CN113774265B - High-entropy intermetallic compound with high strength and wide-temperature-range wear-resistant characteristics - Google Patents
High-entropy intermetallic compound with high strength and wide-temperature-range wear-resistant characteristics Download PDFInfo
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- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 69
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
The invention relates to a high-entropy intermetallic compound with high strength and wide temperature range wear resistance, and the chemical composition of the high-entropy intermetallic compound is Ni1‑x(Al1/3Nb1/3Ti1/3)x、Ni1‑x(Al1/3V1/3Ti1/3)xOr Ni1‑x(Al1/4Nb1/4Ti1/4V1/4)xWherein x =0.25 to 0.5, and the proportion of each element is calculated by atomic percentage. The invention not only has high strength and high hardness, but also shows good high-temperature softening resistance and wide-temperature-range wear resistance, simultaneously has simple preparation process and high performance reliability, and has important application prospect in solving the wear resistance problem of key systems in the high-technology field, in particular the fields of aerospace industry, new energy generation and the like.
Description
Technical Field
The invention relates to the technical field of high-strength wear-resistant alloy materials, in particular to a high-entropy intermetallic compound with high strength and wide temperature range wear resistance.
Background
The material is a material foundation supporting the rapid development of future science and technology and manufacturing industry, and the exploration of novel high-performance materials and the design concept thereof are the permanent targets of the development of materials science. At present, the development of high-end equipment presents the characteristics of complex service environment, extreme working condition, extreme core index, functional performance requirement and the like. The existing wear-resistant materials in China have insufficient technical development level and lack of high-performance materials, and become a key technical bottleneck for restricting the development of high-end equipment. The Ni-Al intermetallic compound has important application prospect in solving the wear-resisting problem of key systems in the high-technology field, particularly the fields of aerospace industry, power generation energy and the like due to excellent specific strength and thermal stability (Acta mater. 2020;185:493 506). Therefore, the further improvement of the bearing capacity and the wide-temperature-range wear-resistant characteristic of the Ni-Al intermetallic compound has profound significance for better solving the high-temperature wear problem of the mechanical motion transmission part of high-end equipment in the advanced manufacturing industry.
In the aspect of improving the strength of the Ni-Al intermetallic compound, based on the traditional single principal element alloying design concept, the main strengthening strategy is to regulate and control the composition, proportion and shape of intermetallic phases in a matrix by introducing alloying elements (such as Cr, Nb, Ti and the like). However, excessive amounts of alloying elements tend to result in substantial precipitation of brittle intermetallic phases, thereby significantly deteriorating the properties of the matrix (Nat Commun. 2018;9: 4063). In the aspect of improving the wide-temperature-range wear resistance of the Ni-Al intermetallic compound, the aim is mainly achieved by introducing a solid lubricant and a hard reinforcing phase, but the problems of mechanical property shock drop after material compounding caused by interface mismatching and metallurgical immiscible among a solid lubricating phase, a wear-resistant phase and an alloy matrix (Tribol. int. 2021;157: 106912) are easily caused. In general, the improvement of the Ni-Al intermetallic compound and the composite material thereof in the aspects of mechanical and tribological properties almost reaches the upper limit, the yield strength at room temperature is difficult to break through 1.5GPa, the apparent hardness is difficult to break through 4.5GPa, and the wear resistance under a wide temperature range is difficult to maintain at 10-5mm3In the order of/Nm or less.
High-entropy alloys are a class of multi-principal-element alloys based on solid-solution high-entropy effect, atomic arrangement long-range lattice order and chemical disorder, and the solid-solution phase of the alloys is often in the middle of a phase diagram and shows the characteristic of 'mass-agent segregation' (Nat Commun. 2020;11: 2390). Meanwhile, based on the influence of the high-entropy effect on the interior of the alloy thermodynamic solution, the high-entropy alloy reflects the remarkable lattice distortion effect and the delayed diffusion effect on the microscopic phase structure level, so that the high-entropy alloy has unique performance combination which cannot be achieved by the traditional alloy, including high strength and hardness, excellent high-temperature softening performance, unique corrosion resistance and oxidation resistance and good tribological performance (Sci. adv. 2018;4: eaat 8712). The novel alloying concept greatly expands the component design space and the structural composition type of the alloy, provides a theoretical basis for developing a new generation of high-performance nickel-based intermetallic compound, and makes the assumption that the intermetallic compound becomes a main phase instead of a second phase in the multi-principal-element alloy possible (Scr mater. 2021;194: 113674).
