CN113070483A - Method for preparing FeCoNi intermediate entropy alloy with low cost and short process - Google Patents

Method for preparing FeCoNi intermediate entropy alloy with low cost and short process Download PDF

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CN113070483A
CN113070483A CN202110321561.1A CN202110321561A CN113070483A CN 113070483 A CN113070483 A CN 113070483A CN 202110321561 A CN202110321561 A CN 202110321561A CN 113070483 A CN113070483 A CN 113070483A
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feconi
entropy alloy
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赵青
都基军
刘承军
李文杰
姜茂发
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Northeastern University China
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F3/1017—Multiple heating or additional steps
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract

The invention provides a method for preparing FeCoNi intermediate entropy alloy with low cost and short flow, which adopts a chemical coprecipitation method, takes a low-cost chemical reagent as a raw material, prepares a FeCoNi intermediate entropy alloy precursor through aging, suction filtration and drying, puts the precursor into a high-temperature ball mill, generates a large amount of active sites along with grinding, refining and uniform mixing of grinding balls to materials in the mechanical alloying process, reduces the chemical reaction activation energy in the reduction process, excites the low-temperature chemical reaction and reduces the energy consumption; in addition, three processes of calcination, reduction and alloying are completed in one device, so that the device has multiple functions, the process flow is greatly shortened, and the introduction of impurities is reduced. Therefore, the method meets the requirements of preparing the FeCoNi intermediate entropy alloy with low cost, low energy consumption, short flow and few impurities.

Description

Method for preparing FeCoNi intermediate entropy alloy with low cost and short process
Technical Field
The invention relates to the technical field of alloy material preparation, in particular to a method for preparing an entropy alloy in FeCoNi with low cost and short process.
Background
Materials play an important role in the development of human history, and metallic materials are more indispensable substances in human life. Metal materials are required for small needles and large aircraft carriers. After the industrial revolution, the single-component metal material cannot meet the requirements of people on the performance of the metal material, so that the metal material performance is optimized by forming an alloy through chemical combination among metals.
According to the magnitude of the entropy value, the alloy can be divided into low-entropy alloy, medium-entropy alloy and high-entropy alloy. Compared with low-entropy alloy, the medium-entropy and high-entropy alloy contains various components, has various varieties and complex components, so the medium-entropy and high-entropy alloy has a plurality of special properties different from those of the low-entropy alloy. However, in recent years, researchers find that although the performance of the high-entropy alloy is excellent, in comparison with the performance-price ratio, the high-entropy alloy contains more components than the medium-entropy alloy, and the performance-price ratio of the high-entropy alloy is not as high as that of the medium-entropy alloy, so that the medium-entropy alloy can replace the high-entropy alloy to a certain extent on the premise of meeting the performance requirement. The FeCoNi intermediate entropy alloy is used as a novel functional material, and has application in the fields of electrocatalysis, hard alloy, magnetic materials and the like due to unique physical and chemical properties.
Chinese patent (CN110576185A) discloses a preparation method of nanocrystalline high-entropy alloy powder, which is prepared by mixing cobalt powder, chromium powder, iron powder, nickel powder, manganese powder, aluminum powder and titanium powder and then carrying out mechanical ball milling. Chinese patent (CN110205537A) mixes aluminum powder, titanium powder, magnesium blocks or particles and lithium blocks or particles; then putting the ball-milling tank into a ball-milling tank, and vacuumizing the ball-milling tank or filling inert protective gas into the ball-milling tank; ball milling is carried out to form the high-entropy alloy powder with the single-phase face-centered cubic structure. In Chinese patent (CN109913717B), metals and non-metals (aluminum powder, copper powder, chromium powder, iron powder, nickel powder and silicon powder) are uniformly mixed according to a certain proportion by means of mechanical alloying, then alloying is carried out, and single-phase solid solution high-entropy alloy powder is successfully prepared by drying the alloy powder. In the technology, the raw materials used for preparing the high-entropy alloy powder basically adopt pure metal simple substance powder, and mechanical alloying is carried out by means of a traditional ball mill, so that the pure metal simple substance powder is subjected to solid solution to form the high-entropy alloy powder. The preparation method of the medium-entropy alloy powder is basically similar to that of the high-entropy alloy powder, namely pure metal simple substance powder is adopted as a raw material for mechanical alloying, and the pure metal simple substance powder is very expensive in selling price. Displaying according to market selling price: in 2021, the high-purity iron powder is about 4 ten thousand yuan/ton, the high-purity cobalt powder is about 30 ten thousand yuan/ton, the high-purity nickel powder is about 13 ten thousand yuan/ton, and the high price is high, and the medium entropy alloy components are more, so that the preparation cost of the FeCoNi medium entropy alloy powder is very high, and the production and application of the FeCoNi medium entropy alloy are greatly limited.
