CN113337746B - Preparation method of carbide-reinforced high-entropy alloy composite material - Google Patents
Preparation method of carbide-reinforced high-entropy alloy composite material Download PDFInfo
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- C22C1/00—Making non-ferrous alloys
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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
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- B22F9/00—Making metallic powder or suspensions thereof
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- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- B22F3/10—Sintering only
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Abstract
The application relates to a scheme for preparing a carbide reinforced high-entropy alloy composite material (HEC) by adopting Mechanical Alloying (MA) and Spark Plasma Sintering (SPS), in particular to a method for preparing a high-entropy compound by simultaneously introducing carbide into a high-entropy alloy in two ways: (1) introducing a hydrocarbon additive into the high-entropy alloy to prepare an in-situ high-entropy alloy composite material, HEC for short, in a manner of generating carbide through a mechanical alloying reactionin(ii) a (2) Preparation of ex-situ high-entropy alloy composite material, HEC for short, by adding carbide particles into high-entropy alloyex. The preparation method of the FeCoNiCrMn high-entropy alloy composite material is described in detail by taking a typical case as follows: five metal powders of Fe, Co, Ni, Cr and Mn and a ball milling control agent C7H16Preparation of FeCoNiCrMn/C powder, i.e. HEC, by mechanical alloyinginAnd (3) powder. Then adding TaC and TiC powder and mixing to obtain FeCoNiCrMn/C/TaC/TiC powder, namely HECexAnd (3) powder. And finally, obtaining the FeCoNiCrMn high-entropy alloy composite material (HEC) through spark plasma sintering.
Description
Technical Field
The application belongs to the field of high-entropy alloy composite materials, and particularly relates to a preparation method of a carbide-reinforced high-entropy alloy composite material (HEC).
Background
The high-entropy alloy as a novel multi-component alloy breaks through the limitation of single main component of the traditional alloy composition, has excellent performance which can be kept stable in a wide temperature range, and generally forms a substitute of the traditional alloy (such as steel or compositions based on aluminum, magnesium and titanium). The FeCoNiCrMn alloy is a typical high-entropy alloy with a single FCC structure, and has higher ductility and higher fracture toughness at room temperature and low temperature. However, the yield strength of pure FeCoNiCrMn alloy is only 800MPa, and the lower yield strength and hardness limit its further application in the structural field. Therefore, how to improve the strength and hardness of the FeCoNiCrMn high-entropy alloy while ensuring the excellent performance of the FeCoNiCrMn high-entropy alloy has important research significance.
At present, in order to further improve the comprehensive mechanical properties of the FeCoNiCrMn alloy, researchers often process the FeCoNiCrMn alloy by severe plastic deformation such as cold-drawing deformation, hot forging and annealing, or change the chemical composition by introducing a metal element Al, a nonmetal element C, N, a ceramic phase TiC or SiC, and the like. Wherein, the ceramic reinforced metal matrix composite material has the advantages of both a tough metal matrix and a hard ceramic. Both TaC and TiC have high melting points, high hardness, good chemical stability and excellent wear resistance. In addition, TiC has good wetting properties and is widely used in metal matrix composites, and TaC is generally used as a grain refiner. The high-entropy alloy composite material (HEC) formed by introducing ceramic particles into the high-entropy alloy can improve the strength, hardness and wear resistance of the high-entropy alloy.
In terms of preparation processes, currently common preparation processes include a smelting method and a powder metallurgy method. The electric arc melting method is adopted, the structure defects such as segregation porosity and the like tend to occur, and the as-cast high-entropy alloy is large in brittleness and small in application range. The powder metallurgy method is used as a common process for preparing the particle-reinforced composite material, but the sintering temperature rise speed of the tubular furnace is low, the heat preservation time is long, the obtained sample structure has large crystal grains, and the high-entropy alloy with excellent comprehensive mechanical properties cannot be obtained. The discharge plasma sintering process is that under the combined action of a temperature field, a pressure field and an electric field, the temperature gradient and instantaneous high temperature formed by pulsating current in a sintering neck and inside particles promote the atomic diffusion process, so that the block material with fine grain structure is obtained. For the preparation of the high-entropy alloy composite material, the high-entropy alloy composite material (HEC) with excellent comprehensive mechanical property can be obtained by adopting a mode of combining Mechanical Alloying (MA) and Spark Plasma Sintering (SPS).