In summary, how to introduce the multi-principal element alloy design concept based on the high entropy effect into the traditional Ni-Al series intermetallic compound has important significance for developing a new generation of high entropy intermetallic compound with excellent mechanical and tribological properties and meeting the requirements of mechanical motion transmission parts in the high technical field on wear-resistant materials and technologies.
Disclosure of Invention
The invention aims to provide a high-entropy intermetallic compound with high strength and wide-temperature-range wear resistance.
In order to solve the above problems, the present invention provides a high-entropy intermetallic compound having both high strength and wide-temperature-range wear resistance, characterized in that: the chemical composition of the high-entropy intermetallic compound is Ni1-x(Al1/3Nb1/3Ti1/3)x、Ni1-x(Al1/3V1/3Ti1/3)xOr Ni1-x(Al1/4Nb1/4Ti1/4V1/4)xWherein x =0.25 to 0.5, and the proportion of each element is calculated by atomic percentage.
The high-entropy intermetallic compound is a compact block high-entropy intermetallic compound prepared by mechanical alloying auxiliary discharge plasma sintering technology of Ni powder, Al powder, Ti powder and Nb powder and/or V powder.
The Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder are all prepared by a laser crushing technology or an argon atomization technology, the shape of the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder is granular or spherical, the granularity is 20-53 mu m, and the purity is more than 99.9%.
The mechanical alloying process comprises the following steps:
the method comprises the following steps of: putting the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and in an argon atmosphere, adding the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder in a ball-to-material ratio of 1-2: 1. mixing for 5-10 h under the condition that the rotating speed is 100-150 r/min to obtain uniformly mixed initial element powder;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 3.5-6: 1. mixing for 30-40 h under the condition that the rotating speed is 250-300 r/min, and intermittently operating for 0.5 h every 5 h to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder with the grain size of 10-50 mu m.
The discharge plasma sintering conditions are that the vacuum degree is lower than 5 Pa, the sintering temperature is 1050-1250 ℃, the applied pressure is 30-40 MPa, the average heating rate is 65-85 ℃/min, and the heat preservation time is 5-10 min.
The heating process in the spark plasma sintering is that the heating rate from room temperature to 700 ℃ is 80-90 ℃/min, and the heating rate from 700 ℃ to 1050-1250 ℃ is 60-70 ℃/min.
Compared with the prior art, the invention has the following advantages:
1. the invention introduces the multi-principal element high entropy effect into the traditional Ni3In Al-based and NiAl-based intermetallic compounds, a novel high-entropy intermetallic compound with high strength and wide-temperature-range wear resistance is designed. On one hand, the lattice distortion effect is enlarged by adding alloying main elements (such as Ti, V and the like) with larger atomic radius and lower mixing enthalpy with Ni atoms, thereby realizing the obvious solid solution strengthening effect; on the other hand, by adding alloying elements (e.g. Al, Nb, etc.) susceptible to tribochemical reactions during high temperature rubbing to form a protective enamel layerThe medium-high temperature wear resistance is ensured, and the wide-temperature-range continuous wear resistance of the high-entropy intermetallic compound is enhanced.
2. The phase structure of the high-entropy intermetallic compound is represented by a coupled solid solution of multi-principal-element hierarchical intermetallic phases, the phase formation is stable, the element distribution is uniform, the density is low, and the material has no structural defects such as microcracks, pores and the like.
3. The high-entropy intermetallic compound has high strength and high hardness: the compressive yield strength at room temperature is not less than 1.5GPa, and the hardness is not less than 4.7 GPa. Simultaneously, the high-temperature softening resistance is good; and the volumetric wear rate can be stably maintained at 10 in a wide temperature range of room temperature to 800 DEG C-5mm3In the order of/Nm or less.
