CN120249775B - High-hardness corrosion-resistant light refractory high-entropy alloy and preparation method thereof - Google Patents
High-hardness corrosion-resistant light refractory high-entropy alloy and preparation method thereofInfo
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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Abstract
The invention relates to the technical field of light refractory high-entropy alloy, in particular to a high-hardness corrosion-resistant light refractory high-entropy alloy and a preparation method thereof. The alloy is prepared by the method. The method comprises the steps of sequentially placing the raw material components with the required mass percentages into a crucible according to the sequence from low melting point to high melting point, placing the crucible into a smelting furnace with air exhausted for smelting, introducing inert gas during smelting, cooling after smelting to obtain an ingot, turning over the ingot, and repeatedly smelting the ingot for 4-7 times to obtain the alloy. The alloy prepared by the invention has high hard corrosion resistance and light weight.
Description
Technical Field
The invention relates to the technical field of light refractory high-entropy alloy, in particular to a high-hardness corrosion-resistant light refractory high-entropy alloy and a preparation method thereof.
Background
Refractory high-entropy alloys are a class of high-density alloys formed from four or more primary refractory elements, the higher density (typically above 9.9 g/cm 3) severely limiting the range of applications for the alloy. The light refractory high-entropy alloy adopts light elements such as Al, ti, zr and the like to replace high-density elements such as Ta, W, re and the like on the basis of the traditional refractory high-entropy alloy, has the characteristics of low density, high hardness, corrosion resistance, high temperature resistance and the like, and has important application value in the aspects of aerospace turbine engines, marine gas turbines and the like.
But the hardness and corrosion resistance of the light refractory high-entropy alloy have a remarkable constraint relation. The density of the alloy can be obviously reduced by adding a large amount of Al and Ti, and the Al and Zr, al and Ti have extremely low mixing enthalpy (-44 KJ/mol and-30 KJ/mol), so that compound phases such as Zr 5Al3 and AlTi and the like are easy to form in the light refractory high-entropy alloy, and are usually hard and brittle phases, thus being an effective way for improving the strength and hardness of the light refractory high-entropy alloy. However, in corrosive solutions, the primary corrosion failure mode of the multi-phase alloy is pitting that occurs at the phase interface, and the presence of intermediate compound phases (such as Zr 5Al3 and AlTi) induces severe pitting phenomena, thereby reducing the corrosion resistance of the lightweight refractory high-entropy alloy.
Therefore, in order to better meet the requirement of the ship gas turbine on the corrosion resistance in the marine corrosion environment, a high-hardness corrosion-resistant light refractory high-entropy alloy and a preparation method thereof are required to be developed so as to solve the problem that the light refractory high-entropy alloy in the prior art has the problem of reduced corrosion resistance due to the existence of intermediate compound phases (such as Zr 5Al3 and AlTi), and simultaneously has higher hardness.
Disclosure of Invention
The invention aims to provide a high-hardness corrosion-resistant light refractory high-entropy alloy and a preparation method thereof, and the specific technical scheme is as follows:
In the first aspect, the invention provides a high-hardness corrosion-resistant light refractory high-entropy alloy which comprises, by mass, 3% -9% of Al, 32% -43% of Nb, 15% -26% of Ti, 1% -4% of V, 15% -18% of Cr and 12% -19% of Mo.
Optionally, the alloy comprises, by mass, 3% -4% of Al, 32% -33% of Nb, 25% -26% of Ti, 3% -4% of V, 16% -17% of Cr and 18% -19% of Mo.
Optionally, each raw material component is metal simple substance particles with purity higher than 99.95%.
Optionally, the alloy is a disordered body-centered cubic solid solution single-phase structure.
Optionally, the hardness of the alloy is above 500 HV.
Alternatively, the alloy has a pitting corrosion resistance voltage of greater than 2.0V in a 3.5 mass% NaCl solution.
