CN116397170B - High-entropy alloy enhanced by atomic clusters and nano precipitated phases and preparation method thereof - Google Patents
High-entropy alloy enhanced by atomic clusters and nano precipitated phases and preparation method thereof Download PDFInfo
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- 230000032683 aging Effects 0.000 claims abstract description 8
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Abstract
The invention relates to a high-entropy alloy reinforced by atomic clusters and nano precipitated phases and a preparation method thereof, wherein the chemical formula of the high-entropy alloy is as follows: fe aMnbNicAldSieCuf, wherein 51 at.%≤a≤62 at.%,19 at.%≤b≤21 at.%,9 at.%≤c≤11 at.%,5 at.%≤d≤7 at.%,5 at.%≤e≤7 at.%,2.5 at.%≤f≤3.5 at.%, and a+b+c+d+e+f=100; the preparation method comprises the steps of vacuum induction melting, homogenizing annealing, cold rolling, solid solution and aging treatment. The high-entropy alloy reinforced by the atomic clusters and the nano precipitated phases is easy to prepare and process, and a large number of nano Cu-rich atomic clusters and nano B2 precipitated phases with a body-centered cubic structure can generate very obvious reinforcing effect, so that the yield strength of the alloy reaches over 900 MPa, and the alloy can be potentially applied to high-speed cutting tools, oil-gas compression bars, automobile engine cylinders and the like.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloy, and particularly relates to a high-entropy alloy reinforced by atomic clusters and nano precipitated phases and a preparation method thereof.
Background
Since the concept of high-entropy alloys was first proposed in 2004, such alloys have gained a great deal of attention from a large number of students in the field of materials. High entropy alloys consist of high concentrations of various elements with high mixed entropy, so such alloys are expected to readily form single phase solid solutions. Numerous studies have shown that high entropy alloys of single phase Face Centered Cubic (FCC) structure generally have excellent plasticity and toughness, and are currently gaining the most widespread attention, but such alloys are generally very low in strength, e.g., the yield strength of the CoCrFeMnNi alloy so far studied is less than 400 MPa, and often fails to meet the requirements of most industrial applications.
Precipitation strengthening has proven to be an effective measure for improving the strength of high-entropy alloys of single-phase FCC structures. If the high strength provided by the precipitated phase and the excellent plasticity of the FCC matrix can be combined, it is apparent that a high entropy alloy having both high strength and high plasticity can be developed. The B2 phase is a common precipitated phase in the FCC structure high-entropy alloy, the strengthening mechanism is Oldham strengthening, and the strengthening contribution is obviously improved along with the reduction of the size and the increase of the volume fraction. Numerous studies have shown that the B2 phase tends to precipitate at grain boundaries or within the intragranular deformation zone, with coarse sizes, generally in the micrometer scale, and that the contribution of the relative strength of such large-sized B2 precipitates is generally no more than 200 MPa. Therefore, the yield strength of the high-entropy alloy of the FCC structure with the reinforced B2 phase is still low, and a higher strengthening effect can be obtained if the dispersed and fine B2 phase can be separated out from the high-entropy alloy of the FCC structure.
Disclosure of Invention
Considering that the yield strength of the existing single-phase FCC structure high-entropy alloy is generally lower (200-500 MPa), and the precipitation of B2 phase is a common measure for strengthening the alloy, but the B2 precipitation phase in the alloy is difficult to generate a remarkable strengthening effect (not more than 200 MPa) due to the large size (micron level), so that the research and development of the FCC structure high-entropy alloy capable of obtaining the fine dispersion of the B2 precipitation phase is a key way for solving the problem that the yield strength of the existing FCC structure high-entropy alloy is generally lower. The high-strength alloy can be potentially applied to high-speed cutting tools, oil-pressure gas compression bars, engine cylinders and the like.
After Cu element is added into the FCC structure high-entropy alloy, stable chemical bonds are difficult to form due to larger mixing enthalpy between Cu atoms and other element atoms, so that dispersed nano-scale Cu-rich clusters can appear in an FCC matrix, and the interface of the Cu-rich clusters can be used as a heterogeneous nucleation site to promote the generation of nano precipitated phases. The method provides an important way for regulating the size and distribution of the B2 precipitated phase in the high-entropy alloy of the FCC structure, namely, the nano-scale B2 precipitated phase in dispersion distribution can be obtained by reasonably adding Cu element. The method not only can promote the strengthening effect of the B2 precipitated phase, but also can play the strengthening effect of the nanoscale Cu-rich atomic clusters at the same time, so that the overall strengthening effect is expected to be very remarkable.
Based on the above consideration, the invention provides the high-entropy alloy reinforced by the atomic clusters and the nano precipitated phases and the preparation method thereof, aiming at the problems that the yield strength of the existing FCC structure high-entropy alloy is low, the size of the B2 precipitated phases is large, and the reinforcing effect is not high.