4. The high-entropy intermetallic compound with high strength and wide temperature range wear resistance has simple preparation process, low cost of prepared raw materials and high performance reliability, and has important application prospect in solving the wear resistance problem of key systems in the high-technology field, particularly the fields of aerospace industry, new power generation energy and the like.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a scanning electron micrograph of an alloying powder prepared by a mechanical alloying process in example 1 of the present invention.
FIG. 2 shows the starting powder, the alloy powder prepared by mechanical alloying and Ni prepared by spark plasma sintering technique in example 1 of the present invention0.75(Al1/4Nb1/4Ti1/4V1/4)0.25XRD diffraction pattern of high entropy intermetallic compound.
FIG. 3 shows Ni prepared in examples 1 to 2 of the present invention0.75(Al1/4Nb1/4Ti1/4V1/4)0.25And Ni0.5(Al1/4Nb1/4Ti1/ 4V1/4)0.5Engineering stress strain curve of high entropy intermetallic compound.
FIG. 4 shows Ni prepared in examples 1 to 2 of the present invention0.75(Al1/4Nb1/4Ti1/4V1/4)0.25And Ni0.5(Al1/4Nb1/4Ti1/ 4V1/4)0.5And (3) high-temperature Vickers hardness test results of the high-entropy intermetallic compound.
FIG. 5 shows Ni prepared in examples 1 to 2 of the present invention0.75(Al1/4Nb1/4Ti1/4V1/4)0.25And Ni0.5(Al1/4Nb1/4Ti1/ 4V1/4)0.5The wear rate of the high entropy intermetallic compound is measured at room temperature, 400 ℃, 600 ℃ and 800 ℃.
FIG. 6 shows Ni prepared by spark plasma sintering according to examples 2 to 4 of the present invention0.5(Al1/4Nb1/4Ti1/ 4V1/4)0.5、Ni0.7(Al1/4Nb1/4Ti1/4V1/4)0.3And Ni0.75(Al1/3Nb1/3Ti1/3)0.25A back-scattered electron image of the high entropy intermetallic compound.
Detailed Description
A high-entropy intermetallic compound with high strength and wide-temperature-range wear resistance features that its chemical composition is Ni1-x(Al1/3Nb1/3Ti1/3)x、Ni1-x(Al1/3V1/3Ti1/3)xOr Ni1-x(Al1/4Nb1/4Ti1/4V1/4)xWherein x =0.25 to 0.5, and the proportion of each element is calculated by atomic percentage.
The high-entropy intermetallic compound is a compact block high-entropy intermetallic compound prepared from Ni powder, Al powder, Ti powder and Nb powder and/or V powder by mechanical alloying auxiliary discharge plasma sintering technology.
Wherein: the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder are all prepared by a laser crushing technology or an argon atomization technology, the shapes of the powders are granular or spherical, the granularity is 20-53 mu m, and the purity is more than 99.9%.
The mechanical alloying process comprises the following steps:
the method comprises the following steps of: putting Ni powder, Al powder, Ti powder and Nb powder and/or V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and in an argon atmosphere, adding a Ni-Ti powder and a Nb-V powder in a ball-to-material ratio of 1-2: 1. mixing for 5-10 h under the condition that the rotating speed is 100-150 r/min to obtain uniformly mixed initial element powder;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 3.5-6: 1. mixing for 30-40 h under the condition that the rotating speed is 250-300 r/min, and intermittently operating for 0.5 h every 5 h to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder with the grain size of 10-50 mu m.
The conditions of spark plasma sintering are that the vacuum degree is lower than 5 Pa, the sintering temperature is 1050-1250 ℃, the applied pressure is 30-40 MPa, the average heating rate is 65-85 ℃/min, and the heat preservation time is 5-10 min. The heating process in the spark plasma sintering is that the heating rate from room temperature to 700 ℃ is 80-90 ℃/min, and the heating rate from 700 ℃ to 1050-1250 ℃ is 60-70 ℃/min.
