CN114686717B - Preparation method of high-entropy alloy - Google Patents
Preparation method of high-entropy alloy Download PDFInfo
- Publication number
- CN114686717B CN114686717B CN202210306308.3A CN202210306308A CN114686717B CN 114686717 B CN114686717 B CN 114686717B CN 202210306308 A CN202210306308 A CN 202210306308A CN 114686717 B CN114686717 B CN 114686717B
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- sintering
- metal
- powder
- ball milling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 131
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 70
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 16
- 229910052987 metal hydride Inorganic materials 0.000 claims description 14
- 150000004681 metal hydrides Chemical class 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010814 metallic waste Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 230000003534 oscillatory effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 34
- 239000000047 product Substances 0.000 description 24
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004663 powder metallurgy Methods 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009694 cold isostatic pressing Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a preparation method of a high-entropy alloy, which comprises the following steps: (1) pressing and sintering the high-entropy alloy element powder to obtain a high-entropy alloy block primary product; (2) and (3) deoxidizing the high-entropy alloy block primary product obtained in the step (1), and cooling to obtain a high-entropy alloy block, namely, completing the preparation of the high-entropy alloy. The preparation method of the high-entropy alloy provided by the invention finally carries out deoxidation on the high-entropy alloy block initial product, so that a metal powder deoxidation process is omitted, the deoxidation method is simple, the operation is simpler and more convenient, the problems in the metal powder deoxidation process are avoided, and the influence caused by the fact that trace oxygen enters the alloy block in the subsequent sintering process can be avoided.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a preparation method of an alloy.
Background
The high-entropy alloy has high strength, high toughness, high corrosion resistance and biocompatibility which cannot be achieved by the traditional alloy, and can be widely applied to the fields of aerospace, automobiles, biomedical treatment and the like. Similar to the conventional alloy, impurities in the alloy have a great influence on the alloy performance, for example, the presence of oxygen in the alloy causes the alloy to become brittle, the toughness to be reduced and the performance to be reduced, so that the content of the impurities in the raw materials and the preparation process needs to be strictly controlled.
The traditional method for preparing the high-entropy alloy is mainly a vacuum melting method, and alloy blocks of all components are continuously melted and cast at the temperature higher than the melting point, and are repeatedly remelted to reduce the impurity content in ingots. In order to obtain a high-entropy alloy product with high purity, less impurities and excellent performance, a pure metal block with high purity and low impurities is required to be used, the preparation cost is fundamentally increased, 5-7 times or even more than 10 times of repeated remelting is required in smelting to achieve a uniform effect, and the operation is complex. In addition, the general melting temperature of the high-entropy alloy prepared by vacuum melting is above 1500 ℃, and for the high-entropy alloy which is difficult to melt, the temperature is above 2000 ℃, but the defects of dendrite segregation, shrinkage porosity and the like can be generated in the cooling process. In addition, after casting is complete, further machining of the product is required to obtain the desired shaped part, adding energy consumption and process complexity to the process.
The more advanced preparation method is a powder metallurgy method, as a near-net-shape forming technology, the die can be customized according to the requirements of different product parts, the effect that products are prepared at one time without subsequent machining can be achieved, and the method is a high-entropy alloy preparation technology widely used in the future. The powder metallurgy method for preparing the high-entropy alloy is to use metal powder to prepare a high-entropy alloy block as the name implies, generally speaking, the high-purity high-performance high-entropy alloy block needs to use metal powder with high purity and few impurities, and the introduction of more impurities caused by force factors in the process flow in the subsequent preparation flow needs to be reduced as much as possible. However, the process for preparing high-purity metal powder is complicated, at present, a molten salt deoxidation method is mainly adopted for purifying the metal powder such as removing oxygen, the oxygen content of the powder is reduced by utilizing the strong affinity of a deoxidizer to oxygen, and a powder product is obtained. If the deoxidation temperature is too low, the deoxidation limit of the alloy powder may not be reached, and the deoxidation effect is not good. Therefore, molten salt deoxidation of metal powder is technically very complicated, operation requirements are high, and the cost of high-purity metal powder is high. Besides, the preparation process of the high-purity powder has high control requirements, and the powder requires to control the size of large particles as much as possible (considering oxygen content and cost), so that the sintering process has high temperature and high densification difficulty. Meanwhile, even if the deoxidized high-purity metal powder is adopted, oxygen cannot be prevented from entering the alloy block in subsequent sintering, and the final high-entropy alloy block is also adversely affected.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a preparation method of a high-entropy alloy which has low requirements on raw materials and is formed by sintering and then deoxidizing control components. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a high-entropy alloy comprises the following steps:
(1) pressing and sintering fine-particle high-entropy alloy element powder to obtain a high-entropy alloy block primary product;
(2) and (2) deoxidizing the high-entropy alloy block primary product obtained in the step (1), and cooling to obtain a high-entropy alloy block, namely completing the preparation of the high-entropy alloy.
