CN115821171B - Trace B element doped modified high-strength high-plasticity multicomponent alloy, and preparation method and application thereof - Google Patents
Trace B element doped modified high-strength high-plasticity multicomponent alloy, and preparation method and application thereof Download PDFInfo
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- 238000003723 Smelting Methods 0.000 claims description 12
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Abstract
The invention provides a trace B element doped modified high-strength high-plasticity multicomponent alloy, a preparation method and application thereof, wherein the multicomponent alloy has a general formula of Fe a Ni b Cr c Cu d Al e Ti f -gB, wherein a, b, c, d, e, f is molar ratio, g is mass fraction, 1.8.ltoreq.a.ltoreq.2.2, 0.8.ltoreq.b.ltoreq.1.2, 0.3.ltoreq.c.ltoreq.0.6, 0.1.ltoreq.d.ltoreq.0.4, 0.1.ltoreq.e.ltoreq.0.4, 0.1.ltoreq.f.ltoreq.0.3, 60 ppm.ltoreq.g.ltoreq.90 ppm. The multicomponent alloy provided by the invention is subjected to simple thermo-mechanical treatment after being doped with trace B elements, so that precipitation of coarse BCC-based Heusler phases at a grain boundary is inhibited, formation of fine BCC-based Heusler phases in the grain boundary is promoted, stress concentration is relieved, and the comprehensive mechanical properties of the alloy are greatly improved.
Description
Technical Field
The invention relates to a multi-component alloy technology, in particular to a trace B element doped modified high-strength high-plasticity multi-component alloy, a preparation method and application thereof.
Background
High-entropy alloys or multicomponent alloys are receiving extensive attention for their special physical, chemical and mechanical properties and are becoming hot spots for metal alloy research in the hope of becoming a future structural function integrated material. Although it is composed of 4 and more principal elements, a single-phase disordered solid solution structure can be maintained in an as-cast state. Achieving both ultra-high strength and reliable ductility in a single face-centered, disordered solid solution structured multi-component alloy remains a challenge. In order for a single face-centered cubic structure multicomponent alloy to have excellent mechanical properties, a matrix phase with good toughness reinforcement is generally required. Among the various conventional strengthening strategies, precipitation strengthening plays a critical role, since the slow diffusion of elements in multicomponent alloys provides a unique opportunity for the formation of fine and stable nanoscale precipitate phases, increasing the strength of the alloy to new levels.
In general, the method of achieving this objective is focused only on adjusting the alloy composition and the thermo-mechanical processing conditions, which is both cumbersome and costly. In contrast, there is still a great challenge to how to design a simple and low cost method to optimize the microstructure to achieve the best balance of strength and ductility of the multi-component alloy.
Disclosure of Invention
Aiming at the problems that the design for improving the comprehensive mechanical property of the alloy is rarely reported and the like by adopting a very low-content doping agent to adjust the microstructure at present, the invention provides a trace B element-doped high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy and a preparation method thereof. In the B-free state, a large number of coarse BCC-based Heusler hard phases are precipitated at the alloy grain boundaries after the thermomechanical treatment, which severely impairs the plasticity of the alloy. Under the same thermo-mechanical treatment condition, the B element with extremely low content is doped to inhibit precipitation of coarse hard phases at the grain boundary, promote formation of fine BCC-based Heusler phases in the grain boundary, relieve stress concentration and greatly improve comprehensive mechanical properties of the alloy. The multi-component alloy of the system has the characteristic of excellent strong plastic balance, and is expected to be widely applied to industrial production.
In order to achieve the above purpose, the invention adopts the following technical scheme: a trace B element doped modified high-strength high-plasticity multi-component alloy has a general formula of Fe a Ni b Cr c Cu d Al e Ti f -gB, wherein a, b, c, d, e, f is molar ratio, g is mass fraction, 1.8.ltoreq.a.ltoreq.2.2, 0.8.ltoreq.b.ltoreq.1.2, 0.3.ltoreq.c.ltoreq.0.6, 0.1.ltoreq.d.ltoreq.0.4, 0.1.ltoreq.e.ltoreq.0.4, 0.1.ltoreq.f.ltoreq.0.3, 60 ppm.ltoreq.g.ltoreq.90 ppm.