Example 1 preparation of Ni0.75(Al1/4Nb1/4Ti1/4V1/4)0.25High entropy intermetallic compound:
according to the mixture ratio shown in table 1, the original metal powder is weighed by an electronic balance and then put into a hard alloy tank, and the mechanical alloying process is carried out by a high-energy ball mill, which comprises the following specific steps:
the method comprises the following steps of: putting Ni powder, Al powder, Ti powder, Nb powder and V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and in an argon atmosphere, adding a mixture of Ni powder, Al powder, Ti powder, Nb powder and V powder in a ball-to-material ratio of 2: 1. mixing for 8 h under the condition that the rotating speed is 150 r/min to obtain initial element powder which is uniformly mixed;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 6: 1. mixing for 35 hours under the condition that the rotating speed is 300 r/min, and intermitting for 0.5 hour every 5 hours of operation to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder with the grain size of 10-50 mu m.
Table 1: alloy raw material ratio (mass ratio wt.%)
The resulting alloyed fine crystalline dry powder was characterized by SEM as shown in figure 1. All the components are uniformly distributed on the surface of the quasi-spherical powder after mechanical alloying, and the particle size of the powder is 10-40 mu m; the obtained alloyed fine crystalline dry powder was characterized by XRD diffraction, and as shown in fig. 2, the mechanical alloying process caused the metal elements to be solid-dissolved into a supersaturated solid solution structure with each other, which was expressed as a solid solution structure with a single-phase supersaturated FCC phase.
Then the obtained alloyed fine-grained dry powder is put into a graphite die (phi 50mm) with graphite paper padded on the periphery, and is placed into a Spark Plasma Sintering (SPS) furnace to start sintering at a preset constant pressure of 30 MPa. Sintering parameters: the vacuum degree is lower than 5 Pa, the sintering temperature is 1250 ℃, the heat preservation time is 8 min, the heating rate from the room temperature to 700 ℃ in the heating process is 90 ℃/min, and the heating rate from 700 ℃ to 1250 ℃ is 70 ℃/min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Ni with high strength and wide temperature range wear resistance0.75(Al1/4Nb1/4Ti1/4V1/4)0.25A high entropy intermetallic compound.
The resulting sintered bulk samples were characterized by XRD diffraction, as shown in FIG. 2, the spark heating and plasticity experienced by FCC single phase supersaturated solid solutions during SPS sinteringUnder the combined action of deformation, the phase is gradually changed into A3 phase and L1 phase2The coupled double has an intermetallic phase structure.
The obtained high-entropy intermetallic compound is machined into a cylindrical compressed sample with the diameter of 4 multiplied by 8 mm, and the sample is polished by metallographic abrasive paper. Adopting WDW-200 mechanics of materials tester to make 2.5X 10-4s-1The compressive properties of the compressed samples were tested and the test was repeated at least three times. As shown in FIG. 3, the high-entropy intermetallic compound has a compressive yield strength of not less than 1.5GPa and an ultimate compressive strength of not less than 1.7 GPa at room temperature. The results show that: the multi-principal element alloying effect realizes remarkable solid solution strengthening.
The obtained high-entropy intermetallic compound was machined into a rectangular hardness test sample of 8X 3 mm, and polished with metallographic abrasive paper. The high temperature hardness was tested using an HTV-PHS30 high temperature durometer with at least 5 test points performed per test temperature. As shown in FIG. 4, the Vickers hardness of the high-entropy intermetallic compound is not less than 4.5GPa at room temperature and not less than 3.1 GPa at 800 ℃. The results show that: the high-entropy intermetallic compound has high hardness and simultaneously shows excellent high-temperature softening resistance.
