CN117004893B - High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof - Google Patents
High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof Download PDFInfo
- Publication number
- CN117004893B CN117004893B CN202311287988.XA CN202311287988A CN117004893B CN 117004893 B CN117004893 B CN 117004893B CN 202311287988 A CN202311287988 A CN 202311287988A CN 117004893 B CN117004893 B CN 117004893B
- Authority
- CN
- China
- Prior art keywords
- strength
- cocrni
- toughness
- entropy alloy
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 124
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 63
- 238000005096 rolling process Methods 0.000 claims abstract description 60
- 238000005098 hot rolling Methods 0.000 claims abstract description 27
- 238000010791 quenching Methods 0.000 claims description 27
- 230000000171 quenching effect Effects 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 239000011258 core-shell material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000203 mixture Substances 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention belongs to the technical field of heat treatment of metal materials, and relates to a high-strength and high-toughness CoCrNi-based medium-entropy alloy and a preparation method thereof, wherein a short-period thermal coupling process of homogenizing annealing, pre-heating rolling, hot rolling and flash annealing is adopted, so that the production period is greatly shortened, the prepared high-strength and high-toughness CoCrNi-based medium-entropy alloy has yield strength exceeding 1.1GPa grade and elongation after breaking of 22-35%, the bottleneck problems of insufficient strength and excessive plasticity of the series alloy are broken, the loaded service capability of the series alloy is improved, the engineering application range of the series alloy is widened, the production energy consumption and economic cost are reduced, the existing industrial production conditions and technical standards are easily matched, and the industrial production process is effectively promoted.
Description
Technical Field
The invention relates to the technical field of heat treatment of metal materials, in particular to a high-strength and high-toughness CoCrNi-based medium-entropy alloy and a preparation method thereof.
Background
The medium-entropy alloy is derived from the concept of high-entropy alloy, and a large number of researches show that the alloy performance can be further optimized by properly reducing the types of main elements on the basis of the composition of the high-entropy alloy. The CoCrNi-based medium-entropy alloy is taken as a classical model, has excellent performances of corrosion resistance, high/low temperature resistance, radiation resistance and the like, is hopeful to be developed into various extreme environment service materials such as deep sea, south-north pole, outer space and the like, and has profound strategic values. However, similar to the conventional face-centered cubic structural alloy, the problem of insufficient strength and excessive plasticity severely restricts the engineering applicability. Based on the above, how to greatly improve the strength on the basis of moderately sacrificing the plasticity and realize good matching with high strength and toughness is a key problem to be solved by the medium-entropy alloy.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a high-strength and high-toughness CoCrNi-based medium-entropy alloy and a preparation method thereof.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
a preparation method of high-strength and high-toughness CoCrNi-based medium-entropy alloy comprises the steps that a matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is in a face-centered cubic structure, a grain structure is in a heterogeneous type partial recrystallization state, and a precipitated phase comprises L1 2 Ordered phases and MC, M 23 C 6 Carbide; the method comprises the following steps:
s1, homogenizing annealing
Carrying out homogenizing annealing on the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1100-1200 ℃ and the annealing time is 4-8 hours;
s2, pre-temperature rolling
Performing pre-temperature rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 10-20%;
s3, hot rolling
Hot rolling the warm rolled material to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 40-60%;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a furnace-entering mode, wherein the flash annealing temperature is 900-950 ℃, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium-entropy alloy.
As a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: the CoCrNi-based medium-entropy alloy comprises the following components in percentage by atom:
Co：29~31.3%，Cr：29~31.3%，Ni：29~31.3%，Al：3~6%，Ti：3~6%，C：0.1~1%。
as a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: the step S1 is preceded by the further step of,
s0, smelting alloy cast ingot
And (3) proportioning according to alloy components, sequentially placing the alloy components into a vacuum induction melting furnace chamber from bottom to top in the order of low melting point, wherein the melting temperature is 1400-1500 ℃, casting into alloy ingots in a vacuum chamber after melting, and cooling to room temperature along with the furnace.
As a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: in the step S1, the cooling mode is water quenching.
As a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: in the step S2, the pre-temperature rolling is divided into 1-2 passes; the initial rolling temperature is 550-600 ℃, and the final rolling temperature is 500-550 ℃.
As a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: in the step S3, hot rolling is divided into 1-3 passes, the initial rolling temperature is 1100-1150 ℃, and the final rolling temperature is 1000-1050 ℃.