Research on preparation of the FeNi27Co3 catalyst powder by a coprecipitation-Co-reduction method [ J ], superhard material engineering, 2009,21(5),37-43) by zhao wendong et al (zhao wendong, xujun, guhong, etc. ] the FeNi27Co3 catalyst powder is prepared by a chemical coprecipitation-Co-reduction method, firstly, chemical reagents are used as raw materials to prepare precursor powder by coprecipitation, then, the precursor is calcined to prepare metal oxide composite powder, then, hydrogen is introduced at 650 ℃ to prepare alloy powder by reduction, and finally, mechanical alloying is carried out. Displaying according to market selling price: in 2021, 3500 yuan/ton of ferric chloride, ferric sulfate and ferric nitrate, 5 ten thousand yuan/ton of cobalt chloride, cobalt sulfate and cobalt nitrate, and 3.5 ten thousand yuan/ton of nickel chloride, nickel sulfate and nickel nitrate. In the technology, the raw materials use chemical reagents to replace pure metal simple substance powder, so that the cost is saved, but the reduction temperature is higher, the energy consumption is higher, the process flow is long, and impurities are easy to introduce.
In conclusion, in the process of preparing the entropy alloy of FeCoNi, the traditional ball mill has the problems of high raw material cost, high energy consumption, long flow and easy introduction of impurities. Therefore, a method for preparing the entropy alloy in FeCoNi with low cost, low energy consumption, short flow and less impurities is urgently needed to be developed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing FeCoNi intermediate entropy alloy with low cost and short flow, which adopts a chemical coprecipitation method, takes a low-cost chemical reagent as a raw material, prepares a FeCoNi intermediate entropy alloy precursor through aging, suction filtration and drying, puts the precursor into a high-temperature ball mill, generates a large number of active sites along with grinding, refining and uniform mixing of the grinding balls to the material in the mechanical alloying process, reduces the activation energy of the chemical reaction in the reduction process, excites the low-temperature chemical reaction, and reduces the energy consumption; in addition, three processes of calcination, reduction and alloying are completed in one device, so that the device has multiple functions, the process flow is greatly shortened, and the introduction of impurities is reduced. Therefore, the method meets the requirements of preparing the FeCoNi intermediate entropy alloy with low cost, low energy consumption, short flow and few impurities.
The technical scheme of the invention is realized as follows:
a method for preparing FeCoNi intermediate entropy alloy with low cost and short process comprises the following specific steps:
(1) preparing an equimolar ratio target alloy mother solution: dissolving the iron source, the cobalt source and the nickel source with equal substance amount into distilled water, and performing ultrasonic dispersion treatment to obtain the target alloy mother liquor.
(2) Preparing a FeCoNi intermediate entropy alloy precursor: dropwise adding a precipitator into the target alloy mother liquor obtained in the step (1) at a dropwise adding speed of 5-20 mL/min by using a peristaltic pump, adjusting the pH value to 9-12 while mechanically stirring, aging for 10-40 h to achieve a chemical coprecipitation effect, generating a composite hydroxide, and performing suction filtration and drying on the composite hydroxide to obtain a FeCoNi intermediate entropy alloy precursor;
(3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 400-700 ℃, the ball milling time to be 10-40 h and the ball-to-material ratio to be 8-20: 1, vacuumizing before starting the equipment, introducing reducing gas in the operation process, and generating FeCoNi intermediate entropy alloy powder after finishing high-temperature ball milling;
(4) preparing FeCoNi intermediate entropy alloy: and (3) filling the FeCoNi medium entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 990-1100 ℃, setting the heating rate to be 45-55 ℃/min, keeping the temperature for 5-15 min after the temperature reaches 990-1100 ℃, keeping the constant axial pressure of 35-45 MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi medium entropy alloy.
Preferably, the iron source, cobalt source and nickel source used in step (1) are from analytical pure chemical reagents: FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2O，Fe2(SO4)3·9H2O、CoSO4·7H2O、NiSO4·6H2O，Fe(NO3)3·6H2O、Co(NO3)2·6H2O and Ni (NO)3)2·6H2And one or more of O is optionally matched.