Disclosure of Invention
The purpose of the invention is as follows: in order to improve the hardness and the strength of the high-entropy alloy, the application provides a preparation method of a carbide-reinforced high-entropy alloy composite material (HEC)
The technical scheme is as follows: the invention provides a preparation method of a carbide reinforced high-entropy alloy composite material (HEC), which comprises the following steps:
step 1: HECinPreparation of the powder
Under the atmosphere of argon as protective gas, powder of five metal elements of Fe, Co, Ni, Cr and Mn and ball milling control agent (PCA) n-heptane C7H16Placing in a stainless steel ball milling tank, adding three kinds of grinding balls with different particle sizes, sealing the stainless steel tank body, fixing on the ball milling machine, and ball milling to obtain mechanical alloying FeCoNiCrMn/C powder (HEC) introducing n-heptane in-situ carbon elementinPowder;
step 2: HECexPreparation of the powder
Adding ceramic carbides TaC, TiC to HECinAfter the powder is ground and mixed again to obtain FeCoNiCrMn/C/TaC/TiC powder which introduces ceramic carbide ex-situ carbon source, namely HEC of next step discharge plasma sinteringexPowder;
and step 3: preparation of HEC bulk Material
HEC by spark plasma sinteringexAnd pressing and sintering the powder into blocks, then cooling the blocks to room temperature along with a sintering furnace, releasing pressure and vacuum, and taking out a final sample to obtain the FeCoNiCrMn high-entropy alloy composite material (HEC).
Preferably, in the step 1, the average particle size of the powder of the five metal elements of Fe, Co, Ni, Cr and Mn is 300 meshes, and the purity is more than or equal to 99.8%; in the step 2, the particle diameter of the TaC and TiC ceramic carbide powder is 100nm, and the purity is more than or equal to 99.9%.
Preferably, in the step 1, the total mass of FeCoNiCrMn and C (C)7H16) The mass ratio of (A) to (B) is 99.5 wt%: 0.5 wt%.
Preferably, in step 2, the HEC is preparedexMiddle and HECinThe mass ratio of the ceramic carbides TaC and TiC to the ceramic carbides TaC and TiC is 95 wt%: 5 wt%, wherein the molar ratio of TaC to TiC is 1: 1.
preferably, in step 1, HECinThe materials of a ball milling tank and grinding balls used in the ball milling process are all hard stainless steel, the volume of the ball milling tank is 1500mL, the diameters of the grinding balls are respectively 5mm, 10mm and 15mm, the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HEC areinThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and the total ball milling time is 40 h.
Preferably, in step 2, HECexThe materials of a ball milling tank and grinding balls used in the ball milling process are all hard stainless steel, the volume of the ball milling tank is 1500mL, the diameters of the grinding balls are respectively 5mm, 10mm and 15mm, the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HEC areexThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and the total ball milling time is 5 h.
Preferably, in step 3, HEC is addedexBefore the powder is put into a graphite die with the inner diameter of 20mm for sintering, graphite foil is filled in the inner cavity of the graphite die and the end face of a punch which is in contact with the powder so as to promote the demoulding of a sintered block sample.
Preferably, in the step 3, the graphite mold is placed in a sintering system in a vacuum environment, a thermocouple is placed for temperature measurement, the graphite mold is subjected to heat preservation and sintering at the temperature of 800-1000 ℃ for 10min at the set temperature, the sintering pressure is 60MPa, the heating rate is set to be 100 ℃/min, after sintering, the sintering furnace is cooled to the room temperature, and the FeCoNiCrMn high-entropy alloy composite material (HEC) is obtained after pressure and vacuum release.
