CN110229991B - Quinary high-entropy alloy with excellent strong plasticity matching and preparation method thereof - Google Patents
Quinary high-entropy alloy with excellent strong plasticity matching and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a quinary high-entropy alloy with excellent strong plasticity matching, and the chemical formula is AlaCobCrcFedNie(a-e are all in moleRatio), wherein 1 is more than or equal to a and more than or equal to 0.5, 1.2 is more than or equal to b and more than or equal to 0.7, 1 is more than or equal to c and more than or equal to 0.4, 1 is more than or equal to d and more than or equal to 0.4, and 2.2 is more than or equal to e and more than or equal to 0.8. Further, the a: e is 1: 1.2 to 2.5. Further, a is 0.8, b is 1, c is 0.6, d is 0.7, and e is 1.1-2.0. Further, the chemical formula of the alloy includes Al0.8CoCr0.6Fe0.7Ni1.1, Al0.8CoCr0.6Fe0.7Ni1.5, Al0.8CoCr0.6Fe0.7Ni1.8 and Al0.8CoCr0.6Fe0.7Ni2.0. The high-entropy alloy has high strength and high plasticity, can overcome the problem of poor obdurability matching of the high-entropy alloy in the prior art, and simultaneously provides a preparation method of a quinary high-entropy alloy with excellent strong plasticity matching, and the method is simple, safe and stable.
Description
Technical Field
The invention relates to the technical field of metal materials and preparation thereof, in particular to a high-entropy alloy with excellent strong plasticity matching and a preparation method thereof.
Background
The high-entropy alloy is an alloy which is composed of five or more elements as main elements, and the atomic percentage of each element is between 5 and 35 percent. Compared with the traditional alloy, the high-entropy alloy has a series of excellent performances due to the unique design concept and microstructure. Such as considerable low-temperature, room-temperature and high-temperature strength, good plasticity and excellent friction and fatigue resistance. However, a great deal of subsequent researches show that the single-phase FCC structure high-entropy alloy has better plasticity and insufficient strength, and the single-phase BCC structure high-entropy alloy has better strength and poorer plasticity, namely the single-phase structure high-entropy alloy cannot meet the requirements of strength and plasticity at the same time, and good strong plasticity matching is realized; designing the high-entropy alloy with the dual-phase structure and the soft/hard phase composite effect is considered to be one of the most effective means for strengthening and toughening the alloy.
Recently, a new type of high-entropy alloy, eutectic high-entropy alloy (EHEA), has been proposed, which is considered to be an alloy in realization of a fine alternating structure of hardness and hardnessHas great potential in the aspect of strong plasticity matching. However, as research progresses, it is difficult to achieve good strong plastic matching for partially eutectic high entropy alloys, such as those in the literature (l.jiang, z.q.cao, j.c.jie, j.j.zhang, y.p.lu, t.m.wang, t.j.li, Effect of Mo and Ni elements on chemical development and mechanical property of the CoFeNixVMoyCoFeNiVMo0.6 and CoFeNi1.4VMo eutectic high entropy Alloys reported in highenthiontopy Alloys, Journal of Alloys and Compounds 649(2015) 585-.
In addition, most high-entropy alloys have the characteristic of delayed diffusion due to multiple principal elements and high concentration, so that element segregation often occurs in the preparation process, the fluidity is poor, and the structure is easy to be uneven. The engineering application and development of the high-entropy alloy are severely restricted by the problems of the preparation process. Therefore, how to reasonably design the eutectic high-entropy alloy with good strong plasticity matching and easy casting forming becomes a technical problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the problem that most high-entropy alloys are poor in obdurability matching, the invention aims to provide a quinary high-entropy alloy with excellent strong plasticity matching, the high-entropy alloy has both strength and plasticity performance, the problem that the existing high-entropy alloy is poor in obdurability matching is solved, and meanwhile, the invention provides a preparation method of the high-entropy alloy with excellent strong plasticity, and the method is simple, safe and stable.
In order to achieve the purpose, the invention adopts the following technical scheme:
a quinary high-entropy alloy with excellent strong plasticity matching has a chemical formula of AlaCobCrcFedNieWherein a, b, c, d and e respectively correspond to the molar ratio of the elements, a is more than or equal to 1 and more than or equal to 0.5, b is more than or equal to 1.2 and more than or equal to 0.7, c is more than or equal to 1 and more than or equal to 0.4, d is more than or equal to 1 and more than or equal to 0.4, and e is more than or equal to 2.2 and more than or equal to 0.8.