Preferably, the dropping speed set by the peristaltic pump in the step (2) is 10 mL/min.
Preferably, the precipitant in step (2) is NaHCO3Solution, NaCO3One or more of solution, ammonia water, urea, NaOH solution and KOH are matched optionally.
Preferably, the pH value is adjusted to 10 in the step (2), and the aging time is 20 h.
Preferably, in the step (2), a suction filter is used for suction filtration of the composite hydroxide, and then the filter cake is placed in a drying oven, the drying temperature is set to be 80-110 ℃, and the heat preservation time is 10-20 hours.
Preferably, in the step (2), a suction filter is used for suction filtration of the composite hydroxide, and then the filter cake is placed in a drying oven, the drying temperature is set to be 90 ℃, and the heat preservation time is 10 hours.
Preferably, the high-temperature ball mill in the step (3) sets the ball milling temperature to be 500 ℃, the ball milling time to be 20h and the ball-to-material ratio to be 12: 1.
Preferably, the reducing gas in the step (3) is CO or H2。
Preferably, in the step (4), the sintering temperature is set to be 1000 ℃, the heating rate is 50 ℃/min, the temperature is kept for 10min after the temperature reaches 1000 ℃, and the constant axial pressure of 40MPa is kept in the sintering process.
The invention has the following beneficial effects:
(1) compared with the prior art that the pure metal simple substance powder is used as the raw material for preparing the medium-entropy alloy powder by using the traditional ball mill, the high-temperature ball mill is used for replacing the pure metal simple substance powder with the commercial analytical pure chemical reagent, so that the limitation of the raw material is broken, and the raw material cost is greatly reduced; in addition, in the mechanical alloying process, along with the grinding, refining and uniform mixing of the grinding balls to the materials, a large number of active sites are generated, the reduction process is promoted in the aspect of dynamics, the activation energy of the chemical reaction is reduced, the low-temperature chemical reaction is excited, and the low-temperature reduction is realized, so that the energy consumption is reduced, and reference is provided for preparing the FeCoNi intermediate entropy alloy with low cost and low energy consumption.
(2) Compared with the prior art for preparing the FeCoNi mid-entropy alloy powder by coprecipitation and reduction, the invention puts the FeCoNi mid-entropy alloy precursor into the high-temperature ball mill, can simultaneously carry out three processes of calcination, reduction and alloying, has multiple purposes, greatly shortens the process flow, reduces the introduction of impurities, and provides reference for preparing the FeCoNi mid-entropy alloy with short process and less impurities.
Drawings
FIG. 1 is a process flow chart of the invention for preparing an entropy alloy in FeCoNi with low cost and short process.
FIG. 2 is an XRD pattern of an entropy alloy in FeCoNi obtained in example 1 of the present invention.
FIG. 3 is an XRD pattern of an entropy alloy in FeCoNi obtained in example 2 of the present invention.
FIG. 4 is an XRD pattern of an entropy alloy in FeCoNi obtained in example 3 of the present invention.
FIG. 5 is an XRD pattern of an entropy alloy in FeCoNi obtained in example 4 of the present invention.
Detailed Description
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description of the embodiments of the present invention taken in conjunction with the accompanying drawings, which are included to illustrate and not to limit the scope of the present invention.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The ball mill used in the following examples is called a high temperature ball mill, which is formed by winding a heating resistance wire around the outside of a commercially available ball mill crucible, and is equipped with a corresponding power supply and a temperature control device, and has a heating function and a temperature control function, and can be evacuated and filled with an atmosphere. The high-temperature ball mill introduces a heating body as a heat source at the outer side of a ball milling tank body, the ball milling heat preservation temperature and time are set through a temperature control program, and the ball milling rotating speed is controlled and adjusted by changing the current frequency. The high temperature ball mill can be selected from a vibration type ball mill or a rotary type ball mill, and the material of the ball milling tank is at least one of alumina, zirconia and calcium carbide. The ball-material ratio refers to the ratio of the mass of the grinding balls to the mass of the raw materials.