The invention is realized by the following technical scheme:
The first aspect of the invention provides a high-entropy alloy enhanced by atomic clusters and nano precipitated phases, which is characterized in that the chemical formula of the high-entropy alloy is Fe aMnbNicAldSieCuf; wherein ,51 at.% ≤ a ≤ 62 at.%,19 at.% ≤ b ≤ 21 at.%,9 at.% ≤ c ≤ 11 at.%,5 at.% ≤ d ≤ 7 at.%,5 at.% ≤ e ≤ 7 at.%,2.5 at.% ≤ f ≤ 3.5 at.%, and a+b+c+d+e+f=100.
The atomic percentage of Fe may be, for example, 51%, 53.95%, 62%, etc.; the atomic percentage of Mn may be, for example, 19%, 20.38%, 21%, etc.; the atomic percentage of Ni may be, for example, 9%, 10.28%, 11%, etc.; the atomic percentage of Al may be, for example, 5%, 6.23%, 7%, etc.; the atomic percentage of Si may be, for example, 5%, 6.22%, 7%, etc.; the atomic percentage of Cu may be, for example, 2.5%, 3.03%, 3.5%, etc.
As a further explanation of the present invention, the ratio of Ni to Al in atomic percent in the alloy is 1.3 to 1.8.
As a further explanation of the present invention, the ratio of atomic percentages of Cu and Al in the high-entropy alloy is 0.3 to 0.7, and the ratio of atomic percentages of Cu and Fe is 0.03 to 0.07. So as to ensure that the alloy forms nanoscale (< 15 nm) Cu-rich atomic clusters with high volume fraction (> 15%) after aging treatment, and the Cu-rich atomic clusters assist B2 phase nucleation and limit B2 phase growth, so as to ensure that nanoscale (< 50 nm) B2 precipitated phases with high volume fraction (> 15%) are formed in a matrix phase of an FCC structure, and the yield strength of the alloy is remarkably improved.
As a further illustration of the present invention, the high entropy alloy consists of a face-centered cubic structured matrix phase, a nanoscale B2 phase, and nanoscale Cu-rich clusters.
As a further illustration of the present invention, the volume fraction of nanoscale Cu-rich atomic clusters in the high-entropy alloy is >15%; the volume fraction of the nanoscale B2 phase is >15%.
A second aspect of the present invention provides a method for preparing a high entropy alloy reinforced by atomic clusters and nano-precipitates as defined in any one of the preceding claims, the method comprising:
Proportioning the high-entropy alloy according to any one of the above materials (adopting pure Fe, pure Mn, pure Ni, pure Al, pure Si and pure Cu with purity not lower than 99.9 wt% as raw materials), and then carrying out vacuum induction smelting on the proportioning materials to obtain an ingot;
Homogenizing and annealing the cast ingot;
dividing the ingot subjected to the homogenizing annealing treatment into plates, and performing multi-pass cold rolling treatment;
Carrying out solution treatment on the cold-rolled plate;
and (5) aging the plate subjected to the solution treatment.
As a further explanation of the invention, the vacuum induction smelting is carried out in a vacuum induction smelting furnace, after each smelting is finished, the ingot casting is turned over firstly, then the next smelting is carried out, the smelting is repeated for 4-6 times, and argon is used as a protective atmosphere.
As a further explanation of the invention, the homogenizing annealing treatment is water-cooling quenching after heat preservation at 1100 ℃ is not less than 6 h under the protection of argon atmosphere.
As a further explanation of the invention, the cold rolling treatment is to divide the cast ingot after the homogenizing annealing treatment into plates, and perform multi-pass cold rolling by a double-roller plate and strip mill, wherein the deformation of each pass is not higher than 5%, and the total deformation is 70%.
As a further explanation of the invention, the solution treatment is to cool and quench the cold-rolled sheet material after the heat preservation at 1050 ℃ under the protection of argon atmosphere, which is not less than 1 h.
As a further explanation of the invention, the aging treatment is water-cooling quenching after the plate subjected to solution treatment is subjected to heat preservation at 600 ℃ in an air environment to be not less than 10 h.
Compared with the prior art, the invention has the following advantages:
The high-entropy alloy reinforced by the atomic clusters and the nano precipitated phases has low cost and simple preparation method, and simultaneously plays the reinforcing role of the nano Cu-rich atomic clusters and the nano B2 phases. Under the conditions of optimal component proportion and optimal solution treatment, the precipitation strengthening effect of the alloy reaches 729 MPa, which is far higher than the highest value (200 MPa) of the B2 phase strengthening effect in the prior FCC structure high-entropy alloy, so that the yield strength of the alloy reaches 947 MPa, and the alloy can be potentially applied to the fields of high-speed cutting tools, oil-gas-pressure rods, engine cylinders and the like with high requirements on the yield strength.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the initial structure of the high-entropy alloy prepared in example 1 and comparative example 2 of the present invention.