Further, the general formula Fe a Ni b Cr c Cu d Al e Ti f -the gB multi-component alloy composition satisfies the following condition: a: b: d: f=20: 10:2:1, c: e=5: 3, and g is more than or equal to 60ppm and less than or equal to 90ppm.
Further, a is more than or equal to 1.9 and less than or equal to 2.1, b is more than or equal to 0.9 and less than or equal to 1.1, c is more than or equal to 0.4 and less than or equal to 0.5, d is more than or equal to 0.1 and less than or equal to 0.2, e is more than or equal to 0.3 and less than or equal to 0.4, f is more than or equal to 0.1 and less than or equal to 0.2, and g is more than or equal to 60ppm and less than or equal to 90ppm in the general formula.
The invention also discloses a preparation method of the trace B element doped modified high-strength high-plasticity multi-component alloy, which comprises the following steps:
stacking the simple substance raw materials Ni, cr, cu, al, ti and the Fe-B intermediate alloy according to the weight ratio, and smelting by adopting a vacuum arc smelting furnace to obtain a multi-component alloy button ingot; and placing the multi-component alloy button ingot into a vacuum heat treatment furnace, carrying out homogenization heat treatment, and then sequentially carrying out high-deformation cold rolling and high-temperature aging heat treatment to obtain the trace B element modified high-strength high-plasticity multi-component alloy.
Further, the purity of the selected elemental metal raw material Ni, cr, cu, al and Ti is 99.95wt.% or more; the purity of the selected Fe-B master alloy raw material is more than or equal to 99 wt%.
Further, when the alloy raw material is smelted, the Fe-B intermediate alloy raw material is placed at the lowest part of the copper crucible so as not to be blown off by a transient arc to influence the B content, and the metal simple substance raw material Ni, cr, cu, al and Ti are covered on the Fe-B intermediate alloy.
Further, the vacuum melting furnace is vacuumized to be 2.9x10 -3 ～3.2×10 -3 pa, and then reversely filling high-purity argon to-0.06 to-0.05 MPa.
Further, when the alloy button ingot is smelted, the current is added to 200-250A, the smelting time is 60-80 s, and the repeated smelting and overturning times are 5-6 times, so that the uniformity of the tissue structure is ensured.
Further, the selected equipment for the homogenization heat treatment, the cold rolling and the high-temperature aging heat treatment are a GSL tube heat treatment furnace, a two-roll cold rolling mill and an MITR desk box furnace respectively.
Further, the homogenizing heat treatment process comprises the following steps: homogenizing at 1100-1200 deg.c for 4-8 hr and water quenching; the cold rolling process comprises the following steps: 80-90% of large deformation; the high-temperature aging heat treatment process comprises the following steps: annealing temperature is 650-1100 ℃, aging time is 1-20 h, and water quenching is carried out.
Further, the tensile strength of the multicomponent alloy is greatly improved by simple thermo-mechanical treatment after doping trace B elements, and the fracture toughness is maintained at a higher level, and the multicomponent alloy is modified within the range of maintaining acceptable cost control, so that the balance of strength and plasticity is realized.
The invention also discloses the application of the trace B element doped modified high-strength high-plasticity multi-component alloy in the fields of hard cutter materials, tank armor, transformers, machine tools, jet aircraft engines, aircraft engine combined blades or engine shells.
Compared with the prior art, the trace B element doped modified high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy has the following advantages:
1. the multicomponent alloy of the invention inhibits the precipitation of coarse BCC-based Heusler phase at the grain boundary through the thermomechanical treatment in the prior art after being doped with trace B elements, promotes the formation of fine BCC-based Heusler phase in the grain boundary, reduces nucleation points of crack sources, thereby relieving stress concentration and realizing balance of strength and plasticity.
2. The multi-component alloy disclosed by the invention has excellent comprehensive mechanical properties, is more uniform in structure after being modified by doping trace B elements, has few casting defects, and greatly improves the problem that the multi-component alloy is difficult to cast and mold.
3. The trace B element doped modified high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy has the advantages of simple preparation process, easy acquisition of materials, and wide development prospect in industrial production of Fe-based multicomponent alloy by modifying within the range of keeping acceptable cost control.
4. The multi-component alloy has excellent mechanical properties in the B-free state, and the yield strength, the tensile strength and the elongation are 793.8MPa, 1153.1MPa and 25.2 percent respectively. After being modified by doping trace B elements, the yield strength and the tensile strength of the multi-component alloy are greatly improved, the yield strength and the tensile strength are respectively increased to 1153.1MPa and 1442.7MPa, and the elongation at break is still kept at a higher level of 21.3%.
