CN114395717B - Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy and preparation method thereof - Google Patents
Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i Is a high-density high-plasticity high-entropy alloy and a preparation method thereof, belonging to the field of high-entropy alloys. The alloy with unequal atomic ratio of Co-Ni-Cr-Fe is used as a matrix, good plasticity is provided, the melting point and density of the alloy are regulated and controlled by adding a certain amount of elements such as W, mo, re, hf, ta, C and the like, and X is one or more of Ta, hf, ru, rh, pd, os, ir and Pt. The component range comprises: a is more than or equal to 28 and less than or equal to 35at percent, b is more than or equal to 28 and less than or equal to 35at percent, c is more than or equal to 10 and less than or equal to 20at percent, d is more than or equal to 10 and less than or equal to 23at percent, e is more than or equal to 1 and less than or equal to 11at percent, f is more than or equal to 0 and less than or equal to 11at percent, g is more than or equal to 0 and less than or equal to 11at percent, h is more than or equal to 0 and less than or equal to 2at percent, and i is more than or equal to 0 and less than or equal to 2at percent. The alloy is smelted and suction cast into a rod through a vacuum consumable/non-consumable arc furnace or a vacuum induction smelting furnace, and the structure of the alloy is optimized through subsequent homogenizing, rolling and annealing processes, so that the high-density high-plasticity high-entropy alloy material is obtained, and the density of the high-density high-plasticity high-entropy alloy material is 8.9-10.2 g/cm 3 The elongation is 17-90%.
Description
Technical Field
The invention belongs to the field of metal materials, and particularly relates to a high-density high-plasticity high-entropy alloy and a preparation method thereof.
Background
High Entropy Alloys (HEAs) are a new class of materials that have been developed in recent years. The compositional composition of HEAs generally comprises five or more elements, each element being present in an equal or near-equal atomic ratio, or the alloy having a configurational entropy greater than 1.5R (R is the gas constant). The high configuration entropy of HEAs enhances the phase stability of solid solutions, thereby promoting the alloy to form simple FCC or BCC solid solutions. The high-entropy alloy system developed at present shows excellent characteristics in the aspect of mechanical behavior, such as high strength, high hardness, high-temperature oxidation resistance, high-temperature softening resistance and the like, and has great application potential in the field of mechanical manufacturing.
High-density alloys play an irreplaceable role in the fields of aerospace, electronic information, energy, metallurgy, military and nuclear industries, etc. At present, they have been widely used in counterweights, sports equipment, armor piercing bullets, shaped charge liners in the weapon industry, and the like.
The high-entropy alloy system is approximatelyThe classification is two types: one kind is an alloy system mainly comprising transition group elements of Fe, co, cr, ni, mn and the like; the refractory high-entropy alloy system mainly comprises refractory metal elements such as Nb, mo, ta, W, V, hf and Re. The refractory high-entropy alloy system has high melting point and high density, but has poor processing plasticity, so that the industrial application of the refractory high-entropy alloy system is limited. The late transition alloy system has good plasticity but melting point: (<1500 ℃ C and a lower density of (C.) (<8.5g/cm 3 ). Wherein, coCrFeNiW 0.4 The high-entropy alloy has higher density which reaches 9.5g/cm 3 However, the FCC solid solution phase of this alloy is unstable and tensile plasticity of more than 30% can be achieved only if the FCC + small amount of intermetallic compound structure is formed under the conditions of the rapid cooling copper mold casting. After high-temperature annealing treatment, the equilibrium structure of the alloy can be converted into a large amount of FCC + compound phases, so that the tensile plasticity is reduced to below 10%. At present, few high-entropy alloy systems having high density, high melting point, high plasticity and high strength at the same time have been reported.
Disclosure of Invention
Aiming at the defects of the transition group alloy system, the invention provides a high-density high-plasticity high-entropy alloy material and a preparation method thereof, which take Co-Ni-Cr-Fe alloy with unequal atomic ratio as a matrix, provide good plasticity, and regulate and control the melting point and the density of the alloy by adding certain amount of W, mo, re, hf, ta, C and other elements.
The invention adopts the following technical scheme:
Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy, and the high-entropy alloy material comprises Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i X is one or more of tantalum, hafnium, osmium, iridium, ruthenium, rhodium, palladium and platinum elements; wherein a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11, f is more than or equal to 0 and less than or equal to 11, h is more than or equal to 0 and less than or equal to 2, a +, b +, c +, d +, e +, f +, g +, h +, i =100. The element proportion in the composition expression is atomic percent.