As a preferable scheme of the preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: in the step S4, the flash annealing time is 3-10 min.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
the high-strength and high-toughness CoCrNi-based entropy alloy is prepared by adopting the preparation method of the high-strength and high-toughness CoCrNi-based entropy alloy.
As a preferable scheme of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: the yield strength of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is 1100-1400 MPa, the tensile strength is 1300-1500 MPa, and the elongation after fracture is 22-35%.
As a preferable scheme of the high-strength and high-toughness CoCrNi-based medium-entropy alloy, the invention comprises the following steps: the matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is in a face-centered cubic structure, the grain structure is in a heterogeneous partial recrystallization state, and the precipitated phase comprises L1 2 Ordered phases and MC, M 23 C 6 Carbide;
part of MC, M in the precipitated phase 23 C 6 The carbide is a core-shell cladding type assembly, the MC type carbide is taken as a core, M 23 C 6 The mold carbide is the shell.
The beneficial effects of the invention are as follows:
the invention provides a high-strength and high-toughness CoCrNi-based medium-entropy alloy and a preparation method thereof, wherein a short-period thermal coupling process of homogenizing annealing, pre-temperature rolling, hot rolling and flash annealing is adopted, so that the production period is greatly shortened, the prepared high-strength and high-toughness CoCrNi-based medium-entropy alloy has the yield strength exceeding 1.1GPa grade and the elongation after breaking of 22-35%, the bottleneck problems of insufficient strength and excessive plasticity of the series of alloy are broken through, the loaded service capacity of the series of alloy is improved, the engineering application range of the series of alloy is widened, the production energy consumption and the economic cost are reduced, the existing industrial production conditions and the existing technical standards are easily matched, and the industrial production process is effectively promoted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a high strength and toughness CoCrNi-based medium entropy alloy prepared according to example 1 of the present invention;
FIG. 2 is a graph showing the mechanical properties of high strength and toughness CoCrNi-based medium entropy alloys prepared in examples and comparative examples of the present invention.
Wherein, 1- "core-shell cladding" MC, M 23 C 6 Carbide composite, 2-MC carbide, 3-M 23 C 6 A type carbide.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments 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.
The invention mainly aims to provide a high-strength and high-toughness CoCrNi-based entropy alloy and a preparation method thereof, wherein strength and toughness are one of the most important research directions in the field of metal materials, and related method exploration and mechanism research are scientific bases for advanced metal material development. From the perspective of microstructure design, the usual toughening means mainly relate to grain structure control, precipitated phase regulation and control, dislocation engineering and the like. However, the evolution of the microstructure is synergistically affected by numerous factors, and it is difficult to achieve synchronous construction of a multi-dimensional target microstructure by a simple process. In addition, medium/high entropy alloys exhibit a unique "slow diffusion effect". The two factors lead to that the medium-high entropy alloy adopts a long period step-by-step regulation strategy, such as heat/cold deformation and long period annealing treatment to realize grain structure regulation, and then long period aging treatment is carried out to regulate and control precipitated phases. The complex process design reduces the production efficiency, causes excessive waste of resources and cost, and seriously hinders the industrial production process. Based on the method, a short-period high-efficiency thermodynamic coupling process is developed, multi-dimensional thermal/dynamic factor synchronous excitation is induced, multi-dimensional target microstructure cooperative construction is realized, and the high-strength and high-toughness CoCrNi-based medium-entropy alloy is prepared, so that the method has important significance.
According to one aspect of the invention, the invention provides the following technical scheme:
a preparation method of high-strength and high-toughness CoCrNi-based medium-entropy alloy comprises the steps that a matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is in a face-centered cubic structure, a grain structure is in a heterogeneous type partial recrystallization state, and a precipitated phase comprises L1 2 Ordered phases and MC, M 23 C 6 Carbide; the method comprises the following steps:
s1, homogenizing annealing
Carrying out homogenizing annealing on the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1100-1200 ℃ and the annealing time is 4-8 hours;
s2, pre-temperature rolling
Performing pre-temperature rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 10-20%;
s3, hot rolling
Hot rolling the warm rolled material to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 40-60%;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a furnace-entering mode, wherein the flash annealing temperature is 900-950 ℃, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium-entropy alloy.