In the above production method, preferably, each composition of the high-entropy alloy element powder is mainly derived from metal scraps having no limitation on oxygen content and particle size. For example, the metallic titanium is derived from titanium scrap. Of course, pure metal powders may also be used, regardless of cost. The raw materials of each component of the high-entropy alloy are derived from metal waste, so that the cost is lower. The scrap metal may be a poor part of producing low oxygen metal powders, such as powders with too high an oxygen content, too large a particle size, etc. Conversion to brittle metal hydride powder after metal hydrogenation can simplify particle size control while reducing high entropy alloy production costs.
In the above preparation method, preferably, the high-entropy alloy element powder is obtained by subjecting each of the metal waste materials to hydrogenation sintering and ball milling; the step of the hydrogenation sintering is to perform hydrogenation sintering on the metal waste materials to completely hydrogenate the metal waste materials to obtain metal hydride; and the ball milling treatment comprises the steps of mixing the metal hydrides, then carrying out ball milling, screening after the ball milling is finished, standing and separating a solid-liquid mixture, and naturally drying the powder to obtain the high-entropy alloy powder. Metal powder is converted into metal hydride through metal hydrogenation treatment, the metal hydride is a brittle compound, the powder with micron grade can be achieved through short-time ball milling, and meanwhile, the particle size of the powder after alloying is controlled to be less than 5 microns.
In the above preparation method, preferably, the sintering temperature is controlled to be higher than the hydrogen absorption temperature of the corresponding metal scrap when the metal scrap is subjected to hydrogenation sintering (i.e. the sintering temperatures are controlled to be different when different metal scraps are subjected to hydrogenation sintering); the ball milling treatment is carried out according to the volume ratio of (7-10): 1, adding ethanol and water as a medium (the adding amount is equivalent to the total mass of the metal hydride), adding polyethylene glycol accounting for 1-5% of the total mass of the metal hydride, placing the mixture in an agate tank for ball milling, controlling the ball milling rotation speed to be 300-400r/min, and controlling the ball milling time to control the average particle size of the powder to be less than 5 microns (generally controlling the ball milling time not to exceed 1 h).
In the above preparation method, preferably, the pressing is to fill the high-entropy alloy powder into a die, to perform oscillating compaction, to further place the die into a cold isostatic press, and to perform press forming.
In the above production method, preferably, the sintering process is performed by sintering the pressed compact in an atmosphere furnace.
In the above preparation method, preferably, the sintering temperature is controlled to be 1000-. For the refractory high-entropy alloy, the high melting point determines that the melting temperature and the sintering temperature are very high, and the sintering and forming can be generally carried out at the temperature of 1500-. The refractory high-entropy alloy is sintered only at the temperature of 1000-1400 ℃, and the high-entropy alloy is prepared by using relatively low temperature, so that the sintering temperature is reduced while the alloy is densified, and the energy consumption is reduced. The result of the low temperature sintering and densification described above is a combination of brittle metal hydride and particle size control.
In the above production method, preferably, the deoxidation treatment is performed by mixing the high-entropy alloy block primary product with a sufficient amount of deoxidation metal and flux, and then performing heat preservation treatment in an atmosphere furnace.