Example 1
A method for preparing FeCoNi intermediate entropy alloy with low cost and short process comprises the following specific steps:
(1) FeCl in equal amount3·6H2O、CoCl2·6H2O、NiCl2·6H2Dissolving O in distilled water, and performing ultrasonic dispersion treatment to obtain a target alloy mother solution;
(2) dropwise adding 8mol/L ammonia water into the target alloy mother liquor obtained in the step (1) at a dropwise adding speed of 5mL/min by using a peristaltic pump, adjusting the pH value to 9 while mechanically stirring, aging for 10 hours to achieve a chemical coprecipitation effect and generate a composite hydroxide, further performing suction filtration on the composite hydroxide generated in the step (2) by using a suction filter, then putting a filter cake into a drying box, setting the drying temperature to be 80 ℃, and keeping the temperature for 20 hours to obtain a FeCoNi intermediate entropy alloy precursor;
(3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 400 ℃, the ball milling time to be 10h, and the ball-to-material ratio to be 8: 1, before the equipment is started, vacuumizing treatment is carried out, and reducing gas is introduced in the operation process. Under the coupling action of a temperature field, a chemical field and a mechanical force field in a high-temperature ball mill, powder is refined, the reaction activity is improved, and the solid solubility between metals is increased, so that a precursor with more uniform element distribution obtained by chemical coprecipitation is calcined, reduced and alloyed to generate FeCoNi intermediate entropy alloy powder with small particle size and more uniform element distribution. The complex physicochemical reactions that occur in high temperature ball mills can be broken down into: calcining the precursor to generate a composite oxide, then carrying out reduction reaction to reduce the composite oxide into a metal simple substance, and further carrying out mechanical alloying to form FeCoNi intermediate entropy alloy powder, wherein the average grain size of the obtained powder is about 20 mu m.
(4) Preparing FeCoNi intermediate entropy alloy: and (4) filling the FeCoNi mid-entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 1000 ℃, the heating rate to be 50 ℃/min, keeping the temperature for 10min after the temperature reaches 1000 ℃, keeping the constant axial pressure of 40MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi mid-entropy alloy.
Example 2
A method for preparing FeCoNi intermediate entropy alloy with low cost and short process comprises the following specific steps:
(1) fe in equal amount2(SO4)3·9H2O、CoSO4·7H2O、NiSO4·6H2Dissolving O in distilled water, and performing ultrasonic dispersion treatment to obtain a target alloy mother solution;
(2) dropwise adding 8mol/L urea aqueous solution into the target alloy mother liquor obtained in the step (1) at a dropwise adding speed of 10mL/min by using a peristaltic pump, adjusting the pH value to 10 while mechanically stirring, aging for 20h to achieve a chemical coprecipitation effect to generate a composite hydroxide, further performing suction filtration on the composite hydroxide generated in the step (2) by using a suction filter, then putting a filter cake into a drying box, setting the drying temperature to be 90 ℃, and keeping the temperature for 20h to obtain a FeCoNi intermediate entropy alloy precursor;
(3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 500 ℃, the ball milling time to be 20h, and the ball-to-material ratio to be 12:1, before the equipment is started, vacuumizing treatment is carried out, and reducing gas is introduced in the operation process. Under the coupling action of a temperature field, a chemical field and a mechanical force field in a high-temperature ball mill, powder is refined, the reaction activity is improved, and the solid solubility between metals is increased, so that a precursor with more uniform element distribution obtained by chemical coprecipitation is calcined, reduced and alloyed to generate FeCoNi intermediate entropy alloy powder with small particle size and more uniform element distribution. The complex physicochemical reactions that occur in high temperature ball mills can be broken down into: calcining the precursor to generate a composite oxide, then carrying out reduction reaction to reduce the composite oxide into a metal simple substance, and further carrying out mechanical alloying to form FeCoNi intermediate entropy alloy powder, wherein the average grain size of the obtained powder is about 15 mu m.
(4) Preparing FeCoNi intermediate entropy alloy: and (4) filling the FeCoNi mid-entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 1000 ℃, the heating rate to be 50 ℃/min, keeping the temperature for 10min after the temperature reaches 1000 ℃, keeping the constant axial pressure of 40MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi mid-entropy alloy.
Example 3
A method for preparing FeCoNi intermediate entropy alloy with low cost and short process comprises the following specific steps:
(1) fe (NO) in equal amount3)3·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2Dissolving O in distilled water, and performing ultrasonic dispersion treatment to obtain a target alloy mother solution;
(2) 4mol/L NaHCO was added dropwise at 15mL/min using a peristaltic pump3And 4mol/L NaOH solution according to a volume ratio of 1: 1, dropwise adding the mixed solution into the target alloy mother solution obtained in the step (1), adjusting the pH value to 11 while mechanically stirring, aging for 30 hours to achieve the effect of chemical coprecipitation to generate composite hydroxide, further performing suction filtration on the composite hydroxide generated in the step (2) by using a suction filter, then putting a filter cake into a drying box, setting the drying temperature to be 100 ℃ and the heat preservation time to be 10 hours to obtain a FeCoNi intermediate entropy alloy precursor;
3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 600 ℃, the ball milling time to be 30h, and the ball-to-material ratio to be 16: 1, before the equipment is started, vacuumizing treatment is carried out, and reducing gas is introduced in the operation process. Under the coupling action of a temperature field, a chemical field and a mechanical force field in a high-temperature ball mill, powder is refined, the reaction activity is improved, and the solid solubility between metals is increased, so that a precursor with more uniform element distribution obtained by chemical coprecipitation is calcined, reduced and alloyed to generate FeCoNi intermediate entropy alloy powder with small particle size and more uniform element distribution. The complex physicochemical reactions that occur in high temperature ball mills can be broken down into: calcining the precursor to generate a composite oxide, then carrying out reduction reaction to reduce the composite oxide into a metal simple substance, and further carrying out mechanical alloying to form FeCoNi intermediate entropy alloy powder, wherein the average grain size of the obtained powder is about 12 mu m.
(4) Preparing FeCoNi intermediate entropy alloy: and (4) filling the FeCoNi mid-entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 1000 ℃, the heating rate to be 50 ℃/min, keeping the temperature for 10min after the temperature reaches 1000 ℃, keeping the constant axial pressure of 40MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi mid-entropy alloy.
Example 4
A method for preparing FeCoNi intermediate entropy alloy with low cost and short process comprises the following specific steps:
(1) FeCl in equal amount3·6H2O、CoSO4·7H2O、Ni(NO3)2·6H2Dissolving O in distilled water, and performing ultrasonic dispersion treatment to obtain a target alloy mother solution;
(2) 4mol/LNa is added at a dropping rate of 20mL/min by using a peristaltic pump2CO3And 4mol/L KOH solution in a volume ratio of 1: 1, dropwise adding the mixed solution into the target alloy mother solution obtained in the step (1), adjusting the pH value to 12 while mechanically stirring, aging for 40 hours to achieve the effect of chemical coprecipitation to generate composite hydroxide, further performing suction filtration on the composite hydroxide generated in the step (2) by using a suction filter, then putting a filter cake into a drying box, setting the drying temperature to be 110 ℃, and keeping the temperature for the time of heat preservation10h, obtaining a FeCoNi intermediate entropy alloy precursor;
3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 700 ℃, the ball milling time to be 40h, and the ball-to-material ratio to be 20:1, before the equipment is started, vacuumizing treatment is carried out, and reducing gas is introduced in the operation process. Under the coupling action of a temperature field, a chemical field and a mechanical force field in a high-temperature ball mill, powder is refined, the reaction activity is improved, and the solid solubility between metals is increased, so that a precursor with more uniform element distribution obtained by chemical coprecipitation is calcined, reduced and alloyed to generate FeCoNi intermediate entropy alloy powder with small particle size and more uniform element distribution. The complex physicochemical reactions that occur in high temperature ball mills can be broken down into: calcining the precursor to generate a composite oxide, then carrying out reduction reaction to reduce the composite oxide into a metal simple substance, and further carrying out mechanical alloying to form FeCoNi intermediate entropy alloy powder, wherein the average grain size of the obtained powder is about 12 mu m.
(4) Preparing FeCoNi intermediate entropy alloy: and (4) filling the FeCoNi mid-entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 1000 ℃, the heating rate to be 50 ℃/min, keeping the temperature for 10min after the temperature reaches 1000 ℃, keeping the constant axial pressure of 40MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi mid-entropy alloy.
Comparative example 1
The raw materials and the method of example 1 are adopted, with the only difference that the ball milling temperature in the step (3) is set to 300 ℃, at which only the calcination of the precursor can be realized to form the composite oxide, and the reduction of the composite oxide to form the metal simple substance cannot be further realized, so that the FeCoNi intermediate entropy alloy powder is not formed.
Comparative example 2
The raw materials and the method in the embodiment 1 are adopted, the only difference is that the precursor obtained in the step (2) is added into a muffle furnace in the step (3), the temperature setting is consistent with that in the embodiment 1, and the heat preservation is carried out for 10 hours at the temperature of 400 ℃, because no grinding ball plays a physical hammering role on the raw materials, namely no mechanical external force is added, only the thermodynamic temperature is ensured, so that the reaction activity of the raw materials is reduced, only the calcination of the precursor can be realized to form the composite oxide, and the reduction of the composite oxide to form the metal simple substance cannot be further realized, so that FeCoNi intermediate entropy alloy powder is not formed.
The above embodiments are merely provided to help understand the method and core principle of the present invention, and the main steps and embodiments of the present invention are described in detail by using specific examples. To those skilled in the art, the various conditions and parameters may be varied as desired in a particular implementation in accordance with the principles of the invention, and in view of the foregoing, the description is not to be taken as limiting the invention.

Claims (10)

1. A method for preparing FeCoNi intermediate entropy alloy with low cost and short process is characterized in that: the method comprises the following specific steps:
(1) preparing an equimolar ratio target alloy mother solution: dissolving the iron source, the cobalt source and the nickel source with equal substance amount into distilled water, and performing ultrasonic dispersion treatment to obtain the target alloy mother liquor.
(2) Preparing a FeCoNi intermediate entropy alloy precursor: dropwise adding a precipitator into the target alloy mother liquor obtained in the step (1) at a dropwise adding speed of 5-20 mL/min by using a peristaltic pump, adjusting the pH value to 9-12 while mechanically stirring, aging for 10-40 h to achieve a chemical coprecipitation effect, generating a composite hydroxide, and performing suction filtration and drying on the composite hydroxide to obtain a FeCoNi intermediate entropy alloy precursor;
(3) preparing FeCoNi intermediate entropy alloy powder: adding the precursor obtained in the step (2) into a high-temperature ball mill, setting the ball milling temperature to be 400-700 ℃, the ball milling time to be 10-40 h and the ball-to-material ratio to be 8-20: 1, vacuumizing before starting the equipment, introducing reducing gas in the operation process, and generating FeCoNi intermediate entropy alloy powder after finishing high-temperature ball milling;
(4) preparing FeCoNi intermediate entropy alloy: and (3) filling the FeCoNi medium entropy alloy powder obtained in the step (3) into a graphite die, setting the sintering temperature to be 990-1100 ℃, setting the heating rate to be 45-55 ℃/min, keeping the temperature for 5-15 min after the temperature reaches 990-1100 ℃, keeping the constant axial pressure of 35-45 MPa in the sintering process, and cooling along with a furnace after sintering to obtain the FeCoNi medium entropy alloy.
2. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: the iron source, cobalt source and nickel source used in step (1) are from analytical pure chemical reagents: FeCl3·6H2O、CoCl2·6H2O、NiCl2·6H2O，Fe2(SO4)3·9H2O、CoSO4·7H2O、NiSO4·6H2O，Fe(NO3)3·6H2O、Co(NO3)2·6H2O and Ni (NO)3)2·6H2And one or more of O is optionally matched.
3. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: and (3) setting the dropping speed of the peristaltic pump in the step (2) to be 10 mL/min.
4. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: the precipitator in the step (2) is NaHCO3Solution, NaCO3One or more of solution, ammonia water, urea, NaOH solution and KOH solution are matched optionally.
5. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: in the step (2), the pH value is adjusted to be 10, and the aging time is 20 h.
6. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: and (3) performing suction filtration on the composite hydroxide by using a suction filter in the step (2), then putting the filter cake into a drying box, setting the drying temperature to be 80-110 ℃, and keeping the temperature for 10-20 hours.
7. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: and (3) performing suction filtration on the composite hydroxide by using a suction filter in the step (2), and then putting a filter cake into a drying box, wherein the drying temperature is set to be 90 ℃, and the heat preservation time is 10 hours.
8. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: in the step (3), the ball milling temperature of the high-temperature ball mill is set to be 500 ℃, the ball milling time is 20 hours, and the ball-to-material ratio is 12: 1.
9. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: the reducing gas in the step (3) is CO or H2。
10. The method for preparing the entropy alloy in FeCoNi in low cost and short flow according to claim 1, wherein the method comprises the following steps: in the step (4), the sintering temperature is set to be 1000 ℃, the heating rate is 50 ℃/min, the temperature is kept for 10min after the temperature reaches 1000 ℃, and the constant axial pressure of 40MPa is kept in the sintering process.
CN202110321561.1A 2021-03-25 2021-03-25 Method for preparing FeCoNi intermediate entropy alloy with low cost and short process Pending CN113070483A (en)

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