Further, the a: e is 1: 1.2 to 2.5.
Further, a is 0.8, b is 1, c is 0.6, d is 0.7, and e is 1.1-2.0.
Further, the chemical formula of the high-entropy alloy is Al0.8CoCr0.6Fe0.7Ni1.1、Al0.8CoCr0.6Fe0.7Ni1.5、Al0.8CoCr0.6Fe0.7Ni1.8And Al0.8CoCr0.6Fe0.7Ni2.0。
Further, the chemical formula of the eutectic quinary high-entropy alloy is Al0.8CoCr0.6Fe0.7Ni1.5The chemical formula of the hypoeutectic quinary high-entropy alloy is Al0.8CoCr0.6Fe0.7Ni1.8。
A preparation method of a quinary high-entropy alloy with excellent strong plasticity matching comprises the following steps:
s1: ultrasonic cleaning: removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning twice, removing and drying after cleaning to obtain five raw materials;
s2: preparing materials: according to the weight ratio of Al: co: cr: fe: accurately weighing 80g of the elemental metal raw material obtained in the step S1 according to the molar percentage of 0.5-1: 0.7-1.2: 0.4-1: 0.8-2.2, and mixing;
s3 arc melting, placing the Al, Co, Cr, Fe and Ni elementary metal raw materials weighed in S2 into a high vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree below 2.5 × 10﹣3Alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is more than or equal to 10min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, turning over the alloy ingot, and repeatedly smelting for more than 4 times to obtain the high-entropy alloy.
Further, the preparation method of the quinary high-entropy alloy with excellent strong plasticity matching is characterized in that the electric arc melting is completed by adopting a high-vacuum non-consumable electric arc melting furnace.
In an Al-Co-Cr-Fe-Ni system, five elements are calculated according to a certain molar ratio to obtain corresponding mixing enthalpy, valence electron concentration, atomic size difference and electronegativity difference. Selecting alloy components through the range of the existing literature criteria, then changing the molar ratio of Ni on the basis of the alloy, controlling the molar fraction ratio of Al/Ni elements to be 1.2-2.5, finding out that the alloy keeps a Face Centered Cubic (FCC) plus Body Centered Cubic (BCC) dual-phase structure along with the increase of the content of the Ni element in the subsequent characterization, presenting the microstructure transformation of equiaxed dendrites-eutectic-hypoeutectic, and finally obtaining the molar ratio of eutectic and hypoeutectic alloy.
Compared with the prior art, the invention has the following beneficial effects:
1. in the high-entropy alloy system, as the content of Ni element is increased, the alloy keeps a Face Centered Cubic (FCC) plus Body Centered Cubic (BCC) dual-phase structure and presents microstructure transformation from equiaxed dendrite-eutectic-hypoeutectic, the eutectic and hypoeutectic high-entropy alloy has narrow crystallization range in the solidification process, good fluidity and casting performance, is not easy to generate element segregation, is easy to machine and form, and solves the preparation problem of the as-cast high-entropy alloy.
2. The high-entropy alloy disclosed by the invention combines a high-plasticity face-centered cubic phase with a high-strength body-centered cubic phase, so that the good combination of strength and plasticity is realized, the eutectic and hypoeutectic high-entropy alloy disclosed by the invention has excellent comprehensive mechanical properties, the yield strength reaches 460MPa, the tensile strength reaches 880MPa, the elongation after fracture reaches 19%, and the properties are very excellent.
3. The preparation method disclosed by the invention is simple and reliable, and the selected elements are nontoxic and convenient to obtain, and have good safety and high economic value.
Drawings
FIG. 1 is an XRD pattern of the high-entropy alloy prepared in examples 1 to 4;
FIG. 2 is an optical micrograph of the high-entropy alloy prepared in examples 1 to 4;
FIG. 3 is a hardness number chart of the high-entropy alloy prepared in examples 1 to 4;
FIG. 4 is a tensile engineering stress-strain curve of the high-entropy alloy prepared in examples 1 to 4.
Detailed Description
The present invention is described in detail below with reference to the attached drawings and specific embodiments so that those skilled in the art can better understand the present invention and can implement the present invention, but the present invention is not limited by the examples.
Instrumentation and equipment
1. 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.