Has the advantages that: compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
(1) the preparation method adopts a two-step method of Mechanical Alloying (MA) and Spark Plasma Sintering (SPS) to realize the preparation of the carbide reinforced high-entropy alloy composite material (HEC), and simultaneously introduces the carbide into the high-entropy alloy in two ways: (1) introducing a hydrocarbon additive into the high-entropy alloy to prepare an in-situ high-entropy alloy composite material, HEC for short, in a manner of generating carbide through a mechanical alloying reactionin(ii) a (2) Preparation of ex-situ high-entropy alloy composite material, HEC for short, by adding carbide particles into high-entropy alloyex。
(2) By adopting the method provided by the application, the method canObtaining a crystal structure consisting of FCC phase, M23C6Phase, M7C3HEC bulk material composed of a phase and a TaC phase of a molten salt (NaCl type) crystal structure, representing a HEA substrate of FCC single-phase solid solution, metal carbide M having precipitation strengthening effect23C6Phase sum M7C3A phase, and a TaC phase having a dispersion strengthening effect.
(5) The nano hardness values of the HEC are all more than 650HV, the yield strength is more than 1400MPa, high yield strength, high hardness and high wear resistance are shown, particularly, the nano hardness value of the HEC at-900 ℃ is 895HV, the yield strength at room temperature is 1760MPa, the elongation at room temperature is 7.85%, the friction coefficient is 0.250, and the material is expected to be used as a hard wear-resistant coating material and has wide application prospect.
Drawings
FIG. 1 is an XRD pattern of HEC samples at different SPS temperatures;
FIG. 2 is a TEM image of HEC samples prepared at SPS temperature of 900 ℃;
FIG. 3 is a room temperature stress-strain curve for different SPS temperature HEC samples;
FIG. 4 is a plot of room temperature coefficient of friction versus wear time for samples of HEC at various SPS temperatures.
Detailed Description
Implementation mode one
a.HECinPreparation of the powder
99.5 wt% HEA (FeCoNiCrMn): 0.5 wt% C (C)7H16) Placing in a 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectively, and sealing the stainless steel tank body, wherein the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HECinThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C powder, namely HEC, is obtained after ball milling for 40 hoursinAnd (3) powder.
b.HECexPreparation of the powder
Mixing 95 wt% HECin: placing 5 wt% ceramic carbide (molar ratio of TaC to TiC is 1: 1) in 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectivelyA stainless steel can body is covered by a rear seal cover, the weight ratio of the grinding balls to the HEC is 5:8:8exThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C/TaC/TiC powder is obtained after ball milling for 5 hours, namely HEC of SPS of next step of spark plasma sinteringexAnd (3) powder.
Preparation of HEC-800 ℃ block material
HEC (American ginseng)exThe powder was placed in a graphite mold with an inner diameter of 20mm filled with graphite foil, and then the graphite mold was placed in a sintering system under vacuum and a thermocouple was placed for temperature measurement. Setting the sintering time at 800 ℃, the heat preservation time at 10min, the sintering pressure at 60MPa and the heating rate at 100 ℃/min. And after sintering, cooling the sintering furnace to room temperature, releasing pressure and vacuum, and taking out to obtain the block material with the temperature of HEC-800 ℃.
d. The nanometer hardness value of the block material at the temperature of HEC-800 ℃ prepared by the experimental process is 656HV, the room-temperature yield strength is 1965MPa, the room-temperature elongation is 1%, and the friction coefficient is 0.443.
Second embodiment
a.HECinPreparation of the powder
99.5 wt% HEA (FeCoNiCrMn): 0.5 wt% C (C)7H16) Placing in a 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectively, and sealing the stainless steel tank body, wherein the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HECinThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C powder, namely HEC, is obtained after ball milling for 40 hoursinAnd (3) powder.
b.HECexPreparation of the powder
Mixing 95 wt% HECin: placing 5 wt% of ceramic carbide (molar ratio of TaC to TiC is 1: 1) in a 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectively, and then sealing the stainless steel tank body, wherein the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HECexThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C/TaC/TiC powder is obtained after ball milling for 5 hours, namely HEC of SPS of next step of spark plasma sinteringexAnd (3) powder.
