × 10-3Introducing high-purity argon in a Pa environment;
step four: firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then, smelting the alloy, and keeping the arc for 10-20 seconds when the sample is completely molten; cooling the alloy, turning over, repeating the process for more than 5 times to obtain (Ni)3.5Co3Cr1.5)90Al5Ti5High entropy alloy.
As can be seen from the metallographic microstructure of FIG. 1, (Ni)3.5Co3Cr1.5)90Al5Ti5The grain of the high-entropy alloy is not obviously refined relative to the NiCoCr matrix, and the grain size range is 100-500 mu m. As can be seen from fig. 2, a high density of nanophase precipitates, with an average size of about 92.6nm, occupy about 66% of the total volume of the matrix. As is clear from FIGS. 3, 4 and 5, the as-cast sample had a tensile yield strength at room temperature of 792MPa, a tensile strength of 1004MPa, an elongation at break of 38.2%, a Vickers hardness of 429HV, a microhardness of 6.45GPa and an elastic modulus of 268 GPa. The large amount of precipitated phases improves the hardness and the strength of the alloy, improves the elastic performance and reduces the ductility.
Comparative example 1
The method comprises the following steps: removing oxide layers on the surfaces of Ni, Co, Cr, Al and Ti metal raw materials with the purity of more than 99.99% by using SiC sand paper, then putting the materials into an ultrasonic cleaner, cleaning the materials by using alcohol, taking the materials out, and naturally drying the materials in the air;
step two: according to composition (Ni)3.5Co3Cr1.5)80Al10Ti10Calculating and weighing pure metal raw materials with the total mass of (50 +/-0.1) g;
step three: sequentially putting the raw materials into a copper mold crucible of a vacuum arc melting furnace from low to high of the melting point of the metal raw materials in sequence, wherein the vacuum degree is at least 3 multiplied by 10-3Introducing high-purity argon in a Pa environment;
step four: firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then melting the alloySmelting, wherein the arc holding time is 10-20 seconds when the sample is completely molten; cooling the alloy, turning over, repeating the process for more than 5 times to obtain the component (Ni)3.5Co3Cr1.5)80Al10Ti10Non-equiatomic ratio NiCoCr-based high entropy alloy.
As can be seen from the metallographic structure of FIG. 1, (Ni)3.5Co3Cr1.5)80Al10Ti10A large amount of dendritic structures appear in the high-entropy alloy. As is clear from Table 1 and FIG. 3, the yield strength at room temperature of 804MPa, the tensile strength of 1096MPa, the Vickers hardness of 560HV and the elongation at break of the cast sample were only 3.6%. It is thus demonstrated that excessive addition of Al and Ti improves the strength and hardness of the material, but the ductility is greatly reduced due to the large amount of dendritic structure, which is not favorable for practical engineering applications.
According to the invention, Al and Ti are selected as alloying elements, a certain amount of Al is added independently, so that the strength and toughness of the material can be improved simultaneously, a proper amount of Al and Ti is added, so that the strength can be greatly improved, and a certain plasticity can be maintained, but the plasticity is seriously reduced due to excessive addition of Al and Ti.
In summary, the present invention is only an embodiment of the present invention. The protection scope of the present invention is not limited thereto, and any modification and modification that can be made by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention.
Table 1 shows the room temperature mechanical properties of the anisotomic NiCoCr medium/high entropy alloys obtained in the examples and comparative examples.
TABLE 1
Figure BDA0002835351220000101
Figure BDA0002835351220000111

Claims (1)

1. A non-equiatomic ratio medium/high entropy alloy containing NiCoCr is characterized in that:
the medium entropy alloy is Ni3.5Co3Cr1.5The room-temperature tensile yield strength of an as-cast sample of the medium-entropy alloy is 147MPa, the tensile strength is 445MPa, the elongation at break is 78.8 percent, the Vickers hardness is 149HV, the microhardness is 2.81GPa, and the elastic modulus is 246 GPa;
the high-entropy alloy is (Ni)3.5Co3Cr1.5)90Al10The high-entropy alloy has an as-cast sample tensile yield strength of 406MPa at room temperature, a tensile strength of 646MPa, an elongation at break of 100.2 percent, a Vickers hardness of 269HV, a microhardness of 4.35GPa and an elastic modulus of 220 GPa; or
The high-entropy alloy is (Ni)3.5Co3Cr1.5)90Al5Ti5The high-entropy alloy is an as-cast sample of which the room-temperature tensile yield strength is 792MPa, the tensile strength is 1004MPa, the elongation at break is 38.2 percent, the Vickers hardness is 429HV, the microhardness is 6.43GPa, and the elastic modulus is 268 GPa;
the non-equiatomic ratio medium/high entropy alloy containing NiCoCr is prepared by the following specific steps:
(1) when the alloy is Ni3.5Co3Cr1.5During medium entropy alloying, SiC sand paper is used for removing oxide layers on the surfaces of Ni, Co and Cr metal raw materials with the purity of more than 99.99wt%, then the materials are placed in an ultrasonic cleaning instrument and cleaned by alcohol, and the materials are taken out and naturally dried;
when the alloy is (Ni)3.5Co3Cr1.5)90Al10When the high-entropy alloy is used, SiC sand paper is used for removing oxide layers on the surfaces of Ni, Co, Cr and Al metal raw materials with the purity of more than 99.99wt%, then the materials are placed in an ultrasonic cleaning instrument and cleaned by alcohol, and the materials are taken out and naturally dried;
when the alloy is (Ni)3.5Co3Cr1.5)90Al5Ti5When the high-entropy alloy is used, SiC sand paper is used for removing oxide layers on the surfaces of Ni, Co, Cr, Al and Ti metal raw materials with the purity of more than 99.99wt%, then the metal raw materials are placed in an ultrasonic cleaning instrument and cleaned by alcohol, and the metal raw materials are taken out and naturally dried;
(2) weighing and proportioning by using an electronic precision balance according to the designed atomic percentage;
(3) sequentially putting the raw materials into a copper mold crucible of a vacuum arc melting furnace from low to high of the melting point of the metal raw materials in sequence, wherein the vacuum degree is at least 3 multiplied by 10-3Introducing high-purity argon in a Pa environment;
(4) firstly, smelting pure titanium to absorb residual oxygen in a furnace chamber; then smelting the alloy, wherein the arc holding time is 10-20 seconds when the sample is completely molten; after the alloy is cooled, turning the alloy for smelting again, and repeating the process for more than 5 times; and (5) obtaining a product.
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