2. The phase, microstructure and mechanical property test characterization information of the obtained high-entropy alloy is as follows:
(1) phase analysis was performed using an X-ray diffractometer (XRD, japan chem company) with an operating voltage and current of 40KV and 100mA, respectively, and an X-ray source of Cu K α (λ 0.1542nm) radiation.
(2) And (3) microstructure: microstructure characterization was performed using a leicdmi 3000M optical microscope.
(3) And (3) hardness testing: a VH1102-01-0040 Wilson Vickers hardness machine is adopted, and a loading force of 2kg is applied and lasts for 13 s;
(4) and (3) testing quasi-static tensile mechanical properties: performing room temperature quasi-static tensile test by adopting an electronic universal tester (CMT4305 type), wherein a test sample is manufactured into a 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。
Example 1
A high-entropy alloy with a dual-phase structure and good strength and plasticity matching has a chemical formula of Al0.8CoCr0.6Fe0.7Ni1.1, wherein the proportion of each element is mole percent and is abbreviated as Ni1.1.
Removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning twice, removing and drying after cleaning to obtain five raw materials;
according to the weight ratio of Al: co: cr: fe: weighing 80g of Al, Co, Cr, Fe and Ni elementary metal raw materials in an accurate molar ratio of Ni to 0.8:1:0.6:0.7:1.1, and mixing;
placing the mixed elementary metal raw material into a high-vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree at 2.4 × 10﹣3And (3) alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is 10min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, overturning the alloy ingot, and repeatedly smelting for more than 4 times to obtain the Ni1.1 high-entropy alloy.
Example 2
A eutectic high-entropy alloy with good strength and plasticity matching has a chemical formula of Al0.8CoCr0.6Fe0.7Ni1.5, wherein the proportion of each element is mole percent and is abbreviated as Ni1.5.
Removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning twice, removing and drying after cleaning to obtain five raw materials;
according to the weight ratio of Al: co: cr: fe: weighing 80g of Al, Co, Cr, Fe and Ni elementary metal raw materials in an accurate molar ratio of Ni to 0.8:1:0.6:0.7:1.5, and mixing;
placing the mixed elementary metal raw material into a high-vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree at 2.4 × 10﹣3And (3) alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is 11min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, overturning the alloy ingot, and repeatedly smelting for more than 4 times to obtain the Ni1.5 high-entropy alloy.
Example 3
A hypoeutectic high-entropy alloy with good strength and plasticity matching has a chemical formula of Al0.8CoCr0.6Fe0.7Ni1.8, wherein the proportion of each element is mole percent and is abbreviated as Ni1.8.
Removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning twice, removing and drying after cleaning to obtain five raw materials;
according to the weight ratio of Al: co: cr: fe: weighing 80g of Al, Co, Cr, Fe and Ni elementary metal raw materials in an accurate molar ratio of Ni to 0.8:1:0.6:0.7:1.8, and mixing;
placing the mixed elementary metal raw material into a high-vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree at 2.3 × 10﹣3And (3) alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is 10min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, overturning the alloy ingot, and repeatedly smelting for more than 4 times to obtain the Ni1.8 high-entropy alloy.
Example 4
A hypoeutectic high-entropy alloy with good strength and plasticity matching has a chemical formula of Al0.8CoCr0.6Fe0.7Ni2.0, wherein the proportion of each element is mole percent and is abbreviated as Ni2.0.
Removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning twice, removing and drying after cleaning to obtain five raw materials;
according to the weight ratio of Al: co: cr: fe: weighing 80g of Al, Co, Cr, Fe and Ni elementary metal raw materials in an accurate molar ratio of Ni to 0.8:1:0.6:0.7:2.0, and mixing;
placing the mixed elementary metal raw material into a high-vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree at 2.4 × 10﹣3And (3) alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is 10min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, overturning the alloy ingot, and repeatedly smelting for more than 4 times to obtain the Ni2.0 high-entropy alloy.
