CN110791693B - High-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and preparation method thereof - Google Patents
High-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and a preparation method thereof, and relates to the technical field of high-entropy alloy materialsxThe material is CoCrFeMnNi, wherein x is the mass ratio of Al element, and the value range is 4.5-5.5%. The invention takes CoCrFeMnNi high-entropy alloy powder and Al powder as raw materials, and adopts a powder metallurgy method to realize a controllable high-entropy alloy with FCC and BCC dual-phase structures, wherein the BCC phase is rich in Cr and Mn elements, and the volume ratio of the BCC phase is 11.2-16.2%. The high-entropy alloy prepared by the invention has the advantages of higher strength, good plasticity and corrosion resistance, simple preparation method process, lower cost, strong practicability and convenient popularization.
Description
Technical Field
The invention relates to the technical field of high-entropy alloy materials, in particular to a high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and a preparation method thereof.
Background
High-entropy alloys (HEAs), also known as multi-principal-element alloys (MEAs), break through the design concept of traditional alloys based on one or two elements, and at least comprise five main elements, wherein the atomic percentage of each component element is between 5 and 35 percent, and no obvious solute or solvent component exists between the components. The high entropy effect, slow diffusion effect, lattice distortion effect, and the cocktail effect produced by the multi-principal elements of the high entropy alloy facilitate the formation of a solid solution phase of simple crystal structure, such as Face Centered Cubic (FCC), Body Centered Cubic (BCC), or close packed Hexagonal (HCP) structure. In 2004, the teaching of Cantor first published a cocrfermni high entropy alloy with a single FCC structure prepared by arc melting, which is also known as Cantor alloy. To date, researchers at home and abroad have reported more than four hundred completely new high-entropy alloy systems. The existing research shows that the high-entropy alloy with the FCC structure has good thermodynamic stability, super-strong ductility and obvious work hardening performance, but low strength; the high-entropy alloy with the BCC structure has high strength but poor ductility. Therefore, high-entropy alloys with dual-phase structures of FCC and BCC have attracted much attention. But how do the BCC phase be introduced in or within the FCC structure? How to further refine grain size and control microstructure? These problems become a bottleneck restricting the application of high-entropy alloy, and need to be solved urgently.
At present, researchers have prepared high-entropy alloys with FCC and BCC dual-phase structures by using traditional methods such as vacuum arc melting, copper mold suction casting and vacuum induction melting, and the like, for example He and the like have prepared the high-entropy alloys with the dual-phase structures (FeCoNiCrMn)100-xAlx(x>8) High entropy alloys (J.Y.He, W.H.Liu, H.Wang, Y.Wu, X.J.Liu, T.G.Nieh, Z.P.Lu, Effects of Al addition on structural evaluation and tension properties of the FeCoNiCrMnhigh-entropy alloy system, actaMat.62 (2014) 105-113.). Kumar et al developed AlCuCrFeMnW high entropy alloys of the above two phase structure (D.Kumar, O.Ma.)ulik, S.Kumar, Y.V.S.S.Prasad, V.Kumar, Phase and thermal study of electronic AlCuCrFeMnW high entry overall process via spot plasma sintering, mater.chem.Phys.210(2018) 71-77.). However, the method inevitably has the defects of high smelting temperature, limited cooling rate and the like, so that the prepared high-entropy alloy has the defects of component segregation, large and thick grains, shrinkage porosity, air holes and the like, and the problem of mismatch between strong plasticity is caused; while the limited shape and size of the HEAs produced by the above-described methods also limit their utility.
In order to improve the defect of low strength of Cantor alloy CoCrFeMnNi with a single FCC structure, gas atomized CoCrFeMnNi high-entropy alloy powder and metal Al powder are used as raw materials, a powder metallurgy method is adopted to controllably prepare a low-Al-content high-entropy alloy with a FCC and BCC dual-phase structure, wherein BCC phase is rich in Cr and Mn elements, and the high-entropy alloy shows excellent comprehensive mechanical properties, namely has high strength, good plasticity and corrosion resistance.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and a preparation method thereof.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance, and the chemical composition of the high-entropy alloy is AlxThe material is CoCrFeMnNi, wherein x is the mass ratio of Al element, and the value range is 4.5-5.5%; high entropy alloys having FCC and BCCThe BCC phase is rich in Cr and Mn elements and accounts for 11.2-16.2% by volume.