Drawings
FIG. 1 shows the microstructure of the multicomponent alloy of example 1 and comparative example 1 of the present invention under the same thermo-mechanical treatment, wherein (a) is the B-free state of comparative example 1 and (B) is the B-state of example 1 containing 60 ppm;
FIG. 2 is an XRD pattern of the multicomponent alloy obtained in example 1 of the present invention and comparative example 1 under the same thermo-mechanical treatment state;
FIG. 3 is a drawing showing the tensile engineering stress-strain curves of the multicomponent alloy obtained in example 1 of the present invention and comparative example 1 under the same heat mechanical treatment.
FIG. 4 shows the microstructure of the multicomponent alloy of the present invention in the same thermo-mechanically treated state as that obtained in example 2 and comparative example 2, wherein (a) is the B-free state of comparative example 2 and (B) is the B-state of example 2 containing 90 ppm;
FIG. 5 is an XRD pattern of the multicomponent alloy obtained in example 2 of the present invention and comparative example 2 under the same thermo-mechanical treatment state;
FIG. 6 is a drawing showing the tensile engineering stress-strain curves of the multicomponent alloys obtained in example 2 of the present invention and comparative example 2 under the same heat mechanical treatment conditions.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a trace B element doped modified high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy, the general formula of which is Fe 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 -60ppm B multicomponent alloy composition.
In the embodiment, the preparation method of the trace B element doped modified high-strength high-plasticity multi-component alloy comprises the following steps: the Fe-B intermediate alloy raw material is placed at the lowest part of a copper crucible according to the weight proportion so as not to be blown off by a transient arc to influence the B content, the metal simple substance raw material Ni, cr, cu, al and Ti are covered on the Fe-B intermediate alloy, the purity of the selected metal simple substance raw material Ni, cr, cu, al and Ti is more than or equal to 99.95 wt%, and the purity of the selected Fe-B intermediate alloy raw material is more than or equal to 99 wt%. Vacuum chamber is pumped to 3.0X10 -3 pa, and then reversely charging high-purity argon to-0.06 MPa.
When the alloy ingot is smelted, the current is added to 250A, the smelting time is 70s, and the overturning and smelting are repeated for 6 times, so that the uniformity of a tissue structure is ensured. Finally obtain the as-cast doped 60ppm B modified Fe 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 Multicomponent alloy button ingot. Placing the multi-component alloy button ingot into a GSL tubular heat treatment furnace, wherein the homogenization heat treatment process is selected to be 1200 ℃ multiplied by 4 hours, and water quenching is performed; the cold rolling treatment was performed, the cold rolling deformation amount was 90%, and each cold rolling amount was 0.1mm and repeated 2 times. Then at high temperatureAnnealing at 1000 ℃ for 1h, and water quenching; then carrying out low-temperature annealing at 700 ℃ for 20h and water quenching. Fe in the thermomechanical treated state of 60ppm B was finally obtained 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 A multicomponent alloy.
Comparative example 1
The alloy of the comparative example has the general formula of Fe 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 The preparation method is basically the same as in example 1, except that the Fe-B master alloy raw material is replaced with elemental metal raw material Fe.
FIG. 1 shows the microstructure of the multicomponent alloy obtained in this example 1 and comparative example 1 under the same heat mechanical treatment. It was found that the alloy, after doping with 60ppm B, was subjected to the same thermo-mechanical treatment, suppressing precipitation of coarse BCC-based Heusler phases at the grain boundaries, while promoting formation of fine BCC-based Heusler phases within the grain boundaries. FIG. 2 shows XRD patterns of the multicomponent alloy obtained in this example 1 and comparative example 1 in the same thermo-mechanically treated state, which is identical in phase structure in the 0B and 60ppm B-containing states, and which is composed of FCC and BCC phases. FIG. 3 is a drawing showing the tensile engineering stress-strain curves of the multicomponent alloy obtained in this example 1 and comparative example 1 under the same heat mechanical treatment. It can be found that the mechanical properties of the multicomponent alloy in the 0B state are excellent, and the yield strength, the tensile strength and the elongation are 793.8MPa, 1153.1MPa and 25.2 percent respectively. After 60ppm B doping modification, the precipitation of coarse hard phases at the grain boundary is inhibited, meanwhile, the formation of fine Heusler phases in the grain boundary is promoted, the stress concentration is relieved, the yield strength and the tensile strength of the alloy are improved, the yield strength and the tensile strength are respectively increased to 961.1MPa and 1270.9MPa, and meanwhile, the fracture elongation is still kept at a higher level of 22.7%.