Preferably, the entropy alloy in the CoCrNi base comprises the following components in atom percent:
Co：29~31.3%，Cr：29~31.3%，Ni：29~31.3%，Al：3~6%，Ti：3~6%，C：0.1~1%。
preferably, the step S1 further comprises,
s0, smelting alloy cast ingot
And (3) proportioning according to alloy components, sequentially placing the alloy components into a vacuum induction melting furnace chamber from bottom to top in the order of low melting point, wherein the melting temperature is 1400-1500 ℃, casting into alloy ingots in a vacuum chamber after melting, and cooling to room temperature along with the furnace. In particular, the smelting temperature may be, for example, but not limited to, any one or a range between any two of 1400 ℃, 1410 ℃, 1420 ℃, 1430 ℃, 1440 ℃, 1450 ℃, 1460 ℃, 1470 ℃, 1480 ℃, 1490 ℃, 1500 ℃;
preferably, in the step S1, the cooling mode is water quenching. Specifically, the annealing temperature may be, for example, but not limited to, any one or a range between any two of 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃, 1200 ℃; the annealing time may be, for example, but not limited to, any one or a range between any two of 4h, 5h, 6h, 7h, 8h;
preferably, in the step S2, the pre-warm rolling is divided into 1-2 passes; the initial rolling temperature is 550-600 ℃, and the final rolling temperature is 500-550 ℃. Specifically, the total deformation of the pre-warm rolling may be, for example, but not limited to, a range between any one or any two of 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%; the start rolling temperature may be, for example, but not limited to, any one or a range between any two of 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃; the finishing temperature may be, for example, but not limited to, any one or a range between any two of 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃.
Preferably, in the step S3, the hot rolling is divided into 1 to 3 passes, the initial rolling temperature is 1100 to 1150 ℃, and the final rolling temperature is 1000 to 1050 ℃. Specifically, the total deformation of the hot rolling may be, for example, but not limited to, any one of 40%, 45%, 50%, 55%, 60% or a range between any two thereof; the start rolling temperature may be, for example, but not limited to, any one or a range between any two of 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃; the finishing temperature may be, for example, but not limited to, any one or a range between any two of 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃.
Preferably, in the step S4, the flash annealing time is 3-10 min. Specifically, the flash annealing temperature may be, for example, but not limited to, any one or a range between any two of 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃; the flash annealing time may be, for example, but not limited to, any one or a range between any two of 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min.
According to another aspect of the invention, the invention provides the following technical scheme:
the high-strength and high-toughness CoCrNi-based entropy alloy is prepared by adopting the preparation method of the high-strength and high-toughness CoCrNi-based entropy alloy.
Preferably, the high-strength and high-toughness CoCrNi-based medium-entropy alloy has the yield strength of 1100-1400 MPa, the tensile strength of 1300-1500 MPa and the elongation after fracture of 22-35%.
Preferably, the matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is in a face-centered stateSquare structure, heterogeneous partial recrystallization of grain structure, precipitated phase containing L1 2 Ordered phases and MC, M 23 C 6 Carbide;
part of MC, M in the precipitated phase 23 C 6 The carbide is a core-shell cladding type assembly, the MC type carbide is taken as a core, M 23 C 6 The mold carbide is the shell.
The technical scheme of the invention is further described below by combining specific embodiments.
The CoCrNi-based medium entropy alloy used in each example was prepared as follows:
and (3) mixing materials according to alloy components, sequentially placing the materials into a vacuum induction smelting furnace chamber from bottom to top according to the sequence of low melting point, smelting at 1450 ℃, casting into alloy ingots in a vacuum chamber after smelting, and cooling to room temperature along with the furnace. The chemical composition of the alloy ingot is shown in table 1.
Table 1 chemical composition (atomic percent) of alloy ingots of CoCrNi-based medium entropy alloys of various examples
Example 1
The embodiment provides a preparation method of a high-strength and high-toughness CoCrNi-based medium-entropy alloy, which comprises the following steps:
s1, homogenizing annealing
Homogenizing annealing the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1200 ℃, the annealing time is 8 hours, and the cooling mode is water quenching;
s2, pre-temperature rolling
Performing 2-pass pre-warm rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 20%, the initial rolling temperature is 600 ℃, and the final rolling temperature is 550 ℃;
s3, hot rolling
Wen Gacai carrying out 3-pass hot rolling to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 60%, the initial rolling temperature is 1100 ℃, and the final rolling temperature is 1050 ℃;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a mode of entering a furnace at the temperature of 900 ℃ for 3min, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium entropy alloy.
