CN114737098A - Preparation method of Nb-Co-Hf-Mo-Sc-Er alloy - Google Patents
Preparation method of Nb-Co-Hf-Mo-Sc-Er alloy Download PDFInfo
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er, wherein the high-entropy alloy comprises the following components in atomic ratio: 18.0-22.0at.% Nb, 18.0-22.0at.% Co, 18.0-22.0at.% Hf, 18.0-22.0at.% Mo, 6.0-14.0at.% Sc, 6.0-14.0at.% Er. The preparation method of the alloy comprises the following steps: s1, weighing the alloy according to the element proportion; s2, putting the weighed powder into a ball milling tank for ball milling according to the ball-to-material ratio of 6: 1-9: 1; s3, sieving and separating the powder and the grinding balls in an argon glove box to obtain the Nb-Co-Hf-Mo-Sc-Er powder; s4, carrying out vacuum hot pressing sintering on the powder after cold pressing; and S5, carrying out deformation treatment on the obtained hot-pressed blank, and then carrying out equal channel angular extrusion treatment to obtain a high-performance product. The invention does not add any process control agent, can prevent the pollution to the powder, and can improve the efficiency of mechanical alloying, and the prepared product has excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er.
Background
In 2004, professor yeasts school leaf-root professor formally proposes a high-entropy alloy, and the high-entropy alloy is defined as: the high-entropy alloy is a multi-principal-element alloy which is composed of 5 or more principal elements with equal molar ratio or nearly equal molar ratio, wherein the atomic fraction of each principal element is between 5 and 35 percent, and a simple solid solution can be formed. The refractory high-entropy alloy mainly comprises refractory elements and has good high-temperature performance. The refractory high-entropy alloy is a novel metal material taking a plurality of refractory elements as main elements, has unique mechanical, physical and chemical properties, and particularly shows excellent performances in the aspects of high-temperature mechanics, radiation resistance and the like. Although the high-entropy alloy systems are classified in a large number, different from the traditional single-principal-element alloy, the high-entropy alloy has the advantages of simple and stable structure due to the microcosmic characteristics of high mixing entropy, high lattice distortion, delayed diffusion and the like, and particularly, the excellent high-temperature mechanical property provides great possibility for replacing the high-temperature-resistant nickel-based high-temperature alloy. The arc melting is the most common method for preparing refractory high-entropy alloy block materials, the melting temperature is high, the closed atmosphere is pure, the impurity content of non-metallic elements is very low, the possibility of slight pollution of a crucible or an electrode material exists, but the phenomenon of segregation of intercrystalline components in the alloy grains in the arc melting is large, and the segregation phenomenon is serious. As elements such as Nb, Co, Hf, Mo, Sc, Er and the like have high chemical activity and larger physical property difference, the reaction heat in the smelting process is high, serious segregation of Nb element and larger burning loss of Co element are easy to occur, and the uniform chemical components of the Nb-Co-Hf-Mo-Sc-Er alloy are difficult to ensure. On the contrary, the block refractory high-entropy alloy prepared by powder metallurgy has more uniform element distribution and finer grain size, and can obviously improve the comprehensive mechanical property at room temperature. The equal channel angular extrusion is a large plastic deformation processing method which utilizes pure shear deformation to refine crystal grains, and can obviously improve the mechanical property of the alloy.
Disclosure of Invention
According to the invention, no process control agent is added, and the Nb-Co-Hf-Mo-Sc-Er powder with uniform element distribution and fine particle size is prepared by reasonably controlling mechanical alloying ball milling parameters and ball milling environment and adopting reasonable protective measures, so that high-quality mechanical alloying powder is provided for subsequent sintering, equal-diameter angular extrusion and other processes. The invention obtains products with excellent performance through thermoplastic extrusion and equal channel angular extrusion. The method has low cost and can be used for mass production. Meanwhile, the obtained alloy has fine crystal grains and excellent comprehensive performance.