Example 2
The embodiment discloses a trace B element doped modified high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy, the general formula of which is Fe 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 -90ppm B multicomponent alloy composition.
In this embodiment, trace B element doping is changedThe preparation method of the high-strength high-plasticity Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy comprises the following steps: the Fe-B intermediate alloy raw material is placed at the lowest part of the copper crucible so as not to be blown off by a transient arc to influence the B content, the metal simple substance raw material Ni, cr, cu, al and Ti are covered on the Fe-B intermediate alloy, the purity of the selected metal simple substance raw material Ni, cr, cu, al and Ti is more than or equal to 99.95wt.%, and the purity of the selected Fe-B intermediate alloy raw material is more than or equal to 99wt.%. Vacuum chamber is pumped to 3.0X10 -3 pa, and then reversely charging high-purity argon to-0.06 MPa.
When the alloy ingot is smelted, the current is added to 250A, the smelting time is 70s, and the overturning and smelting are repeated for 6 times, so that the uniformity of a tissue structure is ensured. Finally obtaining the Fe modified by doping 90ppm B in the as-cast state 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 Multicomponent alloy button ingot. Placing the obtained multi-component alloy button ingot into a GSL tubular heat treatment furnace, wherein the homogenization heat treatment process is selected to be 1200 ℃ multiplied by 4 hours, and water quenching is performed; the cold rolling treatment was performed, the cold rolling deformation amount was 90%, and each cold rolling amount was 0.1mm and repeated 2 times. Then high-temperature annealing is carried out for 1h at 1000 ℃, and water quenching is carried out; then carrying out low-temperature annealing at 700 ℃ for 20h and water quenching. Finally obtaining Fe in the thermomechanical treatment state containing 90ppm B 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 A multicomponent alloy.
Comparative example 2
The alloy of the comparative example has the general formula of Fe 2 NiCr 0.5 Cu 0.2 Al 0.3 Ti 0.1 The preparation method is basically the same as in example 2, except that the Fe-B master alloy raw material is replaced with elemental metal raw material Fe.
FIG. 4 shows the microstructure of the multicomponent alloy obtained in this example 2 and comparative example 2 under the same heat mechanical treatment. Similar to example 1, it was found that the alloy, after doping with 90ppm B, was subjected to the same thermo-mechanical treatment, suppressing precipitation of coarse BCC-based Heusler phases at the grain boundaries, and at the same time promoting formation of fine BCC-based Heusler phases within the grain boundaries. FIG. 5 shows XRD patterns of the multicomponent alloy obtained in this example 2 and comparative example 2 in the same thermo-mechanically treated stateThe phases at 0B and 90ppm B are structurally identical, both of which consist of FCC and BCC phases, but the addition of 90ppm B is reduced (110) BCC The intensity of the peaks indicates a relatively low content of BCC phase therein. FIG. 6 is a drawing showing the tensile engineering stress-strain curves of the multicomponent alloy obtained in this example 2 and comparative example 2 under the same heat mechanical treatment. It can be found that the mechanical properties of the multicomponent alloy in the 0B state are excellent, and the yield strength, the tensile strength and the elongation are 793.8MPa, 1153.1MPa and 25.2 percent respectively. After 90ppm B doping modification, the precipitation of a coarse hard phase at a grain boundary is inhibited, meanwhile, the formation of a fine Heusler phase in the grain boundary is promoted, and the stress concentration is relieved, so that the yield strength and the tensile strength of the alloy are greatly improved and respectively increased to 1153.1MPa and 1442.7MPa, and meanwhile, the fracture elongation is still kept at a higher level of 21.3%. In conclusion, the Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy modified by doping trace B elements has excellent balance of strength and plasticity, so that the Fe-Ni-Cr-Cu-Al-Ti-B multicomponent alloy has broad development prospect in the field of engineering structures.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. A trace B element doped modified high-strength high-plasticity multi-component alloy is characterized in that the general formula is Fe a Ni b Cr c Cu d Al e Ti f -gB, wherein a, b, c, d, e, f is the molar ratio, g is the mass fraction of 1.8.ltoreq.a.ltoreq.2.2, 0.8.ltoreq.b.ltoreq.1.2, 0.3.ltoreq.c.ltoreq.0.6, 0.1.ltoreq.d.ltoreq.0.4, 0.1.ltoreq.e.ltoreq.0.4, 0.1.ltoreq.f.ltoreq.0.3, a: b: d: f=20: 10:2:1, c: e=5: 3, g is more than or equal to 60ppm and less than or equal to 90 ppm;
the preparation method of the trace B element doped modified high-strength high-plasticity multi-component alloy comprises the following steps:
stacking the simple substance raw materials Ni, cr, cu, al, ti and the Fe-B intermediate alloy according to the weight ratio, and smelting by adopting a vacuum arc smelting furnace to obtain a multi-component alloy button ingot; and placing the multi-component alloy button ingot into a vacuum heat treatment furnace, carrying out homogenization heat treatment, and then sequentially carrying out high-deformation cold rolling and high-temperature aging heat treatment to obtain the trace B element modified high-strength high-plasticity multi-component alloy.
2. The trace B element doped modified high strength high plasticity multicomponent alloy according to claim 1, wherein the purity of the selected elemental metal raw material Ni, cr, cu, al and Ti is equal to or greater than 99.95: 99.95 wt%; the purity of the selected Fe-B master alloy raw material is more than or equal to 99wt percent.
3. The trace B element doped modified high strength, high plasticity multi-component alloy as described in claim 1 wherein said Fe-B master alloy material is placed under a copper crucible during melting of the alloy material and elemental metal material Ni, cr, cu, al and Ti are overlaid on top of the Fe-B master alloy.
4. The trace B element doped modified high strength high plasticity multicomponent alloy as defined in claim 1, wherein the vacuum melting furnace is evacuated to 2.9 x 10 -3 ~3.2×10 -3 pa, and then reversely filling high-purity argon to-0.06 to-0.05 MPa.
5. The trace-B-element-doped modified high-strength high-plasticity multi-component alloy according to claim 1, wherein when an alloy button ingot is smelted, current is added to 200-250A, the smelting duration is 60-80 s, and the repeated smelting and overturning times are 5-6 times.
6. The trace B element doped modified high strength high plasticity multi-component alloy as claimed in claim 1, wherein the selected equipments for homogenizing heat treatment, cold rolling and high temperature aging heat treatment are GSL tube heat treatment furnace, two-roll cold rolling mill and MITR bench box furnace, respectively.
7. The trace B element doped modified high strength high plasticity multi-component alloy as set forth in claim 1, wherein the homogenizing heat treatment process comprises: homogenizing at 1100-1200 ℃, annealing for 4-8 hours, and water quenching; the cold rolling process comprises the following steps: 80-90% of large deformation; high-temperature aging heat treatment: the annealing temperature is 650-1100 ℃, the aging time is 1-20 h, and the water quenching is carried out.
8. The use of the trace B element doped modified high strength high plasticity multicomponent alloy as defined in claim 1 in the fields of hard cutter materials, tank armor, transformers, machine tools, jet engines.
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| CN115354202A (en) * | 2022-07-05 | 2022-11-18 | 西北工业大学 | High-toughness material suitable for differential backfill spot welding tool and preparation method |
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| KR101962229B1 (en) * | 2017-09-08 | 2019-03-26 | 포항공과대학교 산학협력단 | Boron-doped High Entropy Alloy and Manufacturing Method of the Same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111850375A (en) * | 2020-08-07 | 2020-10-30 | 沈阳航空航天大学 | Nano precipitation strengthening type high-strength high-plasticity multi-element alloy and preparation method thereof |
| CN114293087A (en) * | 2022-01-04 | 2022-04-08 | 中国科学院兰州化学物理研究所 | Single-phase high-entropy alloy with micron/nano-crystalline grain composite structure |
| CN115141967A (en) * | 2022-06-13 | 2022-10-04 | 哈尔滨工业大学（深圳） | High-entropy alloy composite material and preparation method and application thereof |
| CN115354202A (en) * | 2022-07-05 | 2022-11-18 | 西北工业大学 | High-toughness material suitable for differential backfill spot welding tool and preparation method |
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