The SEM diagram of the high-strength and high-toughness CoCrNi-based medium entropy alloy prepared in the embodiment is shown in figure 1, the matrix of the high-strength and high-toughness CoCrNi-based medium entropy alloy is in FCC single phase, the grain structure is in heterogeneous partial recrystallization state, the high-density dislocation is contained, and the precipitated phase contains L1 2 Ordered phases and MC, M 23 C 6 Carbide, MC, M 23 C 6 The carbide comprises core-shell coated MC, M 23 C 6 Carbide composite 1, MC-type carbide 2, M 23 C 6 The mechanical properties of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared by the embodiment of the carbide 3 are shown in figure 2: the yield strength is 1370MPa, the tensile strength is 1494MPa, and the elongation after breaking is 22%.
Example 2
The embodiment provides a preparation method of a high-strength and high-toughness CoCrNi-based medium-entropy alloy, which comprises the following steps:
s1, homogenizing annealing
Homogenizing annealing the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1200 ℃, the annealing time is 8 hours, and the cooling mode is water quenching;
s2, pre-temperature rolling
Performing 2-pass pre-warm rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 20%, the initial rolling temperature is 600 ℃, and the final rolling temperature is 550 ℃;
s3, hot rolling
Wen Gacai carrying out 3-pass hot rolling to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 60%, the initial rolling temperature is 1100 ℃, and the final rolling temperature is 1050 ℃;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a mode of entering a furnace at the temperature of 900 ℃ for 10min, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium entropy alloy.
The matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared by the embodiment is FCC single phase, the grain structure is heterogeneous part recrystallized, the high-density dislocation is contained, and the precipitated phase contains L1 2 Ordered phases and MC, M 23 C 6 Carbide, part MC, M 23 C 6 The carbide is core-shell coated MC, M 23 C 6 The mechanical properties of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared in the embodiment of the carbide composition are shown in figure 2: the yield strength is 1275MPa, the tensile strength is 1434MPa, and the elongation after breaking is 27%.
Example 3
The embodiment provides a preparation method of a high-strength and high-toughness CoCrNi-based medium-entropy alloy, which comprises the following steps:
s1, homogenizing annealing
Homogenizing annealing the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1200 ℃, the annealing time is 8 hours, and the cooling mode is water quenching;
s2, pre-temperature rolling
Performing 2-pass pre-warm rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 20%, the initial rolling temperature is 600 ℃, and the final rolling temperature is 550 ℃;
s3, hot rolling
Wen Gacai carrying out 3-pass hot rolling to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 60%, the initial rolling temperature is 1100 ℃, and the final rolling temperature is 1050 ℃;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a mode of entering a furnace at the temperature of 950 ℃ for 3min, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium entropy alloy.
The matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared by the embodiment is FCC single phase, the grain structure is heterogeneous part and recrystallized, the matrix contains low-density dislocation, and the precipitated phase contains L1 2 Ordered phases and MC, M 23 C 6 Carbide, part MC, M 23 C 6 Carbonization ofThe object is core-shell coated MC, M 23 C 6 The mechanical properties of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared in the embodiment of the carbide composition are shown in figure 2: the yield strength is 1152MPa, the tensile strength is 1324MPa, and the elongation after breaking is 31%.
Example 4
The embodiment provides a preparation method of a high-strength and high-toughness CoCrNi-based medium-entropy alloy, which comprises the following steps:
s1, homogenizing annealing
Homogenizing annealing the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1200 ℃, the annealing time is 8 hours, and the cooling mode is water quenching;
s2, pre-temperature rolling
Performing 2-pass pre-warm rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 20%, the initial rolling temperature is 600 ℃, and the final rolling temperature is 550 ℃;
s3, hot rolling
Wen Gacai carrying out 3-pass hot rolling to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 60%, the initial rolling temperature is 1100 ℃, and the final rolling temperature is 1050 ℃;
s4, flash annealing:
and (3) performing flash annealing on the hot rolled plate in a mode of entering a furnace at the temperature of 950 ℃ for 10min, and then performing water quenching to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium entropy alloy.
The matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared by the embodiment is FCC single phase, the grain structure is heterogeneous part recrystallized, the high-density dislocation is contained, and the precipitated phase contains L1 2 Ordered phases and MC, M 23 C 6 Carbide, part MC, M 23 C 6 The carbide is core-shell coated MC, M 23 C 6 The mechanical properties of the high-strength and high-toughness CoCrNi-based medium-entropy alloy prepared in the embodiment of the carbide composition are shown in figure 2: the yield strength is 1102MPa, the tensile strength is 1305MPa, and the elongation after breaking is 32%.
Comparative example 1
This comparative example provides a method for preparing a CoCrNi-based medium entropy alloy, which is different from example 1 in that,
step S4 is not performed.
The entropy alloy matrix of the CoCrNi base prepared in the comparative example is FCC single phase, the grain structure is elongated along the rolling direction, the alloy matrix contains ultra-high density dislocation, and the precipitated phase mainly comprises a small amount of MC type carbide and MC and M in a 'core-shell cladding' shape 23 C 6 The mechanical properties of the CoCrNi-based medium entropy alloy prepared in this comparative example are shown in FIG. 2: the yield strength is 1345MPa, the tensile strength is 1494MPa, and the elongation after breaking is 14%.
Comparative example 2
This comparative example provides a method for preparing a CoCrNi-based medium entropy alloy, which is different from example 1 in that,
in step S4, the flash annealing temperature is 850 ℃, and the flash annealing time is 3min.
The entropy alloy matrix of the CoCrNi base prepared in the comparative example is FCC single phase, the grain structure is elongated along the rolling direction, the alloy matrix contains high-density dislocation, and the precipitated phase mainly comprises a small amount of MC type carbide and M 23 C 6 Carbide, "core-shell coated" MC, M 23 C 6 The mechanical properties of the CoCrNi-based medium entropy alloy prepared in this comparative example are shown in FIG. 2: the yield strength is 1338MPa, the tensile strength is 1464MPa, and the elongation after breaking is 17%.
Comparative example 3
This comparative example provides a method for preparing a CoCrNi-based medium entropy alloy, which is different from example 1 in that,
in step S4, the flash annealing temperature is 1000 ℃ and the flash annealing time is 3min.
The entropy alloy matrix in the CoCrNi base prepared by the comparative example is FCC single phase, the grain structure is uniform and completely recrystallized, the crystal phase contains ultra-low density dislocation, the precipitated phase mainly contains a small amount of MC type carbide, the mechanical properties of the entropy alloy in the CoCrNi base prepared by the comparative example are shown as figure 2 (the small right-lower corner graph in figure 2 is the continuation of the mechanical properties of comparative example 3 in figure 2 along the abscissa): the yield strength is 342MPa, the tensile strength is 814MPa, and the elongation after breaking is 81%.
Comparative example 4
This comparative example provides a method for preparing a CoCrNi-based medium entropy alloy, which is different from example 1 in that,
step S3 is not performed.
The entropy alloy matrix of the CoCrNi base prepared in the comparative example is FCC single phase, the grain structure is partially recrystallized, the alloy matrix contains low-density dislocation, and the precipitated phase contains a large amount of M 23 C 6 Carbide and "core-shell coated" MC, M 23 C 6 The mechanical properties of the CoCrNi-based medium entropy alloy prepared in this comparative example are shown in FIG. 2: the yield strength is 1196MPa, the tensile strength is 1366MPa, and the elongation after breaking is 20%.