The specific principle of the invention is as follows: the Nb-Co-Hf-Mo-Sc-Er particles are uniformly diffused to the melt by mechanical stirring of high-energy ball milling and plastic rheology of vacuum hot pressing. Meanwhile, the compactness of the Nb-Co-Hf-Mo-Sc-Er can be effectively enhanced in the vacuum hot pressing process. In addition, the shearing force is utilized to crush the crystal grains in the extrusion process, and dislocation entanglement is caused to provide driving force for dynamic recrystallization of the high-entropy alloy, so that the purpose of refining the crystal grains is achieved. The alloy can be effectively strengthened in the process of carrying out equal channel angular extrusion treatment, thereby obtaining products with excellent mechanical properties.
In order to achieve the purpose, the invention provides a preparation method of Nb-Co-Hf-Mo-Sc-Er, and the high-entropy alloy comprises the following components in atomic ratio: 18.0-22.0at.% Nb, 18.0-22.0at.% Co, 18.0-22.0at.% Hf, 18.0-22.0at.% Mo, 6.0-14.0at.% Sc, 6.0-14.0at.% Er. Which comprises the following steps:
s1, weighing the alloy according to the element proportion;
s2, adding the weighed six element powders into a ball milling tank, and adding three stainless steel grinding balls with different diameters according to a ball-to-material ratio of 6: 1;
s3, vacuumizing the ball milling tank, filling argon, and repeating for 2-4 times;
s4, before high-energy ball milling, mixing powder for 8 hours at a rotating speed of 150-180 r/min, and uniformly mixing element powder, namely placing a ball milling tank on a ball mill for low-energy powder mixing ball milling, wherein the powder mixing time is 8 hours, and stopping the machine for rest for 10 minutes every 1 hour of mixed powder;
s5, performing high-energy ball milling on the ball milling tank in a ball mill for 50-70 h, and stopping the ball milling tank for rest for 20min every 1 h;
s6, standing the ball milling tank in an argon glove box for 24 hours, and then opening an upper cover of the ball milling tank for passivation, wherein the passivation time is not less than 24 hours;
s7, sieving and separating the powder and the grinding ball in an argon glove box to obtain Nb-Co-Hf-Mo-Sc-Er mixed powder, reducing the pollution of the grinding ball and the tank wall to the powder by utilizing a small amount of welding of the powder on the grinding ball and the tank wall, adding no process control agent, reducing the oxidation and pollution of a sample in the mechanical alloying process, and fully diffusing each simple substance atom to prepare the mixed powder with uniformly distributed elements. The mutual solid solution among solid powder atoms is realized by means of higher energy provided by the ball mill, and a plurality of adverse factors caused by different melting points and diffusion coefficients of elements can be effectively avoided; the pollution of the grinding ball and the tank wall to the powder is reduced by utilizing a small amount of welding of the powder on the grinding ball and the tank wall, and no process control agent is added, so that the oxidation and the pollution of a sample are reduced in the mechanical alloying process, and each simple substance atom can be fully diffused;
s8, keeping the pressure of the Nb-Co-Hf-Mo-Sc-Er mixed powder obtained in the step S7 at 400MPa for 10min through cold pressing, and preparing a precast block;
s9, placing the precast block obtained in the step S8 into a graphite mold, and in order to ensure higher compactness of the blank in the hot pressing process, carrying out vacuum hot pressing sintering, wherein the sintering temperature is controlled to be 1500--5Above MPa; after the sintering temperature is reached, controlling the heat preservation time to be 60-120 min to obtain a blank;
s10, performing plastic thermal deformation treatment on the blank obtained in the step S9, wherein the extrusion ratio is controlled to be 16-42, the extrusion rate is controlled to be 1-10 mm/min, and the temperature is controlled to be 1350-; the obtained rod-like material is extruded at an equal channel angle again, the temperature is controlled at 650-700 ℃, the angle is controlled at 110-160 ℃, the number of times of extrusion is controlled at 5-7 times, and the extrusion rate is controlled at 1-10 mm/min.
Preferably, the stainless steel balls have diameters of 5mm, 10mm and 20mm and a mass ratio of 6:4: 1.