Fig. 2 is a Transmission Electron Microscope (TEM) and energy spectrum microscopic analysis (EDS) diagram of a nanoscale microstructure in the high-entropy alloy prepared in example 1 and comparative example 2 of the present invention.
FIG. 3 is a room temperature tensile engineering stress-strain curve of the high entropy alloy prepared in example 1 and comparative example 2 of the present invention.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The high-entropy alloy enhanced by atomic clusters and nano precipitated phases provided by the embodiment is composed of Fe, mn, ni, al, si, cu six elements, and the atomic percentages of the elements are as follows: 53.95% Fe,20.38% Mn,10.28% Ni,6.23% Al,6.22% Si,3.03% Cu.
The preparation method of the alloy comprises the following steps:
S1, taking pure Fe, pure Mn, pure Ni, pure Al, pure Si and pure Cu with purity not lower than 99.9 wt percent as raw materials, obtaining a high-entropy alloy cast ingot through vacuum induction smelting, turning the cast ingot after each smelting is finished, smelting the cast ingot for the next time, repeatedly smelting for 4 times, and adopting argon as a protective atmosphere.
S2, carrying out homogenizing annealing treatment on the cast ingot obtained by vacuum induction smelting under the protection of argon atmosphere, wherein the heat preservation temperature is 1100 ℃, the heat preservation time is 6h, and water cooling quenching is carried out after the treatment is finished.
S3, cutting the cast ingot subjected to the homogenizing annealing treatment into plates through wire cut by electric spark, and carrying out multi-pass cold rolling on the plates by adopting a double-roller plate and strip rolling mill, wherein the deformation of each pass is not higher than 5%, and the total deformation is 70%.
S4, carrying out solution treatment on the cold-rolled sheet under the protection of argon atmosphere, wherein the heat preservation temperature is 1050 ℃, the heat preservation time is 1 h, and water-cooling quenching is carried out after the treatment is completed.
S5, aging the plate subjected to solution treatment in an air environment, wherein the heat preservation temperature is 600 ℃, the heat preservation time is 10 h, and water cooling quenching is performed after the treatment is completed.
The initial structure of the alloy prepared in this example was characterized by SEM, and the results are shown in fig. 1. Fig. 1 (a) shows that the alloy prepared in this example is composed of matrix equiaxial grains of FCC structure, and fig. 1 (B) shows that there is a uniformly distributed high-density nanoscale B2 phase inside the FCC grains, as shown by blue circles.
The nanoscale microstructure of the alloy prepared in this example was characterized by TEM and the results are shown in figure 2. The TEM selective diffraction pattern in fig. 2 (a) demonstrates that the nano-scale ellipsoidal second phase dispersed inside the FCC grains is B2 phase, with a size of 48 nm and a volume fraction of 24%, and the EDS pattern in fig. 2 (B) shows that a large number of nano-scale Cu-rich clusters exist inside the FCC grains at the same time, with a size of 10 nm and a volume fraction of 18%.
According to GB/T228.1-2010 section 1 Metal Material tensile test: the mechanical properties of the alloy prepared in this example were measured in room temperature test method, and the result is shown in fig. 3, wherein the yield strength is 947 MPa and the elongation at break is 10%.
Comparative example 2
The high-entropy alloy provided in the comparative example does not contain Cu element, and consists of Fe, mn, ni, al, si elements, wherein the atomic percentages of the elements are as follows: 58.3% Fe,19.5% Mn,9.8% Ni,6.0% Al,6.4% Si.
The preparation method of the alloy comprises the following steps:
S1, taking pure Fe, pure Mn, pure Ni, pure Al, pure Si and pure Cu with purity not lower than 99.9 wt percent as raw materials, obtaining a high-entropy alloy cast ingot through vacuum induction smelting, turning the cast ingot after each smelting is finished, smelting the cast ingot for the next time, repeatedly smelting for 4 times, and adopting argon as a protective atmosphere.
S2, carrying out homogenizing annealing treatment on the cast ingot obtained by vacuum induction smelting under the protection of argon atmosphere, wherein the heat preservation temperature is 1100 ℃, the heat preservation time is 6h, and water cooling quenching is carried out after the treatment is finished.
S3, cutting the cast ingot subjected to the homogenizing annealing treatment into plates through wire cut by electric spark, and carrying out multi-pass cold rolling on the plates by adopting a double-roller plate and strip rolling mill, wherein the deformation of each pass is not higher than 5%, and the total deformation is 70%.