In the above alloy, when f = g = h = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e It is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11, a +, b +, c +, d +, e =100.
In the above-mentioned Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when g = h = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e Mo f It is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11,0<f≤11，a+b+c+d+e+f＝100。
In the above-mentioned Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when f = h = i =0, the alloy composition may be represented as Co a Ni b Cr c Fe d W e Re g It is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11<g≤11，a+b+c+d+e+g＝100。
In the above-mentioned Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when f = g = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e X h It is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11,0<h≤2，a+b+c+d+e+h＝100。
In the above-mentioned Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when h = i =0, the alloy composition may be represented as Co a Ni b Cr c Fe d W e Mo f Re g Is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11<f≤11，0<g≤11，a+b+c+d+e+f+g＝100。
In the above-mentioned Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when g = i =0, the alloy composition may be represented as Co a Ni b Cr c Fe d W e Mo f X h Is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11<f≤11，0<h≤2，a+b+c+d+e+f+h＝100。
In the above-mentioned Co a Ni b Cr c Fe d WeMo f Re g X h (C,N) i In the alloy, when g =0, the composition thereof is represented by Co a Ni b Cr c Fe d W e Mo f X h (C,N) i It is characterized in that a is more than or equal to 28 and less than or equal to 35, b is more than or equal to 28 and less than or equal to 35, c is more than or equal to 10 and less than or equal to 20, d is more than or equal to 10 and less than or equal to 23, e is more than or equal to 1 and less than or equal to 11<f≤11，0<h≤2，0<i≤2，a+b+c+d+e+f+h+i＝100。
The preparation method of the high-density high-plasticity high-entropy alloy comprises the following steps:
1) Preparing raw materials: removing oxide skin on the surface of the high-purity raw material, converting into mass percent according to the set atomic percent, weighing the raw material by adopting a balance with the precision of 1mg, and carrying out ultrasonic cleaning and drying.
2) Alloy smelting: using consumable/non-consumable arc furnace or vacuum induction smelting furnace to smelt alloy, casting fast-cooling copper mould and pumping high vacuum to 5X 10 -3 Pa, then filling argon, turning over and repeating the smelting for at least 5 times. The Mo, W, re and X refractory elements are added in the form of pure elements or master alloys.
3) Homogenization treatment: and (3) sealing the cast rod in vacuum, filling argon, putting the cast rod into a muffle furnace, heating to 1200-1300 ℃ at the speed of 5-10 ℃/min, preserving the heat for 6-12 h, and carrying out homogenization annealing treatment.
4) Rolling: and cold rolling the cast rod after the homogenizing annealing, wherein the rolling deformation is 50-80%.
5) And (3) annealing treatment: heating the heat treatment furnace to 1000-1300 ℃ at the speed of 5-10 ℃/min, quickly opening the furnace door, putting into a rolling test bar of a vacuum sealed tube, and preserving the heat for 5 min-1 h to form a recrystallized structure.
When Co is present a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i When the alloy is an as-cast sample, the preparation method comprises only the step 1) and the step 2).
The key points of the technology of the invention are as follows:
1. the alloy with unequal atomic ratio of Co-Ni-Cr-Fe is used as a matrix, wherein the content of Co and Ni elements is high (more than or equal to 28 percent), and the content of Fe and Cr elements is low (less than or equal to 23 percent). The high content of Ni and Co elements can reduce the stacking fault energy of the alloy and improve the plasticity of the alloy and the solid solution capability of high-density elements such as W and the like. Compared with the prior CoCrFeNiW 0.4 Compared with the high-entropy alloy (the content of Co and Ni elements is 22.7%), the stability of the FCC phase of the alloy is greatly improved due to the increase of the content of CoCr elements, so that the high-entropy alloy shows excellent equilibrium structure tensile plasticity.
2. The elements W and Mo have very high densities and melting points. The solid solution of W and Mo elements in FCC matrix can obviously improve the strength, density and melting point of the alloy. When g = h = i =0, the composition thereof is expressed as Co a Ni b Cr c Fe d W e Mo f The yield strength is 240-800 MPa, the elongation is 15-65%, and the density is 8.9-10 g/cm 3 The melting point is 1600-1750 ℃.
3. When f = h = i =0, the alloy composition may be represented as Co a Ni b Cr c Fe d W e Re g . The high-density and high-melting-point Re element and Co can be dissolved in each other infinitely, the bonding property with Cr is good, crystal grains can be obviously refined by proper addition, fine grain strengthening is generated, and therefore the strength and the plasticity of the alloy are improved simultaneously.
4. When g = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e Mo f X h The refractory elements such as tantalum, hafnium, osmium, iridium, ruthenium, rhodium, palladium, platinum and the like have higher melting point and density and larger atomic radius, and the melting point, the density and the strength of the alloy can be further improved by properly adding the refractory elements without reducing the plasticity of the alloy.
5. When the composition range is Co a Ni b Cr c Fe d W e Mo f X h (C,N) i The addition of small atoms of C and N can produce interstitial solid solution strengthening, so that the strength and plasticity of the alloy are further improved.
The high-entropy alloy has the following beneficial effects: (1) The invention provides a Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i The high-entropy alloy uses Co-Ni-Cr-Fe alloy with unequal atomic ratio as base material, and adds a certain quantity of W, mo, re, hf, ta, C and other elements to regulate and control the melting point and density of the alloy, and its density is 8.9-10.2 g/cm 3 In the meantime. After rolling and subsequent heat treatment, the structural matrix of the series of high-entropy alloys is FCC, and part of the alloys contain TCP phases (mu phase and sigma phase). (2) Co provided by the invention a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i The high-entropy alloy has high density and high plasticity, and the maximum room-temperature tensile elongation reaches 90%.
Drawings
FIG. 1 is a Co prepared in example 2 of the present invention 30 Ni 30 Cr 10 Fe 21 Mo 4 W 5 Microstructure of the alloy. Wherein (a) is 1000 ℃/1h recrystallization annealing, and (b) is 1200 ℃/1h recrystallization annealing.
FIG. 2 is Co prepared according to example 4 of the present invention 30 Ni 30 Cr 10 Fe 21 W 9 Microstructure diagram of the alloy after 1300 ℃/10min recrystallization.
FIG. 3 is Co prepared according to example 2 of the present invention 30 Ni 30 Cr 10 Fe 21 Mo 4 W 5 Tensile curve of alloy at room temperature. Wherein (a) is 1000 ℃/1h recrystallization annealing, and (b) is 1200 ℃/1h recrystallization annealing.
FIG. 4 shows Co prepared in example 4 of the present invention 30 Ni 30 Cr 10 Fe 21 W 9 The room temperature tensile curve of the alloy after 1300 ℃/10min recrystallization annealing.
Detailed Description
To facilitate an understanding of the present invention, the present invention will be further described with reference to specific examples and drawings, but the present invention is not limited to the following examples.
Example 1
A high-density high-plasticity high-entropy alloy material contains Co 30 Ni 30 Cr 10 Fe 23 Mo 4 W 3 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W and Mo is removed, and the high-purity Cr sheets and Fe blocks do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, ultrasonically cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 3 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, electromagnetically stirring every time to ensure that the components are uniform, and suction casting the mixture into a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
3) Homogenizing: and (3) sealing the cast rod in vacuum, introducing argon, putting the tube into a muffle furnace, heating to 1200 ℃ at the speed of 10 ℃/min, preserving the temperature for 12h, and carrying out homogenization annealing treatment.
4) Rolling: and (4) cold rolling the cast rod after the homogenizing annealing, setting the reduction amount to be 60%, and finally obtaining a plate with the thickness of 4 mm.
5) Annealing treatment: and (3) heating the heat treatment furnace to 1000 ℃ and 1300 ℃ at the speed of 10 ℃/min, quickly opening the furnace door, putting the furnace door into a rolling test bar of a vacuum sealed tube, and respectively preserving heat for 1h and 10min to finish recrystallization.
And (3) analyzing an experimental result:
room temperature tensile properties were measured using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 1.
TABLE 1 Co 30 Ni 30 Cr 10 Fe 23 Mo 4 W 3 Mechanical properties of the alloy
Example 2
A high-density high-plasticity high-entropy alloy material is prepared from Co 30 Ni 30 Cr 10 Fe 21 Mo 4 W 5 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W and Mo is removed, and the high-purity Cr sheets and Fe blocks do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, ultrasonically cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 3 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, electromagnetically stirring every time to ensure that the components are uniform, and suction casting the mixture into a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
3) Homogenization treatment: and (3) sealing the cast rod in vacuum, introducing argon, putting the tube into a muffle furnace, heating to 1200 ℃ at the speed of 10 ℃/min, preserving the temperature for 12h, and carrying out homogenization annealing treatment.
4) Rolling: and (4) cold rolling the cast rod after the homogenizing annealing, setting the reduction amount to be 60%, and finally obtaining a plate with the thickness of 4 mm.
5) And (3) annealing treatment: and (3) heating the heat treatment furnace to 1000 ℃ and 1200 ℃ at the speed of 10 ℃/min, quickly opening the furnace door, putting the furnace door into a rolling test bar of a vacuum sealed tube, and respectively preserving heat for 1h to finish recrystallization.
And (3) analyzing an experimental result:
room temperature tensile property tests were conducted using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 2.
TABLE 2 Co 30 Ni 30 Cr 10 Fe 21 Mo 4 W 5 Mechanical properties of the alloy
The high-density and high-plasticity Co prepared by the embodiment 30 Ni 30 Cr 10 Fe 21 Mo 4 W 5 After the alloy is subjected to heat treatment at 1000 ℃/1h, a large amount of TCP (mu) phase is precipitated, and the crystal grain size of the matrix is below 10 mu m, as shown in FIG. 1 (a). The temperature was further raised to 1200 ℃ and the TCP phase was completely dissolved as shown in fig. 1 (b), whereby the elongation was greatly increased and the strength was decreased. In addition, the density of the alloy is significantly increased by increasing the content of the heavy element W.
Example 3
A high-density high-plasticity high-entropy alloy material is prepared from Co 30 Ni 30 Cr 17 Fe 10 W 3 Mo 4 Re 6 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W, mo and Re is removed, and the high-purity Cr sheets and Fe blocks do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, ultrasonically cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 5 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, performing electromagnetic stirring for each time to ensure that the components are uniform, and performing suction casting to obtain a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
3) Homogenizing: and (3) sealing the cast rod in vacuum, introducing argon, putting the tube into a muffle furnace, heating to 1200 ℃ at the speed of 10 ℃/min, preserving the temperature for 12h, and carrying out homogenization annealing treatment.
4) Rolling: and (4) cold rolling the cast rod after the homogenizing annealing, setting the reduction amount to be 60%, and finally obtaining a plate with the thickness of 4 mm.
5) Annealing treatment: and (3) heating the heat treatment furnace to 1300 ℃ at the speed of 10 ℃/min, quickly opening the furnace door, putting a rolling test bar of the vacuum sealed tube, and preserving heat for 5min to finish recrystallization.
And (3) analyzing an experimental result:
room temperature tensile properties were measured using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 3.
TABLE 3 Co 30 Ni 30 Cr 17 Fe 10 W 3 Mo 4 Re 6 Mechanical properties of the alloy
| Alloy (I) | Yield strength (MPa) | Elongation (%) | Density (g/cm) 3 ) |
| Recrystallization at 1300 ℃/5min | 398 | 59.7 | 9.88 |
As can be seen from tables 1 and 3, the addition of the refractory element Re not only improves the density and strength of the alloy, but also maintains the plasticity at 59.7%.
Example 4
A high-density high-plasticity high-entropy alloy material is prepared from Co 30 Ni 30 Cr 10 Fe 21 W 9 。
1) Preparing raw materials: the oxide skin on the surface of the high-purity Co, ni and WFe alloy is removed, and the high-purity Cr sheet does not need to be polished. Converting into mass percent according to the set atomic percent, wherein the amount of W is prepared by adopting WFe alloy, and then complementing the mass of Fe. The raw materials are weighed by a balance with the precision of 1mg, cleaned by ultrasonic waves and dried.
2) Alloy smelting: mixing raw materialsPutting into a non-consumable vacuum arc furnace from low melting point to high melting point, and vacuumizing to 5 × 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, performing electromagnetic stirring for each time to ensure that the components are uniform, and performing suction casting to obtain a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
3) Homogenizing: and (3) sealing the cast rod in vacuum, introducing argon, putting the tube into a muffle furnace, heating to 1200 ℃ at the speed of 10 ℃/min, preserving the temperature for 12h, and carrying out homogenization annealing treatment.
4) Rolling: and (4) cold rolling the cast rod after the homogenizing annealing, setting the reduction amount to be 60%, and finally obtaining a plate with the thickness of 4 mm.
5) Annealing treatment: and (3) heating the heat treatment furnace to 1300 ℃ at the speed of 10 ℃/min, quickly opening the furnace door, putting a rolling test bar of the vacuum sealed tube, and preserving heat for 10min to finish recrystallization.
And (3) analyzing an experimental result:
room temperature tensile properties were measured using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 4.
TABLE 4 Co 30 Ni 30 Cr 10 Fe 21 W 9 Mechanical properties of the alloy
| Alloy (II) | Yield strength (MPa) | Elongation (%) | Density (g/cm) 3 ) |
| Recrystallization at 1300 ℃/10min | 364 | 32 | 9.80 |
As can be seen from FIG. 3, co prepared in this example 30 Ni 30 Cr 10 Fe 21 W 9 After the alloy is subjected to 1300 ℃/10min heat treatment, only a small amount of TCP (mu) phase exists, so that higher plasticity is maintained. In comparative example 3, it was found that when Mo was replaced with W, the density of the alloy was increased and the precipitation of the μ phase was more likely to be promoted.
Example 5
A high-density high-plasticity high-entropy alloy material is prepared from Co 30 Ni 30 Cr 10 Fe 16.5 Mo 4 W 3 Hf 0.5 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W and Mo is removed, and the high-purity Cr sheets, fe blocks and Hf blocks do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, and carrying out ultrasonic cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 5 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, electromagnetically stirring every time to ensure that the components are uniform, and suction casting the mixture into a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
And (3) analysis of experimental results:
room temperature tensile property tests were conducted using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 5.
TABLE 5 Co 30 Ni 30 Cr 10 Fe 16.5 Mo 4 W 3 Hf 0.5 Mechanical properties of the alloy
| Alloy (I) | Yield strength (MPa) | Elongation (%) | Density (g/cm) 3 ) |
| As-cast condition | 288 | 22.8 | 9.0 |
Example 6
A high-density high-plasticity high-entropy alloy material is prepared from Co 30 Ni 30 Cr 10 Fe 16 Mo 4 W 3 Ta 1 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W, mo and Ta is removed, and the high-purity Cr sheets and Fe blocks do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, and carrying out ultrasonic cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 5 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, electromagnetically stirring every time to ensure that the components are uniform, and suction casting the mixture into a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
And (3) analyzing an experimental result:
room temperature tensile properties were measured using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 6.
TABLE 6 Co 30 Ni 30 Cr 10 Fe 16 Mo 4 W 3 Ta 1 Mechanical properties of the alloy
| Alloy (II) | Yield strength (MPa) | Elongation (%) | Density (g/cm) 3 ) |
| As-cast condition | 301 | 42.9 | 9.11 |
Example 7
A high-density high-plasticity high-entropy alloy material contains Co 30 Ni 30 Cr 10 Fe 15.8 Mo 4 W 3 Ta 1 C 0.2 。
1) Preparing raw materials: the oxide skin on the surfaces of high-purity Co, ni, W, mo and Ta is removed, and high-purity Cr sheets, fe blocks and C particles do not need to be polished. Converting into mass percent according to the set atomic percent, weighing the raw materials by adopting a balance with the precision of 1mg, ultrasonically cleaning and drying.
2) Alloy smelting: putting the raw materials into a non-consumable vacuum electric arc furnace according to the melting point from low to high, and pumping high vacuum to 5 multiplied by 10 -3 Pa, then filling argon, smelting by using 100-290A current, overturning and repeatedly smelting for at least 5 times, after the 2 nd smelting, performing electromagnetic stirring for each time to ensure that the components are uniform, and performing suction casting to obtain a rod, wherein the size of a copper mould is 10 multiplied by 50mm 3 。
And (3) analyzing an experimental result:
room temperature tensile properties were measured using a CMT4105 universal tensile tester, and the density was measured by the drainage method, and the results are shown in table 7.
TABLE 7 Co 30 Ni 30 Cr 10 Fe 15.8 Mo 4 W 3 Ta 1 C 0.2 Mechanical properties of the alloy
| Alloy (II) | Yield strength (MPa) | Elongation (%) | Density (g/cm) 3 ) |
| As-cast condition | 306 | 43.9 | 9.08 |
As can be seen from tables 5-7, the addition of Hf and Ta increases the density of the alloy and still has a higher plasticity. In addition, the addition of the C element improves the strength and the plasticity of the alloy.
Claims (10)
1. The high-density high-plasticity high-entropy alloy of the Co-Ni-Cr-Fe-W system is characterized in that the component of the high-entropy alloy material is Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i X is one or more of tantalum, hafnium, osmium, iridium, ruthenium, rhodium, palladium and platinum elements; wherein a is more than or equal to 28 and less than or equal to 30, b is more than or equal to 28 and less than or equal to 30, c is more than or equal to 17 and less than or equal to 20, d is more than or equal to 15.8 and less than or equal to 23, e is more than or equal to 3 and less than or equal to 11, f is more than or equal to 0 and less than or equal to 11, h is more than or equal to 0 and less than or equal to 2, a +, b +, c +, d +, e +, f +, g +, h +, i +=100; the element proportion in the composition expression is atomic percent;
the preparation method of the Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy,
1) Preparing raw materials: removing oxide skin on the surface of a high-purity raw material, weighing the raw material, and ultrasonically cleaning and drying the raw material;
2) Alloy smelting: melting the alloy using a consumable/non-consumable arc furnace or a vacuum induction melting furnace, evacuating to 5X 10 -3 Pa, then filling argon, turning over and repeatedly smelting for at least 5 times, and adding Mo, W, re and X high-melting-point elements in a pure element or intermediate alloy form;
3) Homogenization treatment: sealing the cast rod in vacuum, filling argon, putting the tube into a muffle furnace, heating to 1200-1300 ℃ at the speed of 5-10 ℃/min, preserving the heat for 6-12h, and carrying out homogenization annealing treatment;
4) Rolling: cold rolling the cast rod after the homogenizing annealing, wherein the rolling deformation is 50-80%;
5) And (3) annealing treatment: heating a heat treatment furnace to 1000 to 1300 ℃ at the speed of 5 to 10 ℃/min, quickly opening a furnace door, putting a rolling test bar of a vacuum sealed tube, and keeping the temperature for 5 to 1 hour to form a recrystallization structure to obtain Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i Alloying;
after rolling and subsequent heat treatment, the Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy structurally adopts FCC (fluid catalytic cracking), and has high density and high plasticity.
2. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is present in an amount sufficient to provide a high-plasticity a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when f = g = h = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e ，28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，a+b+c+d+e=100。
3. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is selected from the group consisting of a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when g = h = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e Mo f ，28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，0<f≤11，a+b+c+d+e+f=100。
4. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is selected from the group consisting of a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when f = h = i =0, the alloy composition may be represented as Co a Ni b Cr c Fe d W e Re g ，28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，0<g≤11，a+b+c+d+e+g=100。
5. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is selected from the group consisting of a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when f = g = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e X h ，28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，0<h≤2，a+b+c+d+e+h=100。
6. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is selected from the group consisting of a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when h = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e Mo f Re g ， 28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，0<f≤11，0<g≤11，a+b+c+d+e+f+g=100。
7. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is selected from the group consisting of a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when g = i =0, the composition thereof is represented as Co a Ni b Cr c Fe d W e Mo f X h ， 28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤11，0<f≤11，0<h≤2，a+b+c+d+e+f+h=100。
8. The Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy according to claim 1, wherein the Co is present in an amount sufficient to provide a high-plasticity a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i In the alloy, when g =0, the composition thereof is represented by Co a Ni b Cr c Fe d W e Mo f X h (C,N) i ， 28≤a≤35，28≤b≤35，10≤c≤20，10≤d≤23，1≤e≤10，2≤f≤10，0<h≤2，0<i≤2，a+b+c+d+e+f+h+i=100。
9. A method for preparing a Co-Ni-Cr-Fe-W high-density high-plasticity high-entropy alloy as claimed in any one of claims 1 to 8, wherein the method comprises the following steps:
1) Preparing raw materials: removing oxide skin on the surface of the high-purity raw material, weighing the raw material, ultrasonically cleaning and drying;
2) Alloy smelting: melting alloy by consumable/non-consumable arc furnace or vacuum induction melting furnace, and pumping high vacuum to 5 × 10 -3 Pa, then filling argon, turning over and repeatedly smelting for at least 5 times, and adding Mo, W, re and X high-melting-point elements in a pure element or intermediate alloy form;
3) Homogenization treatment: sealing the cast rod in vacuum, filling argon, putting the tube into a muffle furnace, heating to 1200-1300 ℃ at the speed of 5-10 ℃/min, preserving the heat for 6-12h, and carrying out homogenization annealing treatment;
4) Rolling: cold rolling the cast rod after the homogenizing annealing, wherein the rolling deformation is 50-80%;
5) Annealing treatment: heating the heat treatment furnace to 1000 to 1300 ℃ at the speed of 5 to 10 ℃/min, quickly opening the furnace door, putting the furnace door into a rolling test bar of a vacuum sealed tube, and preserving heat for 5min to 1h to form a recrystallization structure to obtain Co a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i And (3) alloying.
10. The method of claim 9, wherein Co is used as the binder a Ni b Cr c Fe d W e Mo f Re g X h (C,N) i When the alloy is an as-cast sample, the preparation method comprises only the step 1) and the step 2).
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