Preferably, the total volume of material and grinding balls is no greater than 1/3 of the total volume of the mill pot.
Preferably, in step S4, the rotation speed of the low-energy powder mixing ball mill is 150 to 180 r/min.
Preferably, in step S5, the rotation speed of the high-energy ball mill is 390 r/min.
Preferably, the sieve in step S7 is a 400-mesh stainless steel sieve, and the sieve is washed with alcohol before being sieved.
Preferably, the vacuum degree range in step S9 is 1 × 10-5-3×10-5MPa。
Compared with the prior art, the invention has the following advantages:
(1) the invention realizes solid solution diffusion among atoms in the solid state of the powder, thereby effectively avoiding the problems of Co element burning loss, component segregation and the like in the process of liquid melting in the casting process;
(2) the method does not add any process control agent, can prevent the pollution to the powder, can improve the efficiency of mechanical alloying, can fully diffuse each simple substance atom, and obtains the mechanical alloying Nb-Co-Hf-Mo-Sc-Er powder with uniformly distributed elements. Vacuumizing, filling argon and operating in a glove box filled with argon control the oxidation phenomenon of powder in the mechanical alloying process;
(3) the invention adopts larger ball-material ratio and reasonable matching of grinding balls with different diameters, so that the mechanical alloying has higher powder yield. The powder is uniformly mixed at a low rotating speed before high-energy ball milling, so that the uniform mixing of the single-element powder is facilitated, and the efficiency during high-energy ball milling is improved;
(4) according to the invention, an extrusion process is adopted to crush the crystal grains by utilizing the shearing force, and dislocation entanglement is caused to provide a driving force for dynamic recrystallization of the high-entropy alloy, so that the purpose of refining the crystal grains is achieved; the alloy is further effectively strengthened through the equal channel angular extrusion treatment; the effects of mechanical alloying, hot-pressing sintering, plastic thermal deformation and equal channel angular extrusion synergistic strengthening and toughening of the refractory high-entropy alloy are realized.
Examples
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are further described in detail below with reference to the embodiments.
The first embodiment is as follows:
s1, according to the atomic ratio of the components of the high-entropy alloy: 18.0-22.0at.% of Nb, 18.0-22.0at.% of Co, 18.0-22.0at.% of Hf, 18.0-22.0at.% of Mo, 6.0-14.0at.% of Sc and 6.0-14.0at.% of Er, respectively weighing niobium powder, cobalt powder, hafnium powder, molybdenum powder, scandium powder and erbium powder according to the proportion, and totally 45g of elemental element powder;
s2, adding the weighed single-element powder into a stainless steel ball-milling tank, and putting stainless steel balls with the diameters of 5mm, 10mm and 20mm into the ball-milling tank, wherein the mass of each ball is 147.3g, 98.2g and 24.6g respectively;
s3, vacuumizing the stainless steel ball-milling tank, filling argon, vacuumizing, filling argon, and repeating for 3 times;
s4, placing the stainless steel ball milling tank on a planetary ball mill, and performing low-energy powder mixing ball milling at the rotating speed of 150r/min for 8h, stopping the machine for rest for 10min every 1 h;
s5, performing high-energy ball milling on a stainless steel ball milling tank on a planetary ball mill at a rotating speed of 390r/min for 50h, and stopping the ball milling machine for rest for 20min every 1 h;
s6, standing the stainless steel ball milling tank in a glove box filled with argon for 24 hours, taking down an upper cover of the ball milling tank, and placing the ball milling tank in the glove box for passivation for 72 hours;
s7, separating the grinding balls and the powder in an argon glove box by using a 400-mesh stainless steel sieve to obtain powder, namely the Nb-Co-Hf-Mo-Sc-Er mixed powder. Taking a proper amount of solid solution powder, placing the powder in a copper pipe with the height of 10mm, the inner diameter of 7mm and the outer diameter of 10mm, pressing the copper pipe containing the powder into a round cake with the height of 4mm under a hydraulic press, and measuring the hardness of the powder to be 980 HV;