Preparation of HEC-900 deg.C bulk material
HEC (American ginseng)exThe powder was placed in a graphite mold with an inner diameter of 20mm filled with graphite foil, and then the graphite mold was placed in a sintering system under vacuum and a thermocouple was placed for temperature measurement. Setting the sintering time at 900 ℃, the heat preservation time at 10min, the sintering pressure at 60MPa and the heating rate at 100 ℃/min. And after sintering, cooling the sintering furnace to room temperature, releasing pressure and vacuum, and taking out to obtain the block material with the temperature of HEC-900 ℃.
d. The nanometer hardness value of the block material at the temperature of HEC-900 ℃ prepared by the experimental process is 895HV, the room-temperature yield strength is 1760MPa, the room-temperature elongation is 7.85 percent, and the friction coefficient is 0.250.
Third embodiment
a.HECinPreparation of the powder
99.5 wt% HEA (FeCoNiCrMn): 0.5 wt% C (C)7H16) Placing in a 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectively, and sealing the stainless steel tank body, wherein the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HECinThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C powder, namely HEC, is obtained after ball milling for 40 hoursinAnd (3) powder.
b.HECexPreparation of the powder
Mixing 95 wt% HECin: placing 5 wt% of ceramic carbide (molar ratio of TaC to TiC is 1: 1) in a 1500mL stainless steel ball milling tank, adding three stainless steel grinding balls with diameters of 5mm, 10mm and 15mm respectively, and then sealing the stainless steel tank body, wherein the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HECexThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and FeCoNiCrMn/C/TaC/TiC powder is obtained after ball milling for 5 hours, namely HEC of SPS of next step of spark plasma sinteringexAnd (3) powder.
Preparation of HEC-1000 deg.C block material
HEC (American ginseng)exPlacing the powder into a graphite mold with an inner diameter of 20mm and filled with graphite foil, placing the graphite mold into a sintering system in a vacuum environment, and sinteringThermocouples were placed for temperature measurement. Setting the sintering time to 1000 ℃, the heat preservation time to 10min, the sintering pressure to 60MPa, and the heating rate to 100 ℃/min. And after sintering, cooling the sintering furnace to room temperature, releasing pressure and vacuum, and taking out to obtain the block material with the temperature of HEC-1000 ℃.
d. The nano hardness value of the HEC-1000 ℃ block material prepared by the experimental process is 682HV, the room-temperature yield strength is 1428MPa, the room-temperature elongation is 20.2%, and the friction coefficient is 0.263.
Through performance tests, the average nano hardness of the prepared FeCoNiCrMn high-entropy alloy composite material (HEC) is more than 650HV, and the yield strength is more than 1400 MPa.
Table 1 shows the data of nano vickers hardness, room temperature yield strength, compressive elongation and friction coefficient of FeCoNiCrMn high entropy alloy composite (HEC) obtained at different SPS temperatures. As can be seen from Table 1, as the SPS temperature rises, the hardness and the room temperature yield strength of the HEC show the tendency of increasing and then decreasing, the friction coefficient is reduced and then increased, and the HEC-900 ℃ shows the best comprehensive mechanical property.
Summary of embodiment results:
the invention adopts a two-step method of Mechanical Alloying (MA) and Spark Plasma Sintering (SPS) to realize the preparation of the carbide reinforced high-entropy alloy composite material (HEC), and simultaneously introduces the carbide into the high-entropy alloy in two ways: (1) introducing a hydrocarbon additive into the high-entropy alloy to prepare an in-situ high-entropy alloy composite material, HEC for short, in a manner of generating carbide through a mechanical alloying reactionin(ii) a (2) Preparation of ex-situ high-entropy alloy composite material, HEC for short, by adding carbide particles into high-entropy alloyex. The FeCoNiCrMn high-entropy alloy composite material (HEC) obtained finally has excellent comprehensive mechanics, and the phase structure of the composite material consists of an FCC phase and M23C6Phase, M7C3Phase and TaC phase of fused salt (NaCl type) crystal structure, representing HEA base of FCC single-phase solid solution, with strong precipitationChemically acting metal carbides M23C6Phase sum M7C3A phase, and a TaC phase having a dispersion strengthening effect. The HEC has high yield strength, high hardness and high wear resistance, the average nano-hardness exceeds 650HV, and the yield strength exceeds 1400 MPa. Therefore, the FeCoNiCrMn high-entropy alloy composite material (HEC) with excellent comprehensive mechanical properties can be prepared.
Claims (6)
1. A preparation method of a carbide reinforced high-entropy alloy composite material is characterized by comprising the following steps:
step 1: HECinPreparation of the powder
Under the atmosphere of argon as protective gas, powder of five metal elements of Fe, Co, Ni, Cr and Mn and ball-milling control agent n-heptane C7H16Placing in a stainless steel ball milling tank, adding three kinds of grinding balls with different particle sizes, sealing the stainless steel tank body, fixing on the ball milling machine, and ball milling to obtain mechanical alloying FeCoNiCrMn/C powder (HEC) introducing n-heptane in-situ carbon elementinPowder; in the step 1, the total mass and C of FeCoNiCrMn7H16The mass ratio of (A) to (B) is 99.5 wt%: 0.5 wt%;
step 2: HECexPreparation of the powder
Adding ceramic carbides TaC, TiC to HECinAfter the powder is ground and mixed again to obtain FeCoNiCrMn/C/TaC/TiC powder which introduces ceramic carbide ex-situ carbon source, namely HEC of next step discharge plasma sinteringexPowder; the preparation of HECexMiddle and HECinThe mass ratio of the ceramic carbides TaC and TiC to the ceramic carbides TaC and TiC is 95 wt%: 5 wt%, wherein the molar ratio of TaC to TiC is 1: 1;
and step 3: preparation of HEC bulk Material
HEC by spark plasma sinteringexAnd pressing and sintering the powder into blocks, then cooling the blocks to room temperature along with a sintering furnace, releasing pressure and vacuum, and taking out a final sample to obtain the FeCoNiCrMn high-entropy alloy composite material.
2. The method for preparing the carbide reinforced high-entropy alloy composite material according to claim 1, is characterized in that: in the step 1, the average particle size of the powder of the five metal elements of Fe, Co, Ni, Cr and Mn is 300 meshes, and the purity is more than or equal to 99.8%; in the step 2, the particle diameter of the TaC and TiC ceramic carbide powder is 100nm, and the purity is more than or equal to 99.9%.
3. The method for preparing the carbide reinforced high-entropy alloy composite material according to claim 1, is characterized in that: in step 1, HECinThe materials of a ball milling tank and grinding balls used in the ball milling process are all hard stainless steel, the volume of the ball milling tank is 1500mL, the diameters of the grinding balls are respectively 5mm, 10mm and 15mm, the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HEC areinThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and the total ball milling time is 40 h.
4. The method for preparing the carbide reinforced high-entropy alloy composite material according to claim 1, is characterized in that: in step 2, HECexThe materials of a ball milling tank and grinding balls used in the ball milling process are all hard stainless steel, the volume of the ball milling tank is 1500mL, the diameters of the grinding balls are respectively 5mm, 10mm and 15mm, the weight ratio of the three grinding balls is 5:8:8, and the grinding balls and HEC areexThe mass ratio of the powder is 15:1, the ball milling speed is set to be 400r/min, and the total ball milling time is 5 h.
5. The method for preparing the carbide reinforced high-entropy alloy composite material according to claim 1, is characterized in that: in step 3, HEC is addedexBefore the powder is put into a graphite die with the inner diameter of 20mm for sintering, graphite foil is filled in the inner cavity of the graphite die and the end face of a punch which is in contact with the powder so as to promote the demoulding of a sintered block sample.
6. The method for preparing the carbide reinforced high-entropy alloy composite material according to claim 1, is characterized in that: and 3, placing the graphite mold into a sintering system in a vacuum environment, placing a thermocouple into the sintering system for temperature measurement, carrying out heat preservation sintering at the temperature of 800 plus materials and 1000 ℃ for 10min at the set temperature, wherein the sintering pressure is 60MPa, the heating rate is set to be 100 ℃/min, cooling the sintering furnace to the room temperature after sintering, releasing the pressure and vacuum, and taking out the graphite mold to obtain the FeCoNiCrMn high-entropy alloy composite material.
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