In the above preparation method, preferably, the deoxidized metal is a metal having a strong affinity for oxygen than the metal of each component of the high-entropy alloy, such as Ca, Y, etc.; the fluxing agent comprises CaCl 2 、YCl 3 Or KCl. In the invention, the deoxidized metal can be determined by referring to an Ellingham oxygen potential diagram, and the deoxidized metal has strong metal oxygen affinity for each component of the high-entropy alloyA metal. Different deoxidizing metals are selected according to different high-entropy alloy components, for example, according to the melting point of the refractory high-entropy alloy and the specific delayed diffusion effect of the high-entropy alloy, the metal Y with the melting point of 1522 ℃ is selected as a deoxidizing agent, and during high-temperature deoxidation, the internal structure and the grain size of the high-entropy alloy cannot be greatly changed, so that the deoxidation temperature can be increased while the inside of the metal is not influenced, and the deoxidation limit is further increased. The preparation method of the high-entropy alloy can adjust the types of deoxidizing metal and fluxing agent and control the deoxidizing temperature aiming at different high-entropy alloy components, thereby improving the deoxidizing limit.
In the preparation method, preferably, the heat preservation temperature is controlled to be 900-. The heat preservation temperature is higher than the melting point of the molten salt and lower than the melting point of the deoxidized metal on the premise of not influencing the alloy structure.
In the above preparation method, preferably, the sintered high-entropy alloy block primary product is subjected to subsequent deoxidation treatment. And after the deoxidation treatment, the high-entropy alloy block is naturally cooled, separated, cleaned, ground and polished to complete the preparation of the high-entropy alloy.
In the preparation method, the high-entropy alloy block is prepared by a powder metallurgy method, the block can be rod-shaped, block-shaped, sheet-shaped, plate-shaped and the like, a mould can be customized, and devices with more complex shapes, such as gears, tubes and the like, can be prepared.
The conventional powder metallurgy method for preparing the refractory high-entropy alloy has the advantages that the high melting point of refractory metal can cause the element diffusivity to be reduced in the sintering process, the high melting point element can be gathered and has uneven components, the sintering is carried out at 1500 ℃ to reduce the adverse effect caused by the high melting point, but the high energy consumption and the large resource consumption are caused by the excessively high sintering temperature. In addition, the preparation of the high-entropy alloy with excellent performance in the prior art needs to start with a high-entropy alloy preparation method, a high-purity raw material powder and perform deoxidation treatment on the raw material powder, so that the problems of high cost, complex and high process, large particle size, influence on sintering densification and the like exist. The invention achieves the purpose of improving the alloy performance by adopting the hydrogenated metal powder and controlling the granularity (fine particles) of the initial powder, can be sintered at lower temperature, and the prepared high-entropy alloy has no pores, high compactness and no element accumulation, and can improve the strength and the ductility of the alloy due to the fine-grain strengthening effect caused by small grains. In addition, the invention uses the hydrogenated powder as the raw material, and hydrogen atoms generated in the hydride sintering process contact with the oxide layer on the surface of the powder to react, so that the oxygen content can be reduced, and the performance of the alloy can be controlled. The invention provides a thought for preparing high-entropy alloy by utilizing metal waste and carrying out integral deoxidation on a high-entropy alloy block, the oxygen content of powder is not restricted in the initial stage, waste of various metals can be used as raw materials, the oxygen content is not controlled in the preparation process of the powder raw materials, and all the oxygen content is controlled in the last step by deoxidation. After sintering is finished, the high-entropy alloy block is deoxidized integrally, so that solidification between raw material powder and a deoxidizer or molten salt is avoided, and the purpose of reducing the oxygen content of the high-entropy alloy is achieved.
Compared with the prior art, the invention has the advantages that:
1. in order to control the components of the final product and avoid the increase of oxygen content, the traditional preparation method of the high-entropy alloy generally controls the metal powder to have larger particle size, and simultaneously adopts a very rigorous preparation method. The preparation method of the high-entropy alloy is based on a powder metallurgy method, does not consider the increase of oxygen content, omits a metal powder deoxidation process, activates a sintering process to the maximum extent, reduces the sintering temperature, achieves the aim of low-temperature preparation of the high-density high-entropy alloy, and finally performs one-step deoxidation on the high-entropy alloy block primary product to reduce the oxygen content to a reasonable interval. On the whole, the method of the invention omits the metal powder deoxidation process, has simple deoxidation method and simpler and more convenient operation, avoids the problems existing in the metal powder deoxidation process, and can avoid the influence caused by the fact that trace oxygen enters the alloy block in the subsequent sintering.