S4, carrying out solution treatment on the cold-rolled sheet under the protection of argon atmosphere, wherein the heat preservation temperature is 1050 ℃, the heat preservation time is 1 h, and water-cooling quenching is carried out after the treatment is completed.
S5, aging the plate subjected to solution treatment in an air environment, wherein the heat preservation temperature is 600 ℃, the heat preservation time is 10 h, and water cooling quenching is performed after the treatment is completed.
The initial structure of the alloy prepared in this comparative example was characterized by SEM, and the results are shown in fig. 1. FIG. 1 (c) shows that the alloy prepared in this comparative example is composed of matrix-equivalent axis grains of FCC structure, and FIG. 1 (d) shows that no precipitated phase is generated inside the FCC grains.
The nanoscale microstructure of the alloy prepared in this comparative example was characterized by TEM, and the results are shown in fig. 2. The TEM selective diffraction pattern in fig. 2 (c) demonstrates that no nanoscale B2 phase is generated inside the FCC grains, and the EDS pattern in fig. 2 (d) shows that Ni and Al elements are uniformly distributed inside the FCC grains, and no atomic clusters are formed.
According to GB/T228.1-2010 section 1 Metal Material tensile test: the mechanical properties of the alloy prepared in this comparative example were measured in room temperature test method, and the result is shown in fig. 3, wherein the yield strength is 218 MPa, and the elongation at break is 85%.
As can be seen from the comparison of the example 1 and the comparative example 2, the reasonable addition of Cu element can introduce nanoscale Cu-rich atomic clusters on one hand, and promote precipitation of nanoscale B2 phase on the other hand, and the strength of the Cu-containing high-entropy alloy is obviously higher than that of the Cu-free high-entropy alloy due to the strengthening effect generated by the nanoscale Cu-rich atomic clusters, so that the strength improvement range reaches 729 MPa.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The high-entropy alloy enhanced by atomic clusters and nano precipitated phases is characterized in that the chemical formula of the high-entropy alloy is Fe aMnbNicAldSieCuf; wherein ,51 at.% ≤ a ≤ 53.95at.%,20.38% at.% ≤ b ≤ 21 at.%,10.28% at.% ≤ c ≤ 11 at.%,6.23at.% ≤ d ≤ 7 at.%,5 at.% ≤ e ≤ 7 at.%,2.5 at.% ≤ f ≤ 3.5 at.%, and a+b+c+d+e+f=100deg.C;
The high-entropy alloy consists of a matrix phase with a face-centered cubic structure, a nanoscale B2 phase and nanoscale Cu-rich atomic clusters; the volume fraction of nanoscale Cu-rich atomic clusters in the high-entropy alloy is more than 15%; the volume fraction of the nanoscale B2 phase is >15%;
The preparation method of the high-entropy alloy enhanced by the atomic clusters and the nano precipitated phases comprises the following steps:
proportioning the high-entropy alloy, and then smelting the proportioning by vacuum induction to obtain an ingot;
Homogenizing and annealing the cast ingot;
dividing the ingot subjected to the homogenizing annealing treatment into plates, and performing multi-pass cold rolling treatment;
Carrying out solution treatment on the cold-rolled plate; the solid solution treatment is to cool and quench the cold-rolled plate after the heat preservation at 1050 ℃ is not less than 1h under the protection of argon atmosphere;
Aging the plate subjected to solution treatment; the aging treatment is water-cooling quenching after the heat preservation of the plate subjected to the solution treatment in an air environment at 600 ℃ is not less than 10 h.
2. The high-entropy alloy reinforced by atomic clusters and nano precipitated phases according to claim 1, wherein the vacuum induction melting is performed in a vacuum induction melting furnace, ingot casting is turned over after each melting is finished, then the next melting is performed, the melting is repeated for 4-6 times, and argon is used as a protective atmosphere.
3. The high-entropy alloy reinforced by atomic clusters and nano-precipitates according to claim 1, wherein said homogenizing annealing treatment is water-cooling quenching after heat preservation at 1100 ℃ under argon atmosphere of not less than 6h.
4. The high-entropy alloy reinforced by atomic clusters and nano-precipitates according to claim 1, wherein said cold rolling treatment is to divide the ingot after the homogenizing annealing treatment into sheets and cold-roll it in multiple passes with a twin roll strip mill, each pass having a deformation of not more than 5% and a total deformation of 70%.
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| CN105849287A (en) * | 2013-10-28 | 2016-08-10 | 纳米钢公司 | Metal steel production by slab casting |
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| CN104694808B (en) * | 2015-03-26 | 2017-02-22 | 北京科技大学 | High-entropy alloy with dispersion nano-sized precipitate strengthening effect and preparing method thereof |
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