s8, keeping the pressure of the Nb-Co-Hf-Mo-Sc-Er mixed powder obtained in the step S7 at 400MPa for 10min through cold pressing, and preparing a precast block;
s9, placing the precast block obtained in the step S8 into a graphite mold, and performing vacuum hot-pressing sintering, wherein the sintering temperature is controlled to be 1580 ℃, the axial pressure is controlled to be 20MPa, the heating rate is controlled to be 10 ℃/min, and the vacuum degree is maintained to be 3 multiplied by 10-5MPa. After the sintering temperature is reached, the heat preservation time is controlled to be 60min, and then a blank is obtained. And carrying out plastic thermal deformation treatment on the obtained blank to reduce defects and broken grains, wherein the extrusion ratio is controlled to be 16, the extrusion rate is controlled to be 1mm/min, and the temperature is controlled to be 1350 ℃. The obtained rod-shaped material is subjected to equal channel angular extrusion again, the temperature is controlled to be 650 ℃, the angle is controlled to be 110 ℃, the extrusion frequency is controlled to be 5 times, the extrusion rate is controlled to be 1mm/min, and the ultimate tensile strength of the rod-shaped material is improved by 28.92 percent compared with that of a matrix.
Example two:
s1, according to the atomic ratio of the components of the high entropy alloy: nb 20.0-21.0at.%, Co 20.0-21.0at.%, Hf 20.0-21.0at.%, Mo 20.0-21.0at.%, Sc 8.0-10.0at.%, and Er 8.0-10.0at.%, respectively weighing niobium powder, cobalt powder, hafnium powder, molybdenum powder, scandium powder, and erbium powder in proportion, to total 45g of elemental element powder;
s2, adding the weighed single-element powder into a stainless steel ball milling tank, and adding 360g of stainless steel grinding balls according to the ball-material ratio of 8:1, wherein the diameters of the stainless steel grinding balls are 5mm, 10mm and 20mm, and the weights of the stainless steel grinding balls are 196.4 g, 130.9 g and 32.7g respectively;
s3, vacuumizing the stainless steel ball milling tank, filling argon, vacuumizing, filling argon, and repeating for 3 times;
s4, placing the stainless steel ball milling tank on a planetary ball mill, and performing low-energy powder mixing ball milling at a rotating speed of 180r/min for 8 hours, and stopping the machine for rest for 10min every 1 hour of powder mixing;
s5, performing high-energy ball milling on a stainless steel ball milling tank on a planetary ball mill at a rotating speed of 390r/min for 50h, and stopping the ball milling machine for rest for 20min every 1 h;
s6, standing the stainless steel ball milling tank in a glove box filled with argon for 24 hours, taking down an upper cover of the ball milling tank, and placing the ball milling tank in the glove box for passivation for 72 hours;
s7, separating the grinding balls from the powder by using a stainless steel sieve of 400 meshes to obtain powder, namely Nb-Co-Hf-Mo-Sc-Er mixed powder. Placing a proper amount of Nb-Co-Hf-Mo-Sc-Er mixed powder into a copper pipe with the height of 10mm, the inner diameter of 7mm and the outer diameter of 10mm, pressing the copper pipe containing the powder into a round cake with the height of 4mm under a hydraulic press, and measuring the hardness of the solid solution powder to be 1020 HV;
s8, keeping the pressure of the Nb-Co-Hf-Mo-Sc-Er mixed powder obtained in the step S7 at 400MPa for 10min through cold pressing, and preparing a precast block;
s9, placing the precast block obtained in the step S8 into a graphite mold, and performing vacuum hot-pressing sintering, wherein the sintering temperature is controlled to 1590 ℃, the axial pressure is controlled to 35MPa, the heating rate is controlled to 10 ℃/min, and the vacuum degree is maintained at 1 x 10-5MPa. After the sintering temperature is reached, the heat preservation time is controlled to be 90min, and then a blank is obtained. And carrying out plastic thermal deformation treatment on the obtained blank to reduce defects and broken crystal grains, wherein the extrusion ratio is controlled to be 42, the extrusion speed is controlled to be 10mm/min, and the temperature is controlled to be 1450 ℃. The obtained rod-shaped material is extruded again at equal channel angle, the temperature is controlled at 680 ℃, the angle is controlled at 160 degrees, and the extrusion times are carried outThe extrusion speed is controlled to be 10mm/min for 7 times, and the ultimate tensile strength is improved by 30.67 percent compared with the matrix.