2. The preparation method of the high-entropy alloy firstly controls the shape and then controls the components, can regulate and control the oxygen content of the alloy under the condition of not damaging the appearance of the alloy block, and keeps the integrity of the appearance.
3. The preparation method of the high-entropy alloy has low requirements on raw material powder (metal waste powder with higher oxygen content can be used), and the preparation cost is reduced.
4. The preparation method of the high-entropy alloy uses a powder metallurgy method to prepare the high-entropy alloy block, can prepare the high-entropy alloy at low temperature, and has the advantages of simple operation, stronger safety, energy conservation and emission reduction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the preparation method of the high-entropy alloy of the invention.
Fig. 2 is an SEM image of the metal powder after hydrogenation in example 1: (a) TiH 2 ；(b)TaH 2 ；(c)NbH 2 ；(d)ZrH 2 ；(e)HfH 2 。
FIG. 3 is an SEM photograph of the powder obtained by the ball-milling treatment and the drying in example 1.
FIG. 4 is a graph showing a particle size distribution of the powder obtained by the ball-milling treatment and the drying in example 1.
FIG. 5 is an appearance and morphology diagram of the high-entropy alloy block in example 1.
Fig. 6 is an SEM image of the bulk of the high-entropy alloy in example 1.
Fig. 7 is an XRD pattern of the bulk of the high-entropy alloy in example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
as shown in fig. 1, a method for preparing a high-entropy alloy comprises the following steps:
(1) respectively reacting Ti, Ta, Nb, Zr and Hf wastes at 400 ℃, 600 ℃, 500 ℃, 600 ℃ and 800 ℃ for 4h in a hydrogen atmosphere to obtain corresponding metal hydrides (an SEM picture is shown in figure 2);
(2) according to the following steps of 1: 1: 1: 1: 4.15g of TiH are weighed out in a molar ratio of 1 2 15.211g of TaH 2 7.893g NbH 2 7.735g of ZrH 2 15.012g HfH 2 Adding 45ml of alcohol and 5ml of distilled water into the powder, adding 0.01g of PEG (polyethylene glycol), placing the mixture in an agate tank, setting the rotating speed to be 350r/min, and performing ball milling for 1 hour according to the specified ball milling time;
(3) screening the mixed solution subjected to ball milling in the step (2), and naturally drying the powder;
(4) putting the powder dried in the step (3) (the SEM picture is shown in figure 3, the particle size distribution diagram is shown in figure 4, the average particle size is about 4 microns) into a columnar die, vibrating and compacting, putting into a cold isostatic press, setting the pressure to be 350MPa, and carrying out cold isostatic pressing to obtain a green compact;
(5) placing the pressed blank in the step (4) into a crucible, laying Ti powder around the crucible, placing the crucible into an atmosphere reaction furnace, and performing hydrogen sintering at 1300 ℃ for 4 hours to obtain a high-entropy alloy block primary product;
(6) slicing the high-entropy alloy block primary product obtained in the step (5), cleaning, and carrying out oxygen content test, wherein the oxygen content of the high-entropy alloy obtained by the test is 1.4 wt% after direct sintering;
(7) cutting the residual high-entropy alloy block primary product in the step (6) into strips of 5 x 1cm, and mixing with enough metal Ca and CaCl 2 Mixing, and placing into a stainless steel crucible;
(8) transferring the stainless steel crucible in the step (7) into an atmosphere reaction furnace, and preserving heat for 8 hours at 900 ℃;
(9) cooling and separating the reaction product in the step (8) to obtain a high-entropy alloy block; the appearance topography, SEM and XRD of the high-entropy alloy block product are shown in FIGS. 5, 6 and 7 respectively;
(10) and (4) slicing the high-entropy alloy block product obtained in the step (9), cleaning and carrying out oxygen content test.
In the embodiment, the oxygen content test result in the step (10) shows that the oxygen content in the high-entropy alloy after deoxidation is 0.15 wt%, which is 1.25 wt% lower than the oxygen content in the alloy after direct sintering, and the deoxidation effect is obvious.