The preparation method of the high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance comprises the following steps:
1) accurately weighing commercial CoCrFeMnNi high-entropy alloy powder, and then carrying out Al treatment according to the molecular formulaxWeighing commercially available metal Al powder with corresponding mass by using CoCrFeMnNi, and uniformly mixing the two raw materials by using a mixer at room temperature;
2) and (2) putting the uniformly mixed raw materials into a graphite die, carrying out hot-pressing sintering under a vacuum condition, wherein the sintering temperature is 1000-1100 ℃, the heating rate is 10-15 ℃/min, the sintering pressure is 35-45 MPa, the heat preservation time is 30-60 min, and cooling along with a furnace after the heat preservation is finished to obtain the high-entropy alloy which has low Al content, controllable BCC phase, FCC and BCC dual-phase structures, high strength and toughness matching and acid corrosion resistance.
Furthermore, the purity of the commercial CoCrFeMnNi high-entropy alloy powder is more than or equal to 99.5 percent, the particle size is less than or equal to 60 mu m, and the CoCrFeMnNi high-entropy alloy powder is prepared by a gas atomization method.
Furthermore, the purity of the commercially available metal Al powder is more than or equal to 99.5%, and the average particle size is 30-45 μm.
Furthermore, the sintering temperature is 1050 ℃, and the heating rate is 12 ℃/min.
Further, the sintering pressure is 35MPa, and the heat preservation time is 30 min.
(III) advantageous effects
The invention provides a high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and a preparation method thereof, and the high-entropy alloy has the following beneficial effects:
1. the invention provides a high-entropy alloy with a controllable BCC phase composition and a dual-phase structure by introducing a BCC phase rich in Cr and Mn elements into a Cantor alloy CoCrFeMnNi with a single FCC structure, wherein the volume ratio of the BCC phase is 11.2-16.2%;
2. the high-entropy alloy prepared by the invention has the characteristics of high strength and toughness and good corrosion resistance, wherein the Vickers hardness is 530-570 HV, the yield strength is 1500-1850 MPa, the plastic strain is 15-40%, and the alloy is corroded in 3.5 wt% NaCl solution and 0.05MHClThe current density is 2.6-3.2 x 10-7A/cm2And 2.4 to 2.8X 10-6A/cm2；
3. The invention provides a preparation method of a high-entropy alloy with low Al content, high strength and toughness and good corrosion resistance, and the method has the advantages of simple process, low cost, strong practicability and convenient popularization.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 example 1Al5SEM/EDS picture of CoCrFeMnNi high entropy alloy;
FIG. 2 example 1Al5XRD pictures of CoCrFeMnNi high-entropy alloy;
FIG. 3 example 1Al5A polarization curve picture of the CoCrFeMnNi high-entropy alloy in 3.5 wt% NaCl solution;
FIG. 4 example 1Al5Images of polarization curves of CoCrFeMnNi high-entropy alloy in 0.05MHCl solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the acid corrosion resistant high-entropy alloy with low Al content and high toughness matching is prepared by a powder metallurgy method, and the chemical composition of the alloy is Al5CoCrFeMnNi: weighing CoCrFeMnNi high-entropy alloy prepared by gas atomization method according to stoichiometric ratio of molecular formulaPutting the powder and metal Al powder, specifically 500.0g of CoCrFeMnNi and 25g of Al powder, into a mixer to mix for 2 hours to obtain uniformly mixed raw materials; the raw materials which are uniformly mixed are put into a graphite die and are subjected to hot-pressing sintering under the vacuum condition, the sintering temperature is 1100 ℃, the heating rate is 10 ℃/min, the sintering pressure is 40MPa, the heat preservation time is 60min, the raw materials are cooled along with the furnace after the heat preservation is finished, a BCC phase and FCC (fluid catalytic cracking) dual-phase structure which are rich in Cr and Mn elements are obtained, the content of the BCC phase is 14.5 percent, the Vickers hardness of the high-entropy alloy is 550HV, the yield strength is 1850MPa, the plastic strain is 28 percent, and the corrosion current densities in 3.5 weight percent NaCl solution and 0.05MHCl are respectively 2.9 multiplied by 10-7A/cm2And 2.6X 10-6A/cm2The SEM picture, XRD picture and polarization curve picture of the high-entropy alloy are shown in figure 1, figure 2, figure 3 and figure 4.
Example 2:
the acid corrosion resistant high-entropy alloy with low Al content and high toughness matching is prepared by a powder metallurgy method, and the chemical composition of the alloy is Al4CoCrFeMnNi: weighing CoCrFeMnNi high-entropy alloy powder and metal Al powder prepared by an air atomization method according to the stoichiometric ratio of the molecular formula, specifically 500.0g of CoCrFeMnNi and 20g of Al powder, and placing the powder in a mixer for mixing for 2h to obtain uniformly mixed raw materials; the evenly mixed raw materials are put into a graphite die and are subjected to hot-pressing sintering under the vacuum condition, the sintering temperature is 1050 ℃, the heating rate is 12 ℃/min, the sintering pressure is 35MPa, the heat preservation time is 30min, the raw materials are cooled along with the furnace after the heat preservation is finished, a BCC phase and FCC (fluid catalytic cracking) dual-phase structure rich in Cr and Mn elements are obtained, the content of the BCC phase is 11.2 percent, the Vickers hardness of the high-entropy alloy is 530HV, the yield strength is 1500MPa, the plastic strain is 40 percent, and the corrosion current densities in 3.5 weight percent NaCl solution and 0.05MHCl are respectively 2.6 multiplied by 10-7A/cm2And 2.8X 10-6A/cm2The high entropy alloy of (2).
Example 3:
the acid corrosion resistant high-entropy alloy with low Al content and high toughness matching is prepared by a powder metallurgy method, and the chemical composition of the alloy is Al6CoCrFeMnNi: prepared by a gas atomization method according to the stoichiometric ratio of a molecular formulaThe CoCrFeMnNi high-entropy alloy powder and metal Al powder, specifically 500.0g of CoCrFeMnNi and 30g of Al powder, are placed in a mixer to be mixed for 5 hours to obtain uniformly mixed raw materials; the raw materials which are uniformly mixed are put into a graphite die and are subjected to hot-pressing sintering under the vacuum condition, the sintering temperature is 1000 ℃, the heating rate is 15 ℃/min, the sintering pressure is 45MPa, the heat preservation time is 40min, the raw materials are cooled along with the furnace after the heat preservation is finished, a BCC phase and FCC (fluid catalytic cracking) dual-phase structure which are rich in Cr and Mn elements are obtained, the content of the BCC phase is 16.2 percent, the Vickers hardness of the high-entropy alloy is 570HV, the yield strength is 1750MPa, the plastic strain is 15 percent, and the corrosion current densities in 3.5 weight percent NaCl solution and 0.05MHCl are respectively 2.6 multiplied by 10-7A/cm2And 2.4X 10-6A/cm2The high entropy alloy of (2).
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. The high-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance is characterized in that the chemical composition of the high-entropy alloy is AlxThe material is CoCrFeMnNi, wherein x is the mass ratio of Al element, and the value range is 4.5-5.5%; the high-entropy alloy has FCC and BCC dual-phase structures, the BCC phase is rich in Cr and Mn elements, and the volume ratio of the BCC phase is 11.2-16.2%;
the preparation method of the high-entropy alloy comprises the following steps:
1) accurately weighing commercial CoCrFeMnNi high-entropy alloy powder, and then carrying out Al treatment according to the molecular formulaxWeighing commercially available metal Al powder with corresponding mass by using CoCrFeMnNi, and uniformly mixing the two raw materials by using a mixer at room temperature; the purity of the commercial CoCrFeMnNi high-entropy alloy powder is more than or equal to 99.5 percent, the grain diameter is less than or equal to 60 mu m, and the commercial CoCrFeMnNi high-entropy alloy powder is prepared by a gas atomization method; the purity of the commercially available metal Al powder is more than or equal to 99.5Percent, average grain diameter is 30-45 μm;
2) and (2) putting the uniformly mixed raw materials into a graphite die, carrying out hot-pressing sintering under a vacuum condition, wherein the sintering temperature is 1000-1100 ℃, the heating rate is 10-15 ℃/min, the sintering pressure is 35-45 MPa, the heat preservation time is 30-60 min, and cooling along with a furnace after the heat preservation is finished to obtain the high-entropy alloy which has low Al content, controllable BCC phase, FCC and BCC dual-phase structures, high strength and toughness matching and acid corrosion resistance.
2. The low Al content, high toughness, acid corrosion resistant high entropy alloy of claim 1, wherein in step 2), the sintering temperature is 1050 ℃ and the temperature rise rate is 12 ℃/min.
3. The low Al content, high toughness, acid corrosion resistant high entropy alloy of claim 1, wherein in step 2), the sintering pressure is 35MPa and the holding time is 30 min.
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| CN115740502A (en) * | 2022-12-27 | 2023-03-07 | 山东大学 | Method for preparing BCC and FCC two-phase FeCoCrNi series high-entropy alloy with low aluminum content |
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