The obtained high-entropy intermetallic compound was machined into a rectangular sample of 18.5X 4 mm, and polished using metallographic sandpaper, followed by ultrasonic treatment in ethanol. The wear performance was tested using a commercial high temperature friction machine of the HT-1000 ball and disk type. The auxiliary is Si3N4The test distance of the ceramic ball is 360 m, the normal load is 5N, the friction radius is 5.5 mm, and the sliding speed is 0.2 m/s; the test temperatures were set at room temperature, 400 ℃, 600 ℃ and 800 ℃. After the test was completed, the samples were tested for wear rate as measured by the ratio of wear volume to the product of sliding distance and applied load using a MicroXAM-800 model non-contact three-dimensional profilometer. As shown in FIG. 5, the wear rate of the high-entropy intermetallic compound increases with the temperature increase from room temperature to 600 ℃, decreases after the temperature increases to 800 ℃, and the wear rate from room temperature to 800 ℃ is maintained at (1.1-4.2) × 10-5mm3Of the order of/Nm. Table of experimental resultsBright Ni0.75(Al1/4Nb1/4Ti1/4V1/4)0.25The high-entropy intermetallic compound has excellent wide-temperature wear resistance.
Example 2 preparation of Ni0.5(Al1/4Nb1/4Ti1/4V1/4)0.5High entropy intermetallic compound:
according to the mixture ratio shown in table 2, the original metal powder is weighed by an electronic balance and then put into a hard alloy tank, and the mechanical alloying process is carried out by a high-energy ball mill, which comprises the following steps:
the method comprises the following steps of: putting Ni powder, Al powder, Ti powder, Nb powder and V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and performing ball-to-material ratio of 1.5 in an argon atmosphere: 1. mixing for 10 h under the condition that the rotating speed is 150 r/min to obtain initial element powder which is uniformly mixed;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 4: 1. mixing for 40 h under the condition that the rotating speed is 250 r/min, and intermitting for 0.5 h every 5 h of operation to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder.
Table 2: alloy raw material ratio (mass ratio wt.%)
Then the obtained alloyed fine-grained dry powder is put into a graphite die (phi 50mm) with graphite paper padded on the periphery, and is placed into a Spark Plasma Sintering (SPS) furnace to start sintering at a preset constant pressure of 40 MPa. Sintering parameters: the vacuum degree is lower than 5 Pa, the sintering temperature is 1050 ℃, the heat preservation time is 8 min, the heating rate from the room temperature to 700 ℃ in the heating process is 80 ℃/min, and the heating rate from 700 ℃ to 1250 ℃ is 60 ℃/min. BakingCooling to room temperature along with the furnace after the sintering is finished to obtain the Ni with high strength and wide temperature range wear resistance0.5(Al1/4Nb1/4Ti1/4V1/4)0.5A high entropy intermetallic compound.
The texture morphology of the obtained high-entropy intermetallic compound is characterized by a scanning electron microscope (SEM-BSE), and as shown in fig. 6, the high-entropy intermetallic compound is composed of a multi-principal-element graded dual-phase intermetallic phase, wherein a (Al, Nb, Ti, V) -enriched B2 phase is at the grain boundary, and a Ni-enriched A3 intermetallic phase is inside the grain.
The obtained high-entropy intermetallic compound is machined into a cylindrical compressed sample with the diameter of 4 multiplied by 8 mm, and the sample is polished by metallographic abrasive paper. Adopting WDW-200 mechanics of materials tester to make 2.5X 10-4s-1The compressive properties of the compressed samples were tested and the test was repeated at least three times. As shown in FIG. 3, the high-entropy intermetallic compound has a compressive yield strength at room temperature of not less than 2.0 GPa and an ultimate compressive strength of not less than 2.3 GPa. The results show that: the multi-principal element alloying effect realizes obvious solid solution strengthening and obtains the strength superior to that of the traditional nickel-based high-temperature alloy.
The obtained high-entropy intermetallic compound was machined into a rectangular hardness test sample of 8X 3 mm, and polished with metallographic abrasive paper. The high temperature hardness was tested using an HTV-PHS30 high temperature durometer with at least 5 test points performed per test temperature. As shown in FIG. 4, the Vickers hardness of the high-entropy intermetallic compound is not less than 5.7 GPa at room temperature and not less than 3.7 GPa at 800 ℃. The results show that: the high-entropy intermetallic compound has high hardness and simultaneously shows excellent high-temperature softening resistance.