According to the invention, the grain structure, dislocation and precipitated phase can be reasonably regulated and controlled by the process, the multidimensional synergistic microstructure configuration is obtained, and good strong plastic matching is realized. The invention adopts a short-period thermal coupling process of homogenizing annealing, pre-temperature rolling, hot rolling and flash annealing, greatly shortens the production period, ensures that the prepared high-strength and high-toughness CoCrNi-based medium-entropy alloy has yield strength exceeding 1.1GPa grade and elongation after breaking of 22-35%, breaks through the bottleneck problems of insufficient strength and excessive plasticity of the series of alloy, improves the loading service capability of the series of alloy, widens the engineering application range of the series of alloy, reduces the production energy consumption and economic cost, is easy to match the existing industrial production conditions and process technical standards, and effectively promotes the industrial production process.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. The preparation method of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is characterized by comprising the following steps of: co:2931.3%, cr: 29-31.3%, ni: 29-31.3%, al: 3-6%, ti: 3-6%, C: 0.1-1%; the matrix of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is in a face-centered cubic structure, the grain structure is in a heterogeneous partial recrystallization state, and the precipitated phase comprises L1 2 Ordered phases and MC, M 23 C 6 Carbide; the method comprises the following steps:
s1, homogenizing annealing
Carrying out homogenizing annealing on the alloy ingot to obtain an annealed ingot, wherein the annealing temperature is 1100-1200 ℃ and the annealing time is 4-8 hours;
s2, pre-temperature rolling
Performing pre-temperature rolling on the annealed ingot to obtain Wen Gacai, and then performing water quenching to room temperature; the total deformation of the pre-warm rolling is 10-20%;
s3, hot rolling
Hot rolling the warm rolled material to obtain a hot rolled material, and then quenching the hot rolled material with water to room temperature; the total deformation of the hot rolling is 40-60%;
s4, flash annealing:
performing flash annealing on the hot rolled plate in a furnace-entering mode, wherein the flash annealing temperature is 900-950 ℃, the flash annealing time is 3-10 min, and then water quenching is performed to room temperature to obtain the high-strength and high-toughness CoCrNi-based medium-entropy alloy;
the yield strength of the high-strength and high-toughness CoCrNi-based medium-entropy alloy is 1100-1400 MPa, the tensile strength is 1300-1500 MPa, and the elongation after fracture is 22-35%.
2. The method for preparing a high strength and toughness CoCrNi-based medium entropy alloy according to claim 1, wherein the step S1 is preceded by the steps of,
s0, smelting alloy cast ingot
And (3) proportioning according to alloy components, sequentially placing the alloy components into a vacuum induction melting furnace chamber from bottom to top in the order of low melting point, wherein the melting temperature is 1400-1500 ℃, casting into alloy ingots in a vacuum chamber after melting, and cooling to room temperature along with the furnace.
3. The method for preparing a high-strength and high-toughness CoCrNi-based medium-entropy alloy according to claim 1, wherein in the step S2, the pre-warm rolling is divided into 1-2 passes.
4. The method for preparing a high strength and toughness CoCrNi-based medium entropy alloy according to claim 1, wherein in the step S2, the initial rolling temperature is 550-600 ℃ and the final rolling temperature is 500-550 ℃.
5. The method for preparing a high strength and toughness CoCrNi-based medium entropy alloy according to claim 1, wherein in the step S3, the initial rolling temperature is 1100-1150 ℃ and the final rolling temperature is 1000-1050 ℃.
6. The high-strength and high-toughness CoCrNi-based entropy alloy is characterized by being prepared by adopting the preparation method of the high-strength and high-toughness CoCrNi-based entropy alloy as claimed in any one of claims 1 to 5.
7. The high strength and toughness CoCrNi-based isentropic alloy according to claim 6, wherein the matrix of the high strength and toughness CoCrNi-based isentropic alloy is of face-centered cubic structure, the grain structure is heterogeneous, the grain structure is recrystallized, and the precipitated phase comprises L1 2 Ordered phases and MC, M 23 C 6 Carbide;