Phase analysis was performed on the high-entropy alloys prepared in examples 1 to 4, and X-ray diffraction (XRD) patterns thereof are shown in fig. 1, and it can be seen that the samples of examples 1 to 4 each consist of solid solution phases of face-centered cubic (FCC) and body-centered cubic (BCC) structures;
the microstructure analysis of the high-entropy alloys prepared in examples 1 to 4 was performed, and the optical micrograph thereof is shown in fig. 2, and it can be seen from fig. 2 that the high-entropy alloy prepared in example 1 shows a typical equiaxed dendrite-interdendritic structure; the high entropy alloy prepared in example 2 exhibited a typical fine lamellar eutectic structure; the high entropy alloys prepared in examples 3 to 4 exhibited equiaxed dendrites (primary phases) + fine lamellar eutectic structures;
hardness tests were performed on the high-entropy alloys prepared in examples 1 to 4, fig. 3 is a hardness data graph of a sample, and as can be seen from table 1, the hardness of the alloys is about 300 HV;
quasi-static tensile mechanical property tests are carried out on the high-entropy alloys prepared in the embodiments 1 to 4, and tensile engineering stress-strain curves of the high-entropy alloys are shown in fig. 4, so that the high-entropy alloys prepared in the embodiments 2 to 3 have good strong plasticity matching, and the yield strength, the tensile strength and the post-fracture length of the alloys are respectively more than or equal to 460MPa, more than or equal to 850MPa and more than or equal to 15 percent;
finally, it should be noted that the above mentioned embodiments are only preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, many modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be regarded as the protection scope of the present invention.
Claims (6)
1. A quinary high-entropy alloy with excellent strong plasticity matching is characterized in that: the chemical formula of the high-entropy alloy is AlaCobCrcFedNieWherein a, b, c, d and e respectively correspond to the molar ratio of each element; the a is 0.8, the b is 1, the c is 0.6, the d is 0.7, and the e is 1.1-2.0.
2. The quinary high-entropy alloy with excellent strong plasticity matching property according to claim 1, wherein the alloy comprises the following components in percentage by weight: the chemical formula of the alloy is Al0.8CoCr0.6Fe0.7Ni1.1、Al0.8CoCr0.6Fe0.7Ni1.5、Al0.8CoCr0.6Fe0.7Ni1.8Or Al0.8CoCr0.6Fe0.7Ni2.0。
3. A strongly plastic web according to claim 2The excellent five-element high-entropy alloy is characterized in that: the chemical formula of the alloy is Al0.8CoCr0.6Fe0.7Ni1.5。
4. The quinary high-entropy alloy with excellent strong plasticity matching property according to claim 2, wherein the alloy comprises the following components in percentage by weight: the chemical formula of the alloy is Al0.8CoCr0.6Fe0.7Ni1.8。
5. The quinary high-entropy alloy with excellent strong plastic matching property according to any one of claims 1 to 4, wherein: the purities of the simple substances Al, Co, Cr, Fe and Ni are all 99.9 wt%.
6. A preparation method of a quinary high-entropy alloy with excellent strong plasticity matching is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, ultrasonic cleaning: removing impurities and oxides on the surface of the elementary metal raw materials of Al, Co, Cr, Fe and Ni with the purity of more than or equal to 99.9 wt% by using SiC sand paper and a sand wheel machine, then putting the raw materials into a container, adding an alcohol solution, ultrasonically cleaning the raw materials twice, and blowing the cleaned raw materials to dry to obtain five raw materials;
s2: preparing materials: according to the weight ratio of Al: co: cr: fe: accurately weighing 80g of the elemental metal raw material obtained in the step S1 according to the molar percentage of 0.8:1:0.6:0.7: 1.1-2.0, and mixing;
s3, arc melting, namely placing the elementary metal raw materials of Al, Co, Cr, Fe and Ni weighed in the step S2 into a high-vacuum non-consumable arc melting furnace, and under the protection of argon, keeping the vacuum degree lower than 2.5 × 10-3Alloying and smelting under MPa, stirring continuously in the smelting process, wherein the smelting time is more than or equal to 10min each time, obtaining alloy liquid, cooling to obtain an alloy ingot, turning over the alloy ingot, and repeatedly smelting for more than 4 times to obtain the high-entropy alloy.
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| CN112210705A (en) * | 2020-09-14 | 2021-01-12 | 西安理工大学 | CuCrCoFeNiZrx high-entropy alloy and preparation method thereof |
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| CN113981292A (en) * | 2021-10-28 | 2022-01-28 | 西北工业大学 | High-entropy alloy with excellent strong plasticity and preparation method thereof |
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| CN115323242B (en) * | 2022-09-22 | 2023-12-01 | 哈尔滨工业大学 | High-strength and high-toughness high-entropy alloy in as-cast state and preparation method thereof |
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