The obtained high-entropy intermetallic compound was machined into a rectangular sample of 18.5X 4 mm, and polished using metallographic sandpaper, followed by ultrasonic treatment in ethanol. The wear performance was tested using a commercial high temperature friction machine of the HT-1000 ball and disk type. The auxiliary is Si3N4The test distance of the ceramic ball is 360 m, the normal load is 5N, the friction radius is 5.5 mm, and the sliding speed is 0.2 m/s; the test temperature was set at room temperature, 400 deg.C, 600 deg.C and800 ℃. After the test was completed, the samples were tested for wear rate as measured by the ratio of wear volume to the product of sliding distance and applied load using a MicroXAM-800 model non-contact three-dimensional profilometer. As shown in FIG. 5, the wear rate of the high-entropy intermetallic compound increases with the temperature increase from room temperature to 600 ℃, decreases after the temperature increases to 800 ℃, and the wear rate from room temperature to 800 ℃ is maintained at (0.6-11.8) × 10-6mm3Of the order of/Nm. The experimental result shows that Ni0.5(Al1/4Nb1/4Ti1/4V1/4)0.5The high-entropy intermetallic compound has excellent wide-temperature wear resistance.
Example 3 preparation of Ni0.7(Al1/4Nb1/4Ti1/4V1/4)0.3High entropy intermetallic compound:
according to the mixture ratio shown in table 3, the original metal powder is weighed by an electronic balance and then put into a hard alloy tank, and the mechanical alloying process is carried out by a high-energy ball mill, which comprises the following specific steps:
the method comprises the following steps of: putting Ni powder, Al powder, Ti powder, Nb powder and V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and performing ball-to-material ratio of 1: 1. mixing for 5 h under the condition that the rotating speed is 100 r/min to obtain uniformly mixed initial element powder;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 3.5: 1. mixing for 30 hours at the rotating speed of 250 r/min, and intermittently keeping for 0.5 hour every 5 hours of operation to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder.
Table 3: alloy raw material ratio (mass ratio wt.%)
Then the obtained alloyed fine-grained dry powder is put into a graphite die (phi 50mm) with graphite paper padded on the periphery, and is placed into a Spark Plasma Sintering (SPS) furnace to start sintering at a preset constant pressure of 35 MPa. Sintering parameters: the vacuum degree is lower than 5 Pa, the sintering temperature is 1150 ℃, the heat preservation time is 8 min, the heating rate from the room temperature to 700 ℃ in the heating process is 85 ℃/min, and the heating rate from 700 ℃ to 1150 ℃ is 65 ℃/min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Ni with high strength and wide temperature range wear resistance0.7(Al1/4Nb1/4Ti1/4V1/4)0.3A high entropy intermetallic compound.
The morphology of the obtained high-entropy intermetallic compound is characterized by a scanning electron microscope (SEM-BSE), and as shown in FIG. 6, the high-entropy intermetallic compound is composed of multi-principal-element graded two-phase intermetallic phase, wherein (Al, Nb, Ti, V) Ni is enriched at the grain boundary3Al-based L12Phase, in which Ni-enriched eta-type Ni is present3A3 intermetallic phase of Ti type.
Example 4 preparation of Ni0.75(Al1/3Nb1/3Ti1/3)0.25High entropy intermetallic compound:
according to the mixture ratio shown in table 4, the original metal powder is weighed by an electronic balance and then put into a hard alloy tank, and the mechanical alloying process is carried out by a high-energy ball mill, which comprises the following specific steps:
the method comprises the following steps of: putting Ni powder, Al powder, Ti powder and Nb powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and in an argon atmosphere, adding a Ni-based powder, an Al-based powder, a Ti-based powder and an Nb-based powder in a ball-to-material ratio of 1.5: 1. mixing for 8 h under the condition that the rotating speed is 150 r/min to obtain initial element powder which is uniformly mixed;
the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 4: 1. mixing for 35 hours under the condition that the rotating speed is 300 r/min, and intermitting for 0.5 hour every 5 hours of operation to finally obtain alloyed fine grain powder;
drying: and drying the alloyed fine grain powder to constant weight, and sieving to obtain the alloyed fine grain dry powder.