Example three:
s1, according to the atomic ratio of the components of the high-entropy alloy: respectively weighing niobium powder, cobalt powder, hafnium powder, molybdenum powder, scandium powder and erbium powder according to a proportion, wherein the total amount of the powder is 45g of simple substance element powder, and the Nb content is 20.0at.%, the Co content is 20.0at.%, the Hf content is 20.0at.%, the Mo content is 20.0at.%, the Sc content is 10.0at.%, and the Er content is 10.0 at.%;
s2, adding the weighed single-element powder into a stainless steel ball milling tank, and adding 405g of stainless steel grinding balls according to the ball-material ratio of 8:1, wherein the diameters of the stainless steel grinding balls are 5mm, 10mm and 20mm, and the weights of the stainless steel grinding balls are 220.9 g, 147.3g and 36.8g respectively;
s3, vacuumizing the stainless steel ball milling tank, filling argon, vacuumizing, filling argon, and repeating for 3 times;
s4, placing the stainless steel ball milling tank on a planetary ball mill to perform low-energy powder mixing ball milling at the rotating speed of 150r/min for 8 hours, and stopping the machine for rest for 10min every 1 hour of powder mixing;
s5, performing high-energy ball milling on a stainless steel ball milling tank on a planetary ball mill at a rotating speed of 390r/min for 70h, and stopping the ball milling machine for rest for 20min every 1 h;
s6, standing the stainless steel ball milling tank in a glove box filled with argon for 24 hours, taking down an upper cover of the ball milling tank, and placing the ball milling tank in the glove box for passivation for 72 hours;
s7, separating the grinding balls from the powder by using a stainless steel sieve of 400 meshes to obtain powder, namely Nb-Co-Hf-Mo-Sc-Er mixed powder. Placing a proper amount of solid solution in a copper pipe with the height of 10mm, the inner diameter of 7mm and the outer diameter of 10mm, pressing the copper pipe containing the powder into a round cake with the height of 4mm under a hydraulic press, and measuring the hardness of the solid solution powder to be 995 HV;
s8, keeping the pressure of the Nb-Co-Hf-Mo-Sc-Er mixed powder obtained in the step S7 at 400MPa for 10min through cold pressing, and preparing a precast block;
s9, putting the precast block obtained in the step S8 into a graphite mould, and carrying out vacuum hot-pressing sintering, wherein the sintering temperature is controlled to 1600 ℃, the axial pressure is controlled to 50MPa, the heating rate is controlled to 10 ℃/min, and the vacuum degree is kept at 2 x 10-5MPa. To achieve the purpose of burningAnd after the junction temperature, controlling the heat preservation time to be 120min, and then obtaining a blank. And carrying out plastic thermal deformation treatment on the obtained blank to reduce defects and broken crystal grains, wherein the extrusion ratio is controlled to be 42, the extrusion rate is controlled to be 10mm/min, and the temperature is controlled to be 1400 ℃. The obtained rod-shaped material is subjected to equal channel angular extrusion again, the temperature is controlled to be 650 ℃, the angle is controlled to be 110 ℃, the extrusion frequency is controlled to be 7 times, the extrusion rate is controlled to be 10mm/min, and the ultimate tensile strength of the rod-shaped material is improved by 29.88% compared with that of a matrix.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation method of a refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er comprises the following components in atomic ratio: 18.0-22.0at.% Nb, 18.0-22.0at.% Co, 18.0-22.0at.% Hf, 18.0-22.0at.% Mo, 6.0-14.0at.% Sc, 6.0-14.0at.% Er; the method is characterized in that: which comprises the following steps:
s1, weighing the alloy according to the element proportion;
s2, adding the weighed six element powders into a ball milling tank, and adding three stainless steel grinding balls with different diameters according to a ball-to-material ratio of 6: 1;
s3, vacuumizing the ball milling tank, filling argon, and repeating for 2-4 times;