part of MC, M in the precipitated phase 23 C 6 The carbide is a core-shell cladding type assembly, the MC type carbide is taken as a core, M 23 C 6 The mold carbide is the shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311287988.XA CN117004893B (en) | 2023-10-08 | 2023-10-08 | High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311287988.XA CN117004893B (en) | 2023-10-08 | 2023-10-08 | High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117004893A CN117004893A (en) | 2023-11-07 |
| CN117004893B true CN117004893B (en) | 2023-12-22 |
Family
ID=88574750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311287988.XA Active CN117004893B (en) | 2023-10-08 | 2023-10-08 | High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117004893B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5195917A (en) * | 1974-12-27 | 1976-08-23 | ONKANOYOBINETSUKANKAKOYOKOGUKO | |
| CN110157970A (en) * | 2019-06-11 | 2019-08-23 | 沈阳航空航天大学 | A kind of high strength and ductility CoCrNi medium entropy alloy and preparation method thereof |
| WO2020085697A1 (en) * | 2018-10-24 | 2020-04-30 | 포항공과대학교 산학협력단 | Medium-entropy alloy having high strength and high toughness, and manufacturing method therefor |
| CN111961918A (en) * | 2020-07-29 | 2020-11-20 | 东北大学 | NiMnCu medium-entropy alloy and preparation method thereof |
| CN112853237A (en) * | 2021-01-05 | 2021-05-28 | 中北大学 | Preparation method of high-yield-strength CoCrNi-based medium-entropy alloy |
| CN113444958A (en) * | 2021-06-28 | 2021-09-28 | 威海蓝谷材料分析研究院有限公司 | High-strength high-toughness lamellar isomeric medium-entropy alloy and preparation method thereof |
| CN113737078A (en) * | 2021-08-27 | 2021-12-03 | 西安交通大学 | High-strength and high-plasticity multi-stage heterostructure medium-entropy alloy and preparation method thereof |
| CN114086049A (en) * | 2021-11-17 | 2022-02-25 | 沈阳航空航天大学 | 2.0GPa grade CoCrNi-based medium entropy alloy with ultrahigh yield strength and plasticity and preparation method thereof |
| WO2022041693A1 (en) * | 2020-08-31 | 2022-03-03 | 华东理工大学 | Tic strengthened cocrni medium-entropy alloy composite material and preparation method therefor |
| CN114395714A (en) * | 2021-12-20 | 2022-04-26 | 东北大学 | Ultrahigh-strength Co-based medium-entropy alloy and preparation method thereof |
| CN114427060A (en) * | 2022-01-28 | 2022-05-03 | 临清市同兴轴承锻造有限公司 | Fe reinforced by TiC dispersed phase50Mn25Ni10Cr15Method for medium entropy alloying |
| CN114606423A (en) * | 2022-03-27 | 2022-06-10 | 西北工业大学 | Low-temperature-wear-resistant medium-entropy alloy and preparation method thereof |
| CN115198162A (en) * | 2022-09-19 | 2022-10-18 | 太原理工大学 | Entropy alloy in high-toughness heterogeneous multi-phase core-shell organization structure and preparation method thereof |
| CN115233077A (en) * | 2022-09-19 | 2022-10-25 | 太原理工大学 | CoCrNi-based medium entropy alloy with high aluminum content and high titanium content and strengthened nano coherent precipitation and preparation method thereof |
| CN116676521A (en) * | 2023-05-15 | 2023-09-01 | 西安交通大学 | CrCoNi-based medium entropy alloy with heterogeneous grain heterostructure and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200109467A1 (en) * | 2018-10-04 | 2020-04-09 | City University Of Hong Kong | High entropy alloy structure and a method of preparing the same |
-
2023
- 2023-10-08 CN CN202311287988.XA patent/CN117004893B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5195917A (en) * | 1974-12-27 | 1976-08-23 | ONKANOYOBINETSUKANKAKOYOKOGUKO | |
| WO2020085697A1 (en) * | 2018-10-24 | 2020-04-30 | 포항공과대학교 산학협력단 | Medium-entropy alloy having high strength and high toughness, and manufacturing method therefor |
| CN110157970A (en) * | 2019-06-11 | 2019-08-23 | 沈阳航空航天大学 | A kind of high strength and ductility CoCrNi medium entropy alloy and preparation method thereof |
| CN111961918A (en) * | 2020-07-29 | 2020-11-20 | 东北大学 | NiMnCu medium-entropy alloy and preparation method thereof |
| WO2022041693A1 (en) * | 2020-08-31 | 2022-03-03 | 华东理工大学 | Tic strengthened cocrni medium-entropy alloy composite material and preparation method therefor |
| CN112853237A (en) * | 2021-01-05 | 2021-05-28 | 中北大学 | Preparation method of high-yield-strength CoCrNi-based medium-entropy alloy |
| CN113444958A (en) * | 2021-06-28 | 2021-09-28 | 威海蓝谷材料分析研究院有限公司 | High-strength high-toughness lamellar isomeric medium-entropy alloy and preparation method thereof |
| CN113737078A (en) * | 2021-08-27 | 2021-12-03 | 西安交通大学 | High-strength and high-plasticity multi-stage heterostructure medium-entropy alloy and preparation method thereof |
| CN114086049A (en) * | 2021-11-17 | 2022-02-25 | 沈阳航空航天大学 | 2.0GPa grade CoCrNi-based medium entropy alloy with ultrahigh yield strength and plasticity and preparation method thereof |
| CN114395714A (en) * | 2021-12-20 | 2022-04-26 | 东北大学 | Ultrahigh-strength Co-based medium-entropy alloy and preparation method thereof |
| CN114427060A (en) * | 2022-01-28 | 2022-05-03 | 临清市同兴轴承锻造有限公司 | Fe reinforced by TiC dispersed phase50Mn25Ni10Cr15Method for medium entropy alloying |
| CN114606423A (en) * | 2022-03-27 | 2022-06-10 | 西北工业大学 | Low-temperature-wear-resistant medium-entropy alloy and preparation method thereof |
| CN115198162A (en) * | 2022-09-19 | 2022-10-18 | 太原理工大学 | Entropy alloy in high-toughness heterogeneous multi-phase core-shell organization structure and preparation method thereof |
| CN115233077A (en) * | 2022-09-19 | 2022-10-25 | 太原理工大学 | CoCrNi-based medium entropy alloy with high aluminum content and high titanium content and strengthened nano coherent precipitation and preparation method thereof |
| CN116676521A (en) * | 2023-05-15 | 2023-09-01 | 西安交通大学 | CrCoNi-based medium entropy alloy with heterogeneous grain heterostructure and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Influence of annealing temperatures on the microstructure and deformation behavior of a CrCoNi based medium-entropy alloy;Liu Qiancheng;《Journal of Alloys and Compounds》(第960期);1-12 * |
| 退火和退火-时效工艺对热轧中锰钢组织及性能的影响;白韶斌;《金属热处理》;第47卷(第1期);245-249 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117004893A (en) | 2023-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103556020B (en) | There is the high Mn content high-damping mn-cu-based alloy of excellent mechanical property | |
| CN108546812A (en) | A kind of preparation method of high-strength medium managese steel plate | |
| CN106191661B (en) | A kind of manufacture method of the tough Thin Specs 9Ni steel plates of high strength and low cost | |
| CN108486492B (en) | 1200 MPa-grade high-strength high-plasticity low-density steel plate and manufacturing method thereof | |
| CN104928456B (en) | A kind of manufacture method for improving general chill ferritic lightweight steel ductility | |
| CN109440014B (en) | Low-chromium low-nickel duplex stainless steel and preparation method thereof | |
| CN103469089A (en) | Cake-shaped crystal grain deep-draw double-phase steel plate and preparation method thereof | |
| JP2024504210A (en) | High entropy austenitic stainless steel and its manufacturing method | |
| CN111187977B (en) | 690 MPa-grade anti-seismic, corrosion-resistant and fire-resistant medium-thickness plate steel and manufacturing method thereof | |
| CN108624820B (en) | Automobile high-strength ductile steel with strength-elongation product of more than 45 GPa% and preparation method thereof | |
| CN117004893B (en) | High-strength and high-toughness CoCrNi-based medium-entropy alloy and preparation method thereof | |
| CN102162073A (en) | Preparation method of low-carbon low-silicon cold-rolled hot-galvanized dual-phase steel for extra-deep drawing | |
| CN109593927A (en) | A method of pure iron is orientated using double annealing production crystal grain | |
| CN103805909A (en) | Preparation method of austenitic hot-work die steel | |
| CN108866435B (en) | A kind of automobile combined microalloying medium managese steel and its manufacturing method | |
| CN107502818B (en) | A kind of high intensity low density is anti-corrosion extraordinary forging steel and preparation method thereof | |
| CN115652235A (en) | GH4151 alloy fine-grain bar and preparation method and application thereof | |
| CN109371301A (en) | A kind of room temperature high plastic magnesium alloy and preparation method thereof | |
| CN112342352B (en) | Corrosion-resistant high-manganese austenitic steel plate and preparation method thereof | |
| CN114717460A (en) | High-strength iron-cobalt soft magnetic alloy strip and preparation method thereof | |
| CN117512463B (en) | Medium manganese steel and preparation method thereof | |
| CN114540721B (en) | Ferritic stainless steel and preparation method and application thereof | |
| CN115478209B (en) | Hot-rolled pickled enamel steel with good drawing performance and production method thereof | |
| CN115161548B (en) | Ti-Zr composite microalloyed 700 MPa-grade high-strength and high-toughness steel plate and preparation method thereof | |
| CN113814269B (en) | Rolling process for refining M-A component in low-carbon bainite steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |