CN114703415A - High-entropy alloy based on interstitial solid solution and replacement solid solution strengthening effect and preparation method thereof - Google Patents
High-entropy alloy based on interstitial solid solution and replacement solid solution strengthening effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of alloy materials, and particularly provides a high-entropy alloy based on interstitial solid solution and replacement solid solution strengthening effects and a preparation method thereof. The general formula of the high-entropy alloy is B in terms of atomic molar ratioxAl2Ti1(CrFeNi)97‑xWherein, 0<x<2. The invention realizes the structure regulation and the strengthening and toughening of the high-entropy alloy by the synergistic action of two mechanisms of replacement solid solution strengthening and interstitial solid solution strengthening, and provides a B-Al-Ti-Cr-Fe-Ni high-entropy alloy system with high strength and high plasticity.
Description
Technical Field
The invention relates to the technical field of alloy materials, in particular to a high-entropy alloy based on interstitial solid solution and replacement solid solution strengthening effects and a preparation method thereof.
Background
The traditional alloy consists of one or two main elements, the high-entropy alloy is different from the traditional alloy, and the high-entropy alloy consists of five or more main elements with equal or similar equal quantity. Researches find that the high-entropy alloy has four effects of a high-entropy effect, a lattice distortion effect, a delayed diffusion effect, a cocktail effect and the like. Compared with the traditional alloy, the high-entropy alloy has some remarkable properties such as high strength, high hardness, good ductility, good thermal stability, good fatigue resistance, and excellent corrosion resistance and wear resistance. Co element is a strategic scarce element and is expensive, so that an alloy system which does not contain Co element and still can keep excellent mechanical property is developed, not only can thought and research foundation be provided for development of a low-cost high-entropy alloy system, but also economic cost can be reduced, and the application process of the high-entropy alloy is promoted greatly.
Based on the current research on high-entropy alloy, the research difficulty lies in how to prepare an alloy system with high matching of strong plasticity, namely, the strength and the hardness of the alloy are improved while a part of plasticity is sacrificed, so that the alloy is difficult to be widely applied as a structural material. At present, the obtained alloy with high strength and high plasticity mainly has four strengthening mechanisms, namely dislocation strengthening, fine crystal strengthening, second phase strengthening and solid solution strengthening. The invention realizes the structure regulation and the strengthening and toughening of the high-entropy alloy by the synergistic action of two strengthening mechanisms of replacement solid solution strengthening and interstitial solid solution strengthening, and provides a novel high-entropy alloy with high strength and high plasticity, and the high-plasticity matching of the novel high-entropy alloy is high.
Therefore, how to obtain the alloy with high strength and high plasticity is a research hotspot in the field of high-entropy alloy, and has important research significance, and the application is provided in view of the fact.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-entropy alloy based on interstitial solid solution and replacement solid solution strengthening effects and a preparation method thereof.
The high-entropy alloy based on the interstitial solid solution and replacement solid solution strengthening effects has a general formula B in terms of atomic molar ratioxAl2Ti1(CrFeNi)97-xWherein, 0<x<2。
As a case, the general formula of the high-entropy alloy is B0.25Al2Ti1(CrFeNi)96.75。
As a case, the general formula of the high-entropy alloy is B0.5Al2Ti1(CrFeNi)96.5。
As a case, the general formula of the high-entropy alloy is B1Al2Ti1(CrFeNi)96。
As a case, the general formula of the high-entropy alloy is B1.5Al2Ti1(CrFeNi)95.5。
As one example, the high entropy alloy has a single phase FCC structure, being a dendritic structure.
As a case, the high-entropy alloy B1.5Al2Ti1(CrFeNi)95.5The yield strength and the maximum tensile strength of the steel respectively reach 252.1MPa and 603.7MPa, and the elongation after tensile fracture is 26.9 percent.
The invention provides a preparation method of any one of the high-entropy alloys based on the interstitial solid solution and replacement solid solution strengthening effects, which comprises the step of adding Al into Al2Ti1(CrFeNi)97And adding B element into the matrix according to the formula amount for smelting to obtain the high-entropy alloy based on the interstitial solid solution and replacement solid solution strengthening effect.
As a case, the preparation method comprises the following steps:
(1) removing surface impurities and oxides of simple substances B, Al, Ti, Cr, Fe and Ni by using No. 60 SiC sand paper and a sand turbine, cleaning by using acetone, weighing B, Al, Ti, Cr, Fe and Ni according to a formula, and ultrasonically cleaning;
(2) b, Al, Ti, Cr, Fe and Ni which are subjected to ultrasonic cleaning are placed in a high-vacuum non-consumable arc melting furnace, and the vacuum degree is less than or equal to 1.0 multiplied by 10 under the protection of argon-3Arc melting is carried out under MPa to obtain alloy liquid, and the alloy liquid is stirred and cooled to obtain an alloy ingot;
(3) turning over the alloy ingot, and repeating the arc melting, stirring and cooling processes in the step (1);
(4) repeating the step (3) to obtain the B based on the gap and replacement solid solution strengthening effectxAl2Ti1(CrFeNi)97-xHigh entropy alloy.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention provides a high-entropy alloy with high strong plasticity matching, namely, the microstructure and the mechanical property of a matrix high-entropy alloy are regulated and controlled by adding a proper amount of interstitial solid solution strengthening and replacement solid solution strengthening elements.
2. In the invention, Al2Ti1(CrFeNi)97B atoms are added into the high-entropy alloy to serve as interstitial atoms, Al atoms and Ti atoms serve as substitutional atoms, the mechanical property of the alloy is improved through a solid solution strengthening mechanism, and the application range of the high-entropy alloy is expanded.
3. The invention removes common but expensive Co element in the high-entropy alloy, provides a B-Al-Ti-Cr-Fe-Ni high-performance high-entropy alloy system with relatively low cost, and improves the economic benefit.
4. Further, the present invention is directed to Al2Ti1(CrFeNi)97In the matrix, B elements with different proportions are added to obtain various alloys with improved properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is BxAl2Ti1(CrFeNi)97-xX-ray diffraction pattern of the system high-entropy alloy.
FIG. 2 is BxAl2Ti1(CrFeNi)97-xOptical microscope photograph of the high entropy alloy of system.
FIG. 3 is BxAl2Ti1(CrFeNi)97-xVickers hardness diagram of the system high-entropy alloy.
FIG. 4 is BxAl2Ti1(CrFeNi)97-xQuasi-static tensile stress-strain curves for high entropy alloys.
FIG. 5 is BxAl2Ti1(CrFeNi)97-xQuasi-static compressive stress-strain curves for high entropy alloys.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. 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.
Examples
The invention provides a novel high-entropy alloy which has a general formula B in terms of atomic molar ratioxAl2Ti1(CrFeNi)97-xWherein, 0<x＜2。
When the values of x are different, specific alloys of different cases are obtained, and the compositions of the high-entropy alloys of the cases are shown in the following table 1.
TABLE 1
| Serial number | Value of x | |
| 1 | 0 | Al2Ti1(CrFeNi)97 |
| 2 | 0.25 | B0.25Al2Ti1(CrFeNi)96.75 |
| 3 | 0.5 | B0.5Al2Ti1(CrFeNi)96.5 |
| 4 | 1 | B1Al2Ti1(CrFeNi)96 |
| 5 | 1.5 | B1.5Al2Ti1(CrFeNi)95.5 |
The high-entropy alloy of each case is obtained by adopting the following preparation method:
(1) removing surface impurities and oxides of simple substances B, Al, Ti, Cr, Fe and Ni by using No. 60 SiC abrasive paper and a sand turbine, cleaning by using acetone, weighing the B, Al, Ti, Cr, Fe and Ni with the total mass of 100g according to the formula of each case, and ultrasonically cleaning twice.
(2) B, Al, Ti, Cr, Fe and Ni which are subjected to ultrasonic cleaning are placed in a high-vacuum non-consumable arc melting furnace, and the vacuum degree is less than or equal to 1.0 multiplied by 10 under the protection of argon-3Arc melting is carried out under MPa to obtain alloy liquid, and the alloy liquid is stirred and cooled to obtain an alloy ingot.
(3) And (2) turning over the alloy ingot, and repeating the arc melting, stirring and cooling processes in the step (1).
(4) Repeating the step (3) for 2 times to obtain corresponding BxAl2Ti1(CrFeNi)97-xHigh entropy alloy.
The purity of the elements B, Al, Ti, Cr, Fe and Ni used in each case was 99.9 wt.%.
The high vacuum non-consumable arc melting furnace is a DHL-400 type high vacuum non-consumable arc melting furnace produced by Shenyang scientific instruments GmbH of Chinese academy of sciences.
Examples of effects
The following characterization analyses were performed on the mechanical property test, the texture structure and the thermal stability of the high-entropy alloy obtained in each case:
(1) phase analysis: the phase analysis was carried out using a smart lab X-ray diffractometer, a japan physical company, with operating voltages and currents of 40KV and 190mA, respectively, and an X-ray source of CuK α (λ ═ 0.1542nm) radiation.
(2) And (3) microstructure: microstructural characterisation was carried out using a JSM-6610LV type cold field emission scanning electron microscope (SEM, Merlin Compact).
(3) And (3) testing quasi-static tensile mechanical properties: a CMT4305 type microcomputer electronic universal testing machine is adopted to carry out room temperature quasi-static tensile test, the test sample is made into an I-shaped piece sample according to the relevant regulations in the national standard of the metal material room temperature tensile test method (GB/T228.1-2010), and the strain rate is 10-3s-1。
(4) Testing the mechanical properties of quasi-static compression: a CMT4305 type microcomputer electronic universal tester is adopted to carry out a room temperature quasi-static compression test, and a test sample is made into a cylindrical sample with the diameter of 4mm and the height of 6mm according to the relevant regulations in the national standard of a metal material room temperature compression test method (GB 7314-87).
The test results obtained are shown in FIGS. 1 to 4.
FIG. 1 is BxAl2Ti1(CrFeNi)97-xThe X-ray diffraction pattern of the high-entropy alloy system. As can be seen from the figure, all alloys exhibit a single phase FCC structure. It can be seen that2Ti1(CrFeNi)97Compared with the high-entropy alloy, the B content is gradually increased, and the B content is gradually increasedxAl2Ti1(CrFeNi)97-xThe diffraction peak of the (111) crystal face of the FCC phase in the high-entropy alloy shifts to a low angle, which shows that the B atom with smaller atomic radius is dissolved in the FCC crystal lattice.
FIG. 2 is BxAl2Ti1(CrFeNi)97-xAnd (3) carrying out high-entropy alloy optical microscope photo on the system. FIG. 2 shows Al in this order2Ti1(CrFeNi)97，B0.25Al2Ti1(CrFeNi)96.75，B0.5Al2Ti1(CrFeNi)96.5，B1Al2Ti1(CrFeNi)96，B1.5Al2Ti1(CrFeNi)95.5OM diagram of the alloy. Analysis by combining XRD pattern results shows that the alloy has an FCC structure. As the content of the B element is increased, the size of the dendrite is gradually reduced, and the size of the interdendritic region is slightly increased. When the content of the B element is 0, the dendritic region is about 60 to 80 μm; as the B content increases, the dendrite region is about 25 to 35 μm when the B content is 1.5%.
FIG. 3 is BxAl2Ti1(CrFeNi)97-xThe Vickers hardness diagram of the system high-entropy alloy. As can be seen from the figure, Al can be seen from the figure2Ti1(CrFeNi)97，B0.25Al2Ti1(CrFeNi)96.75，B0.5Al2Ti1(CrFeNi)96.5，B1Al2Ti1(CrFeNi)96，B1.5Al2Ti1(CrFeNi)95.5The hardness of the alloy was 175.1HV, 166.9HV, 169.67HV, 176.1HV and 200.3HV, respectively. Relative to Al2Ti1(CrFeNi)97Alloy, B0.25Al2Ti1(CrFeNi)96.75，B0.5Al2Ti1(CrFeNi)96.5，B1Al2Ti1(CrFeNi)96，B1.5Al2Ti1(CrFeNi)95.5The hardness change is not significant in the alloy due to the low B content added. However, it is noteworthy that B1.5Al2Ti1(CrFeNi)95.5The hardness of the alloy is obviously improved compared with Al2Ti1(CrFeNi)97The change of the hardness of the alloy reaches 33.35HV, and the amplification is 19.97 percent. The analysis suggests that the main reason for the gradual increase in hardness is the solid solution strengthening effect of the elements B, Al, and Ti.
FIG. 4 is BxAl2Ti1(CrFeNi)97-xTensile stress-strain bending of high entropy alloysA wire. Specific values of yield strength, maximum tensile strength and elongation are shown in Table 2-BxAl2Ti1(CrFeNi)100-xThe mechanical property parameter value of the system high-entropy alloy.
The experimental results of table 2 show that as the content of B element is added from 0 to 1.5 at%, the yield strength and tensile strength of the alloy increase from 224.1MPa, 503.7MPa to 225.174MPa, 588.712MPa, respectively. However, the elongation gradually decreases. But, in contrast, B0.25Al2Ti1(CrFeNi)96.75Alloy, B0.5Al2Ti1(CrFeNi)96.5The alloy still maintains excellent elongation of 41.8% and 31.4%.
TABLE 2
| High entropy alloy | Yield strength (MPa) | Tensile strength (MPa) | Elongation (%) |
| Al2Ti1(CrFeNi)97 | 224.1 | 503.0 | 42.6 |
| B0.25Al2Ti1(CrFeNi)96.75 | 199.8 | 522.8 | 41.8 |
| B0.5Al2Ti1(CrFeNi)96.5 | 231.8 | 585.7 | 31.4 |
| B1Al2Ti1(CrFeNi)96 | 225.1 | 588.7 | 26.1 |
| B1.5Al2Ti1(CrFeNi)95.5 | 252.1 | 603.8 | 26.9 |
As can be seen, B increases with the amount of the element B addedxAl2Ti1(CrFeNi)97-xThe yield strength and the tensile strength of the high-entropy alloy of the system are obviously improved, and analysis shows that after B, Al and Ti elements are added into a CrFeNi matrix, B atoms generate an interstitial solid solution strengthening effect, and Al atomic nucleus Ti atoms generate a replacement solid solution strengthening effect, so that the alloy strength is improved. B is1.5Al2Ti1(CrFeNi)95.5The tensile strength of the high-entropy alloy is 603.7MPa, and the elongation after tensile fracture is 26.9%.
FIG. 5 is BxAl2Ti1(CrFeNi)97-xCompressive stress-strain curves for high entropy alloys. The content of the B element is increased from low to high, and the yield strengths of the B element are 238MPa, 251.3MPa, 294.6MPa and 391MPa respectively. Obviously, BxAl2Ti1(CrFeNi)97-xThe yield strength of the high-entropy alloy increases with the content of the B element. It is considered that when B, Al and Ti elements are added to the CrFeNi matrix, a solid solution strengthening effect is produced so thatThe yield strength of the alloy increases. As can be seen from the figure, BxAl2Ti1(CrFeNi)97-xThe high-entropy alloy is not broken by pressing, and the good plasticity is reflected.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The high-entropy alloy based on the interstitial solid solution and replacement solid solution strengthening effects is characterized in that the general formula of the high-entropy alloy is B in terms of atomic molar ratioxAl2Ti1(CrFeNi)97-xWherein, 0<x<2。
2. A high entropy alloy based on interstitial solid solution and substitutional solid solution strengthening effect according to claim 1, wherein the general formula of the high entropy alloy is B0.25Al2Ti1(CrFeNi)96.75。
3. A high entropy alloy based on interstitial and substitutional solid solution strengthening effects according to claim 1, wherein the general formula of the high entropy alloy is B0.5Al2Ti1(CrFeNi)96.5。
4. A high entropy alloy based on interstitial solid solution and substitutional solid solution strengthening effect according to claim 1, wherein the general formula of the high entropy alloy is B1Al2Ti1(CrFeNi)96。
5. A high entropy alloy based on interstitial solid solution and substitutional solid solution strengthening effect according to claim 1, wherein the general formula of the high entropy alloy is B1.5Al2Ti1(CrFeNi)95.5。
6. A high entropy alloy based on interstitial and substitutional solid solution strengthening effects according to any of claims 1-5, characterized in that the high entropy alloy has a single phase FCC structure, being a dendritic structure.
7. A high entropy alloy based on interstitial and substitutional solid solution strengthening effects according to claim 5, characterized in that the high entropy alloy B is1.5Al2Ti1(CrFeNi)95.5The yield strength and the maximum tensile strength of the steel respectively reach 252.1MPa and 603.7MPa, and the elongation after tensile fracture is 26.9 percent.
8. Method for preparing high-entropy alloy based on interstitial solid solution and substitutional solid solution strengthening effect according to any one of claims 1 to 7, and comprising Al2Ti1(CrFeNi)97And adding B element into the matrix according to the formula amount for smelting to obtain the high-entropy alloy based on the interstitial solid solution and replacement solid solution strengthening effect.
9. The method of claim 8, comprising the steps of:
(1) removing surface impurities and oxides of simple substances B, Al, Ti, Cr, Fe and Ni by using No. 60 SiC abrasive paper and a sand turbine, cleaning by using acetone, weighing B, Al, Ti, Cr, Fe and Ni according to a formula, and ultrasonically cleaning;
(2) b, Al, Ti, Cr, Fe and Ni which are subjected to ultrasonic cleaning are placed in a high-vacuum non-consumable arc melting furnace, and the vacuum degree is less than or equal to 1.0 multiplied by 10 under the protection of argon-3Arc melting is carried out under MPa to obtain alloy liquid, and the alloy liquid is stirred and cooled to obtain an alloy ingot;
(3) turning over the alloy ingot, and repeating the arc melting, stirring and cooling processes in the step (1);
(4) repeating the step (3) to obtain the B based on the gap and replacement solid solution strengthening effectxAl2Ti1(CrFeNi)97-xHigh entropy alloy.
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| CN105755324A (en) * | 2016-03-02 | 2016-07-13 | 北京理工大学 | High-entropy alloy with high strength and toughness and preparation method thereof |
| CN110229991A (en) * | 2019-07-03 | 2019-09-13 | 青海大学 | A kind of five yuan of high-entropy alloys and preparation method thereof of strong plasticity good match |
| CN110438385A (en) * | 2019-09-05 | 2019-11-12 | 青海大学 | A kind of Al-Co-Cr-Ni quaternary high-entropy alloy system and preparation method thereof |
| CN112813332A (en) * | 2021-01-07 | 2021-05-18 | 青海大学 | High-entropy alloy based on solid solution and precipitation strengthening effect and preparation method thereof |
| CN113699423A (en) * | 2021-08-30 | 2021-11-26 | 青海大学 | Medium-entropy alloy and preparation method thereof |
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| CN105755324A (en) * | 2016-03-02 | 2016-07-13 | 北京理工大学 | High-entropy alloy with high strength and toughness and preparation method thereof |
| CN110229991A (en) * | 2019-07-03 | 2019-09-13 | 青海大学 | A kind of five yuan of high-entropy alloys and preparation method thereof of strong plasticity good match |
| CN110438385A (en) * | 2019-09-05 | 2019-11-12 | 青海大学 | A kind of Al-Co-Cr-Ni quaternary high-entropy alloy system and preparation method thereof |
| CN112813332A (en) * | 2021-01-07 | 2021-05-18 | 青海大学 | High-entropy alloy based on solid solution and precipitation strengthening effect and preparation method thereof |
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