s4, before high-energy ball milling, mixing powder for 8 hours at a rotating speed of 150-180 r/min, uniformly mixing element powder, namely placing a ball milling tank on a ball mill for low-energy powder mixing ball milling, wherein the powder mixing time is 8 hours, and stopping the machine for rest for 10 minutes every 1 hour of powder mixing;
s5, performing high-energy ball milling on the ball milling tank in a ball mill for 50-70 h, and stopping the ball milling tank for rest for 20min every 1 h;
s6, standing the ball milling tank in an argon glove box for 24 hours, and then opening an upper cover of the ball milling tank for passivation, wherein the passivation time is not less than 24 hours;
s7, sieving and separating the powder and the grinding ball in an argon glove box to obtain Nb-Co-Hf-Mo-Sc-Er mixed powder, reducing the pollution of the grinding ball and the tank wall to the powder by utilizing a small amount of welding of the powder on the grinding ball and the tank wall, adding no process control agent, reducing the oxidation and pollution of a sample in the mechanical alloying process, and fully diffusing each simple substance atom to prepare the mixed powder with uniformly distributed elements;
the mutual solid solution among solid powder atoms is realized by means of higher energy provided by the ball mill, and a plurality of adverse factors caused by different melting points and diffusion coefficients of elements can be effectively avoided; the powder is welded on the grinding ball and the tank wall in a small amount to reduce the pollution of the grinding ball and the tank wall to the powder, and no process control agent is added to reduce the oxidation and the pollution of a sample in the mechanical alloying process so that each simple substance atom can be fully diffused;
s8, keeping the pressure of the Nb-Co-Hf-Mo-Sc-Er mixed powder obtained in the step S7 at 400MPa for 10min through cold pressing, and preparing a precast block;
s9, placing the precast block obtained in the step (8) into a graphite die, and in order to ensure higher compactness of the blank in the hot pressing process, carrying out vacuum hot pressing sintering, wherein the sintering temperature is controlled to be 1500--5Is more than MPa; after the sintering temperature is reached, controlling the heat preservation time to be 60-120 min to obtain a blank;
s10, performing plastic thermal deformation treatment on the obtained blank, wherein the extrusion ratio is controlled to be 16-42, the extrusion rate is controlled to be 1-10 mm/min, and the temperature is controlled to be 1350-; the obtained rod-like material is extruded at an equal channel angle again, the temperature is controlled at 650-700 ℃, the angle is controlled at 110-160 ℃, the number of times of extrusion is controlled at 5-7 times, and the extrusion rate is controlled at 1-10 mm/min.
2. The method for preparing the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er by mechanical alloying according to claim 1, is characterized in that: the diameters of the stainless steel balls are 5mm, 10mm and 20mm, and the mass ratio is 6:4: 1.
3. The method for preparing the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er by mechanical alloying according to claim 1, is characterized in that: the total volume of the materials and the grinding balls is not more than 1/3 of the total volume of the ball milling tank.
4. The method for preparing the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er by mechanical alloying according to claim 1, is characterized in that: in step S4, the low-energy powder mixing ball milling speed is 150-180 r/min.
5. The method for preparing the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er by mechanical alloying according to claim 1, is characterized in that: in step S5, the rotation speed of the high-energy ball mill is 390 r/min.
6. The method for preparing the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er by mechanical alloying according to claim 4, is characterized in that: the sieve in step S7 is a 400 mesh stainless steel sieve, and before sieving, the sieve is cleaned with alcohol.
7. The preparation method of the refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er according to claim 1, characterized in that: the vacuum degree range in step S9 is 1X 10-5-3×10-5MPa。
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