Table 4: alloy raw material ratio (mass ratio wt.%)
Then the obtained alloyed fine-grained dry powder is put into a graphite die (phi 50mm) with graphite paper padded on the periphery, and is placed into a Spark Plasma Sintering (SPS) furnace to start sintering at a preset constant pressure of 30 MPa. Sintering parameters: the vacuum degree is lower than 5 Pa, the sintering temperature is 1050 ℃, the heat preservation time is 8 min, the heating rate from the room temperature to 700 ℃ in the heating process is 90 ℃/min, and the heating rate from 700 ℃ to 1050 ℃ is 70 ℃/min. Cooling to room temperature along with the furnace after sintering is finished to obtain the Ni with high strength and wide temperature range wear resistance0.75(Al1/3Nb1/3Ti1/3)0.25A high entropy intermetallic compound.
The morphology of the obtained high-entropy intermetallic compound is characterized by a scanning electron microscope (SEM-BSE), as shown in FIG. 6, and the high-entropy intermetallic compound is composed of multi-principal component grading dual-phase intermetallic phase, wherein the grain boundary is rich in (Al, Nb, Ti) Ni3Al-based L12Phase, in which Ni-enriched eta-type Ni is present3A3 intermetallic phase of Ti type.
Claims (3)
1. A high-entropy intermetallic compound having both high strength and wide temperature range wear resistance characteristics, characterized in that: the chemical composition of the high-entropy intermetallic compound is Ni1-x(Al1/3Nb1/3Ti1/3)x、Ni1-x(Al1/3V1/3Ti1/3)xOr Ni1-x(Al1/4Nb1/ 4Ti1/4V1/4)xWherein x = 0.25-0.5, and the proportion of each element is calculated by atomic percentage; the high-entropy intermetallic compound is prepared from Ni powder, Al powder, Ti powder and Nb powderAnd/or the dense block high-entropy intermetallic compound is prepared by V powder through mechanical alloying auxiliary discharge plasma sintering technology; the mechanical alloying process comprises the following steps: the method comprises the following steps of: putting the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder into a hard alloy tank equipped with a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, and in an argon atmosphere, adding the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder in a ball-to-material ratio of 1-2: 1. mixing for 5-10 h under the condition that the rotating speed is 100-150 r/min to obtain uniformly mixed initial element powder; the method comprises the following steps of: putting the uniformly mixed initial element powder into a high-energy ball mill, taking a hard alloy ball with the diameter of 3-10 mm as a grinding ball, taking absolute ethyl alcohol as a process control agent, and adding a mixture of the absolute ethyl alcohol and the anhydrous ethyl alcohol in an argon atmosphere at a ball-to-material ratio of 3.5-6: 1. mixing for 30-40 h under the condition that the rotating speed is 250-300 r/min, and intermittently operating for 0.5 h every 5 h to finally obtain alloyed fine grain powder; drying: drying the alloyed fine grain powder to constant weight and sieving to obtain alloyed fine grain dry powder with the grain size of 10-50 mu m; the discharge plasma sintering conditions are that the vacuum degree is lower than 5 Pa, the sintering temperature is 1050-1250 ℃, the applied pressure is 30-40 MPa, the average heating rate is 65-85 ℃/min, and the heat preservation time is 5-10 min.
2. A high entropy intermetallic compound having both high strength and wide temperature range wear resistance characteristics according to claim 1 wherein: the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder are all prepared by a laser crushing technology or an argon atomization technology, the shape of the Ni powder, the Al powder, the Ti powder and the Nb powder and/or the V powder is granular or spherical, the granularity is 20-53 mu m, and the purity is more than 99.9%.
3. A high entropy intermetallic compound having both high strength and wide temperature range wear resistance characteristics according to claim 1 wherein: the heating process in the spark plasma sintering is that the heating rate from room temperature to 700 ℃ is 80-90 ℃/min, and the heating rate from 700 ℃ to 1050-1250 ℃ is 60-70 ℃/min.
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