In a second aspect, the invention provides a preparation method of the high-hardness corrosion-resistant light refractory high-entropy alloy, which comprises the following steps:
s1, sequentially putting the raw material components with the required mass percentages into a crucible from bottom to top according to the sequence of the melting point from low to high;
s2, placing the crucible into a smelting furnace which discharges air for smelting, and introducing inert gas during smelting;
And step S3, cooling after smelting to obtain an ingot, and repeating the step S2 for repeatedly smelting the ingot for 4-7 times after turning over the ingot to obtain the alloy, wherein the ingot is required to be turned over before each repeated smelting.
Optionally, in the step S2, a vacuum pump is used to exhaust air in the smelting furnace, and the vacuum pumping is controlled to 4×10 -3~6×10-3 Pa.
Optionally, the inert gas comprises argon, the purity of the argon is 99.99%, and the pressure of the inert gas in the smelting furnace is 0.04-0.06 MPa.
Optionally, the smelting furnace comprises a vacuum arc smelting furnace, wherein the adopted smelting temperature is 2300-2800 ℃ and the smelting time is 5-10 min during smelting.
The application of the technical scheme of the invention has at least the following beneficial effects:
(1) The high-hardness corrosion-resistant light refractory high-entropy alloy provided by the invention has high-hardness corrosion-resistant light property. Specifically, three elements with corrosion resistance are adopted, and the mass percentage content of Al, nb and Ti is regulated and controlled, so that the mixing enthalpy of the alloy is controlled to be between-13.7 KJ/mol and-8.3 KJ/mol, and the higher mixing enthalpy value can inhibit the formation of intermetallic compound phases, so that the alloy maintains a single disordered body-centered cubic solid solution single-phase structure, namely a BCC_A2 structure, thereby avoiding the pitting phenomenon at phase interfaces among different phases and effectively improving the corrosion resistance of the alloy. In addition, the atomic radiuses of the Nb element and the Al and Ti elements are greatly different, and the proportion of the Al element with smaller atomic radius in the alloy in a lattice is improved by improving the content of the Al element, so that the lattice distortion is remarkably aggravated, the solid solution strengthening effect is enhanced, and the hardness of the alloy is improved. In addition, a large amount of low-density Al and Ti elements are adopted in the alloy, so that the density of the alloy is 6.42-6.53 g/cm 3, which is far lower than that of the traditional refractory high-entropy alloy (the density is more than or equal to 9.9 g/cm 3), and the application limit of the light refractory high-entropy alloy is broken through.
(2) The invention provides a preparation method of a high-hardness corrosion-resistant light refractory high-entropy alloy, which comprises the steps of sequentially placing raw material components into a crucible from bottom to top according to the sequence of melting points from bottom to top, wherein the raw material components are used for ensuring that the crucible is placed in a smelting furnace, sequentially approaching the heat source in the smelting furnace above the crucible as a base point according to the sequence of melting points from top to bottom, facilitating the full melting of the raw material components, discharging air from the smelting furnace by adopting the step S2, introducing inert gas during smelting, preventing the oxidation of the alloy during smelting from generating a mixed compound phase, further reducing the corrosion resistance of the alloy, and repeatedly smelting by adopting the step S3, and ensuring the full smelting to obtain the BCC_A2 structural alloy.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is an X-ray diffraction chart of the alloy obtained in examples 1 to 3;
FIG. 2 is a microstructure of the alloy obtained in example 1;
FIG. 3 is a microstructure of the alloy obtained in example 2;
FIG. 4 is a microstructure of the alloy obtained in example 3;
FIG. 5 is an electrochemical polarization curve of the alloy obtained in examples 1-3 in a NaCl solution with a mass percentage of 3.5%.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Example 1:
A preparation method of the high-hardness corrosion-resistant light refractory high-entropy alloy comprises the following steps:
S1, weighing the raw material components with the required mass percentage, sequentially placing the raw material components into a crucible from bottom to top according to the sequence of the melting point from bottom to top, wherein the raw material components are used for ensuring that the crucible is placed in a smelting furnace, and sequentially approaching the heat source in the smelting furnace above the crucible according to the sequence of the melting point from top to bottom to facilitate the raw material components to be sufficiently melted, wherein the raw material components comprise 8.8% of Al, 42.6% of Nb, 15.7% of Ti, 3.3% of V, 17% of Cr and 12.6% of Mo, the raw material components are metal simple substance particles with the purity higher than 99.95%, and the mass error of the raw material components is within +/-0.1 g during weighing;
s2, placing the crucible into a smelting furnace which discharges air for smelting, and introducing inert gas during smelting;
And S3, cooling by a water-cooling copper mold after smelting to obtain a button-shaped ingot, and repeating the step S2 for 5 times after turning over the ingot to obtain the alloy, wherein the ingot is required to be turned over before each repeated smelting.
In the step S2, a vacuum pump is adopted to exhaust air in the smelting furnace, and the vacuum pumping is controlled to be 5 multiplied by 10 -3 Pa.
The inert gas is argon, the purity of the argon is 99.99%, and the pressure of the inert gas in the smelting furnace is 0.05MPa.
The smelting furnace is a vacuum arc smelting furnace, and the adopted smelting temperature is 2450+/-50 ℃ and the smelting time is 6min during smelting.
Example 2:
unlike example 1, the mass percentages of the raw material components are Al 6.1%, nb 33.2%, ti 23.3%, V1.7%, cr 16.9% and Mo 18.8%.
Example 3:
Unlike example 1, the mass percentages of the raw material components are Al 3.4%, nb 32.5%, ti 25.9%, V3.2%, cr 16.6% and Mo 18.4%.
Comparative example 1:
Unlike example 1, the mass percentages of the raw material components are Al 1.7%, nb 29.6%, ti 30.5%, V3.2%, cr 16.6% and Mo 18.4%.
Comparative example 2:
unlike example 1, the mass percentages of the raw material components are 26.3% Nb, 13.5% Ti, 14.4% V, 9.2% Cr, 20.4% Mo and 16.2% Zr.
Comparative example 3:
unlike example 1, the air in the melting furnace was not exhausted by a vacuum pump, and the inert gas was not introduced.
Comparative example 4:
unlike example 1, smelting was repeated 3 times.
The alloys obtained in examples 1 to 3 were phase-analyzed by means of an advanced D8X-ray diffractometer, using a Cu K alpha radiation source, with an acceleration voltage of 0 KV, a current of 40 mA, a diffraction angle in the range of 20 DEG to 100 DEG, and a scanning speed ofAnd (3) minutes. The results are shown in FIG. 1.
As shown in fig. 1, the alloys obtained in examples 1 to 3 have characteristic diffraction peaks corresponding to the (110), the (200), the (211) and the (220) crystal planes, which indicates that the alloys obtained in examples 1 to 3 have disordered bcc_a2 single-phase structures.
Further, the microstructure of the alloy obtained in examples 1 to 3 was analyzed by using a JXA-8530F electron probe microanalyzer. As can be seen from fig. 2 to 4, the alloys obtained in examples 1 to 3 formed a distinct dendrite structure, but no precipitated phase appeared. This illustrates that the alloys obtained in examples 1-3 are single phase structures, which are disordered bcc_a2 single phase structures, as is known from fig. 1.
Further, the alloys obtained in examples 1 to 3 and comparative examples 1 to 4 were sampled respectively for density, hardness and corrosion resistance test, and the test results are shown in table 1. The density measurement method comprises the following step of measuring the density by using an Archimedes method at 25 ℃ by taking water as an immersion medium. Hardness testing method the alloy hardness was measured on the polished surface using a vickers hardness tester with a load of 500 g and a hold time of 15 seconds, 5 points per sample were tested to calculate the average hardness. The corrosion resistance testing method comprises the steps of measuring electrochemical characteristics of an alloy by using a Prlington VERSA STAT 4 electrochemical workstation, using a platinum plate as an auxiliary electrode and using a Saturated Calomel Electrode (SCE) as a reference electrode, cutting a 10 multiplied by 3 multiplied by mm high-hardness corrosion-resistant light refractory high-entropy alloy sample serving as a working electrode, and polishing the surface of the sample by using sand paper. The polarization voltage and current density of the sample were measured in a 3.5% mass percent NaCl solution, the scan rate was set at 1 mV/s, starting from an initial potential of-1.0V, and ending until the current density reached 0.01A/cm 2. FIG. 5 is an electrochemical polarization curve of the alloy samples obtained in examples 1-3.
TABLE 1 Density, hardness and Corrosion resistance test results
As shown in the data of Table 1, the alloy obtained in the invention in the examples 1-3 has higher hardness and higher pitting corrosion voltage on the premise of lower density, and shows light weight, high hardness and corrosion resistance.
As is clear from comparative example 1 and comparative example 1, in comparative example 1, the amount of Al was reduced and the amount of Ti was increased, so that the alloy hardness and pitting voltage were lowered, while the density was not greatly changed. This is because the reduction of the amount of Al reduces the proportion of Al elements with smaller atomic radius in the alloy in the lattice, reduces lattice distortion, thereby weakening the solid solution strengthening effect and reducing the hardness of the alloy, while the high amount of Ti is liable to form a second phase with Nb, cr and Mo, and pitting occurs at the phase interface, so that the pitting voltage is reduced. The reason why the density change is not large is that the Al element and the Ti element are both light elements, and the alloy density change is not large under the condition of reducing the Al consumption and increasing the Ti consumption.
As is clear from comparative example 1 and comparative example 2, in comparative example 2, al was not used, but Zr was added, so that the alloy density was increased, and the pitting voltage was decreased, but the influence on hardness was not large. This is because, instead of using Al, zr is added to form a brittle second phase of Cr 2 Zr in the alloy, which reduces corrosion resistance and reduces pitting voltage, but has little effect on hardness. The density is increased because Zr density is larger than Al density, so that alloy density is increased.
As is clear from the comparison between example 1 and comparative example 3, in comparative example 3, the air in the melting furnace was not exhausted by using a vacuum pump, and no inert gas was introduced, so that the pitting voltage was lowered. This is because the presence of discontinuous oxides in the alloy reduces the corrosion resistance, resulting in a drop in pitting voltage.
As is clear from the comparison between example 1 and comparative example 4, too small a number of melting times in comparative example 4 causes a serious element segregation phenomenon in the non-uniform melting of the raw material components, resulting in a significant decrease in alloy hardness and pitting voltage.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
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| CN115094291A (en) * | 2022-06-24 | 2022-09-23 | 大连理工大学 | Ti-V-Al-Cr-M series light high-strength high-entropy alloy and preparation method thereof |
| CN118086753A (en) * | 2023-12-29 | 2024-05-28 | 河南平高电气股份有限公司 | Refractory high entropy alloy powder and refractory high entropy alloy coating |
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| KR101831056B1 (en) * | 2016-06-01 | 2018-02-21 | 한국기계연구원 | High entropy alloy |
| KR101884442B1 (en) * | 2017-02-10 | 2018-08-01 | 서울대학교산학협력단 | High entropy alloy overcoming strength-ductility trade-off |
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| CN115094291A (en) * | 2022-06-24 | 2022-09-23 | 大连理工大学 | Ti-V-Al-Cr-M series light high-strength high-entropy alloy and preparation method thereof |
| CN118086753A (en) * | 2023-12-29 | 2024-05-28 | 河南平高电气股份有限公司 | Refractory high entropy alloy powder and refractory high entropy alloy coating |
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