As can be seen from fig. 2, 3 and 4, the hydrogenated powder has an irregular shape and a corresponding particle size, and the particle size is greatly reduced by ball milling, resulting in irregular particle morphology. FIG. 6 shows that the alloy after sintering achieves densification without significant porosity, the black dots in the figure are few zirconium particles, the microstructure consists of light and dark phases, and the overall grain size is less than 10 microns. The XRD pattern of fig. 7 also reflects the multiphase composition shown in the SEM of fig. 6.
Example 2:
as shown in fig. 1, a method for preparing a high-entropy alloy comprises the following steps:
(1) reacting the Ti, Ta, Nb, Zr and Hf waste materials for 4 hours at 400 ℃, 600 ℃, 500 ℃, 600 ℃ and 800 ℃ in a hydrogen atmosphere to obtain corresponding metal hydride;
(2) according to the following steps of 1: 1: 1: 1: 4.15g of TiH are weighed out in a molar ratio of 1 2 15.211g of TaH 2 7.893g NbH 2 7.735g of ZrH 2 15.012g HfH 2 Adding 45ml of alcohol and 5ml of distilled water into the powder, adding 0.01g of PEG (polyethylene glycol), placing the mixture in an agate tank, setting the rotating speed to be 350r/min, and performing ball milling for 1 hour according to the specified ball milling time;
(3) screening the mixed solution subjected to ball milling in the step (2), and naturally drying the powder;
(4) putting the powder (with average particle size of about 4 microns) dried in the step (3) into a columnar die, oscillating and compacting, putting into a cold isostatic press, setting the pressure to be 350MPa, and carrying out cold isostatic pressing to obtain a green compact;
(5) placing the pressed blank in the step (4) into a crucible, laying Ti powder around the pressed blank, placing the pressed blank into an atmosphere reaction furnace, and performing hydrogen sintering at 1400 ℃ for 4 hours to obtain a high-entropy alloy block primary product;
(6) slicing the high-entropy alloy block primary product obtained in the step (5), cleaning, and carrying out oxygen content test, wherein the oxygen content of the high-entropy alloy obtained by the test is 1.86 wt% after direct sintering;
(7) cutting the residual high-entropy alloy block in the step (6) into 2mm thin slices and sufficient metal Y and YCl 3 Mixing, and placing into a stainless steel crucible;
(8) transferring the stainless steel crucible in the step (7) into an atmosphere reaction furnace, and preserving heat for 12 hours at 1000 ℃;
(9) cooling and separating the reaction product in the step (8) to obtain a high-entropy alloy block;
(10) and (4) slicing the high-entropy alloy block product obtained in the step (9), cleaning and carrying out oxygen content test.
In the embodiment, the oxygen content analysis result in the step (10) shows that the oxygen content in the high-entropy alloy after deoxidation is 0.12 wt%, which is 1.74 wt% lower than the oxygen content in the alloy after direct sintering, and the deoxidation effect is obvious.
The absolute densities (before deoxidation) of the raw material powders and the high-entropy alloy bulk products in examples 1 to 2 and the oxygen contents before and after deoxidation are specifically shown in table 1 below.
Table 1: comparison of absolute densities of raw material powder and high-entropy alloy bulk product and oxygen contents before and after deoxidation in examples 1-2
Example 3:
as shown in fig. 1, a method for preparing a high-entropy alloy comprises the following steps:
(1) respectively reacting the Ti, Ta, Nb and V wastes at 400 ℃, 600 ℃, 500 ℃ and 750 ℃ for 4h in a hydrogen atmosphere to obtain corresponding metal hydride;
(2) according to the following steps of 1: 1: 1: 1: 6.12g of TiH are weighed out in a molar ratio of 1 2 22.432g of TaH 2 11.639g NbH 2 VH of 6.500g 2 3.309g of Al powder, adding 45ml of alcohol and 5ml of distilled water, adding 0.02g of PEG (polyethylene glycol), placing in an agate pot, setting the rotating speed to 350r/min, and setting the ball milling time to be 1h for ball milling;
(3) screening the mixed solution subjected to ball milling in the step (2), and naturally drying the powder;
(4) putting the powder dried in the step (3) into a columnar mold, vibrating and compacting, putting into a cold isostatic press, setting the pressure to be 350MPa, and carrying out cold isostatic pressing to obtain a pressed blank;
(5) placing the pressed blank in the step (4) into a crucible, laying Ti powder around the crucible, placing the crucible into an atmosphere reaction furnace, and performing hydrogen sintering at 1300 ℃ for 4 hours to obtain a high-entropy alloy block primary product;
(6) slicing the high-entropy alloy block primary product in the step (5), cleaning, and carrying out oxygen content test, wherein the oxygen content of the high-entropy alloy after direct sintering is 1.1 wt%;
(7) cutting the residual high-entropy alloy block primary product in the step (6) into a wafer with the diameter of 5mm, and mixing with enough metal Ca and CaCl 2 Mixing, and placing into a stainless steel crucible;
(8) transferring the stainless steel crucible in the step (7) into an atmosphere reaction furnace, and preserving heat for 10 hours at 900 ℃;
(9) cooling and separating the reaction product in the step (8) to obtain a high-entropy alloy block;
(10) and (5) slicing the high-entropy alloy block product obtained in the step (9), cleaning and testing the oxygen content.
In the embodiment, the oxygen content test result in the step (10) shows that the oxygen content in the deoxidized high-entropy alloy is 0.2 wt%, which is 0.9 wt% lower than that of the alloy after direct sintering, and the deoxidation effect is obvious.
Claims (6)
1. A preparation method of a high-entropy alloy is characterized by comprising the following steps:
(1) pressing and sintering the high-entropy alloy element powder to obtain a high-entropy alloy block primary product;
(2) deoxidizing the high-entropy alloy block primary product obtained in the step (1), and cooling to obtain a high-entropy alloy block, namely, completing the preparation of the high-entropy alloy;
the high-entropy alloy element powder is obtained by carrying out hydrogenation sintering and ball milling treatment on metal waste; the step of the hydrogenation sintering is to perform hydrogenation sintering on the metal waste materials to completely hydrogenate the metal waste materials to obtain metal hydride; the ball milling treatment is to mix all metal hydrides, then carry out ball milling, sieve the mixture after the ball milling is finished, collect the powder and dry the powder to obtain the high-entropy alloy element powder;
the sintering temperature is controlled to be 1000-1400 ℃ during the sintering treatment, the sintering time is 3-6h, and the sintering atmosphere is hydrogen atmosphere, argon atmosphere or hydrogen-argon mixed atmosphere;
the deoxidation treatment is to mix the high-entropy alloy block primary product with sufficient deoxidation metal and fluxing agent and then carry out heat preservation treatment in an atmosphere furnace;
the deoxidized metal is a metal with strong metal-oxygen affinity for each component of the high-entropy alloy, and the fluxing agent comprises CaCl 2 、YCl 3 Or KCl.
2. The production method according to claim 1, wherein each composition component of the high-entropy alloy element powder is mainly derived from metal scraps having no limitation on oxygen content and particle size.
3. The production method according to claim 1, wherein the sintering temperature is controlled to be higher than the hydrogen absorption temperature of the respective metal scrap when each metal scrap is subjected to the hydrogenation sintering; the ball milling treatment is carried out according to the volume ratio of (7-10): 1, adding polyethylene glycol accounting for 1-5% of the total mass of the metal hydride, placing the mixture in an agate tank for ball milling, controlling the ball milling rotation speed to be 300-400r/min, and controlling the ball milling time to control the average particle size of the powder to be less than 5 microns.
4. The production method according to any one of claims 1 to 3, wherein the pressing is carried out by charging the high-entropy alloying element powder into a die, carrying out oscillatory compaction, and then putting the die into a cold isostatic press for press forming.
5. The production method according to any one of claims 1 to 3, wherein the sintering treatment is sintering by placing the pressed compact in an atmosphere furnace.
6. The preparation method as claimed in claim 1, wherein the heat-preserving temperature is controlled to 900-1400 ℃ and the heat-preserving time is 1-50 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210306308.3A CN114686717B (en) | 2022-03-25 | 2022-03-25 | Preparation method of high-entropy alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210306308.3A CN114686717B (en) | 2022-03-25 | 2022-03-25 | Preparation method of high-entropy alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114686717A CN114686717A (en) | 2022-07-01 |
| CN114686717B true CN114686717B (en) | 2022-08-16 |
Family
ID=82139887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210306308.3A Expired - Fee Related CN114686717B (en) | 2022-03-25 | 2022-03-25 | Preparation method of high-entropy alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114686717B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734324A (en) * | 2016-03-04 | 2016-07-06 | 中南大学 | Preparing method for powder metallurgy high-entropy alloy based composite material |
| CN113414386A (en) * | 2021-05-28 | 2021-09-21 | 中南大学 | Method for preparing block alloy by gradient reduction of oxide at low temperature |
| CN113880580A (en) * | 2021-11-12 | 2022-01-04 | 内蒙古工业大学 | High-entropy carbide ultra-high temperature ceramic powder and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
-
2022
- 2022-03-25 CN CN202210306308.3A patent/CN114686717B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734324A (en) * | 2016-03-04 | 2016-07-06 | 中南大学 | Preparing method for powder metallurgy high-entropy alloy based composite material |
| CN113414386A (en) * | 2021-05-28 | 2021-09-21 | 中南大学 | Method for preparing block alloy by gradient reduction of oxide at low temperature |
| CN113880580A (en) * | 2021-11-12 | 2022-01-04 | 内蒙古工业大学 | High-entropy carbide ultra-high temperature ceramic powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114686717A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106756148B (en) | The method that a kind of foundry alloy method of low oxygen content prepares MIM418 alloys | |
| CN104278167B (en) | Manufacturing method of high-quality titanium-aluminum alloy target | |
| CN110408833A (en) | A kind of preparation method of NbTaTiZr high-entropy alloy and its powder | |
| CN104704139B (en) | Cu Ga alloy sputtering targets and its manufacture method | |
| WO2017014675A1 (en) | A method for obtaining electrodes from alloys based on nickel aluminide | |
| CN1164782C (en) | Vacuum induction smelting process of Ti-Ni and Ti-Ni-Nb marmem | |
| CN113122764A (en) | Preparation method of CuCrFeCoNixTi high-entropy alloy thin strip | |
| CN104651662B (en) | The vacuum induction melting method of titanium-aluminium alloy target material | |
| CN114686717B (en) | Preparation method of high-entropy alloy | |
| CN114892064B (en) | FeCrCuVCo high-entropy alloy and preparation method thereof | |
| CN113414386B (en) | Method for preparing block alloy by gradient reduction of oxide at low temperature | |
| CN114717462B (en) | C-containing eutectic high-entropy alloy and preparation method thereof | |
| CN114433859B (en) | High-quality electrode for titanium alloy powder, and preparation and application thereof | |
| CN114672744B (en) | Endogenetic porous titanium reinforced magnesium-based amorphous composite material and preparation method thereof | |
| CN114682784A (en) | Low-cost powder preparation method and printing method of 1900 MPa-grade ultrahigh-strength steel for SLM | |
| JP2749165B2 (en) | TiA-based composite material and method for producing the same | |
| CN113512675B (en) | Ti-Zr-RE-Mg rare earth magnesium alloy grain refiner and preparation method thereof | |
| CN116752008B (en) | Al-Ti-Nb-B intermediate alloy and preparation method and application thereof | |
| CN111822722B (en) | TiAl/TiB for additive manufacturing 2 Preparation method of powder material | |
| JP3413921B2 (en) | Method for producing Ti-Al based intermetallic compound sintered body | |
| JPS6347344A (en) | Production of low oxygen alloy molding | |
| JPH06100969A (en) | Production of ti-al intermetallic compound sintered body | |
| CN116765409A (en) | Niobium-silicon alloy powder for powder metallurgy and preparation method thereof | |
| KR100259334B1 (en) | Producing method of a true-density ti5si3-based intermetallic compound alloy by elemental powder metallurgy | |
| CN116288075A (en) | Multi-scale endogeneous reinforced magnesium-based amorphous composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220816 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |