CN101386928B - Method for preparing high-entropy alloy containing immiscible element - Google Patents
Method for preparing high-entropy alloy containing immiscible element Download PDFInfo
- Publication number
- CN101386928B CN101386928B CN2008102334779A CN200810233477A CN101386928B CN 101386928 B CN101386928 B CN 101386928B CN 2008102334779 A CN2008102334779 A CN 2008102334779A CN 200810233477 A CN200810233477 A CN 200810233477A CN 101386928 B CN101386928 B CN 101386928B
- Authority
- CN
- China
- Prior art keywords
- powder
- alloy
- entropy alloy
- entropy
- sintering
- 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 128
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005275 alloying Methods 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000004080 punching Methods 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 241000500881 Lepisma Species 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000713 high-energy ball milling Methods 0.000 abstract description 9
- 239000006104 solid solution Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000011160 research Methods 0.000 description 7
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010587 phase diagram Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001325 element alloy Inorganic materials 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method for a novel high-entropy alloy structure material. A plurality kinds of alloy element powder which can not form a miscible system are used as raw materials, thereby solving the solid solution problem of the alloy elements without solid solution region during the high-entropy alloy preparation, that is, mixing the powders in a planetary high-energy ball milling machine and obtaining ultra-fine powder of an immiscible system simultaneously through strong mechanical alloying function. When the alloy powder is pressed into a pressing blank, the heating treatment process condition is controlled to allow the alloy elements to diffuse through a short path and form a uniform multi-principal element mixing body containing no intermetal compound in a blank body, and a single-phase solid solution is obtained. The novel alloy prepared by the method is widely used in engine parts made of a high-temperature and creep resistance material, skins and tails of large thrust weight ratio high-speed aircrafts, corrosion resistant and wear resistant parts, wear-resistant materials such as pipes, gears and bearings and other structural material fields.
Description
Technical field
The present invention relates to alloy material preparation science field, particularly relate to the preparation method who contains the immiscible element high-entropy alloy.
Background technology
Known high-entropy alloy present Research: 20 end of the centurys, known conventional alloys is near maturation and state of saturation, the conventional alloys idea has been difficult to the new alloy system of the recreation alloy that breaks in other words in old alloy system, but the high-entropy alloy idea can produce many alloy systems, produces many interesting characteristics.So-called polynary (nanometer) high-entropy alloy is exactly the alloy of multiple element, and wherein each principal element all has high atomic percent, and the someone defines the principal element number of high-entropy alloy more than or equal to 5, but its atomic percent all is no more than 35%.That is to say that high-entropy alloy contains a principal element more than 50% unlike conventional alloys.Known conventional alloys experience makes the people think that a plurality of principal element alloys will produce multiple intermetallic compound by mistake easily, not only is difficult to analysis but also material and becomes fragile, and lacks applicability.Yet by discovering, this experience is not suitable for high-entropy alloy, because metallic element for a long time, high entropy effect can promote the mixing between element on the contrary, form body-centered cubic structure BCC or face-centred cubic structure FCC or non-crystal structure, do not form brittle intermetallic compound and be not inclined to.Known Gibbs one after another is thought, the number p=n+1 of the equilibrium phase that the alloy system of n kind element can produce, the number of phases p that when nonequilibrium freezing, forms〉n+1, but it is in fact really not so, in many pivots high-entropy alloy, the alloy system of n kind element only can form simple body-centered cubic structure BCC or single or limited several items such as face-centred cubic structure FCC or non-crystal structure, and the number of phases that is not the prediction of Gibbs one after another is a lot.The new feature of this alloy makes such alloy have a lot of new character, usually has the magnetic electricity performance of high high-temp stability, solidity to corrosion, high strength, high rigidity, high anti-oxidation character, excellence etc., and alloy compositions can in very large range be adjusted, for metallic substance has been started a new field, become a kind of brand-new material that has development potentiality, related application holds out broad prospects.
The preparation of traditional sosoloid is all according to the dependency rule of equilibrium phase diagram, but can not solid solution between in fact a lot of element, and an aspect is the solid solubility restriction, and other then do not dissolve each other fully.The early-stage Study of this seminar finds, causes that complete immiscible major cause is electronic structure and atomic property between the element, and is not only that known tradition is thought factors such as electronegativity and atomic size.The known element that do not dissolve each other is difficult to form sosoloid, in the preparation of high-entropy alloy, Many researchers has been avoided the interpolation of unmixing element, method is mentioned casting as is well known, spray deposition, rapid solidification methods etc. are main means with rapid solidification method especially, segregation can not take place because only could guarantee the alloying element that reaches the 5-9 kind in the high-entropy alloy in the process of quench solidification, perhaps cause intermetallic compound to form.The main institute of international known high-entropy alloy is the Taiwan, and research is less relatively, perhaps at the early-stage at home.
Summary of the invention
The high-entropy alloy preparation method that this patent is mentioned, can satisfy dissolving each other between the arbitrary element, add the element that alloy only limits to form sosoloid thereby can solve,, can expand the nature and extent of high-entropy alloy greatly for the high-entropy alloy preparation of new special composition provides possibility.The alloy material that the characteristics of this patent are to adopt the mechanical alloying method of high-energy ball milling can be formed arbitrarily in principle, material is by constantly collision in the high-energy ball milling process, cold welding, grind, recrystallize etc. make the continuous refinement of particle can obtain nano-powder material, owing to itself do not dissolve each other between the element that adds, the alloy that forms is actually the miscible complex construction of a kind of standard, and what obtain is non-equilibrium phase or the tissue that does not have on the equilibrium phase diagram.Because high-energy ball milling method can make all even grain refining of high-entropy alloy material structure of many pivots, thereby make high entropy material have new performance and character, this method is applied to the novel non-equilibrium alloy phase that the exploitation of accurate miscible system material can obtain not having on the phasor, thereby researchs and develops out the type material of difference and conventional alloys.
The present invention is that have strong novelty a kind of novel contains difficult miscible high-entropy alloy material preparation method, its objective is and propose a kind of preparation technology who solves unmixing system high-entropy alloy, reach the preparation high function alloys of many pivots (being defined as many pivots alloy of 5 ~ 13 yuan at present), be another alloy world outside the known alloys, because the magnetic electricity performances of its high high-temp stability, solidity to corrosion, high strength, high rigidity, high anti-oxidation character, excellence etc. are frontiers of metallic substance.This patent is a raw material with the multiple alloying element powder that can not form miscible system, solved the alloying element solid solution problem that does not have the solution area in the high-entropy alloy preparation process, its preparation technology's method is reasonable, and the use character and the range of application of novel high-entropy alloy are increased greatly.
The present invention realizes by following scheme.Adopt the pure metal powder; pure non-metal powder is (as silicon; boron etc.) or powdered alloy; the element of shared weight percent and adding requires to adjust according to predetermined alloy material; raw material calculates the stoichiometric ratio of each alloying element by particular requirement; will be through the further refinement in high energy ball mill of the material after the batching; the process argon shield of mechanical alloying; the high-entropy alloy powder of preparation is handled in a vacuum; the mould of under vacuum or protective atmosphere, powder being packed into; adopt the two-way compacting of punching block; and, put into sintering oven and carrying out the sample sintering under argon gas or the reducing atmosphere or under the vacuum condition with the further compression moulding of cold isostatic press.
Described high-entropy alloy is the alloy that contains multiple element, and wherein each principal element all has high atomic percent, and the principal element number is more than or equal to 5, but its atomic percent all is no more than 35%.
Described pure metal powder or alloy powder need be avoided oxidation in operating process, need anneal under hydrogen or other reducing atmosphere before the operation that experimentizes, and guarantee the purity of powder.
It is described that to carry out mechanical alloying in high energy ball mill be that the powder that screening is good is put into planetary high-energy ball mill; abrading-ball and mill jar employing corundum or agate material preparation; milling atmosphere adopts argon shield, rotating speed 800-1200rad/min, 10-60 hour ball milling time.
The two-way compacting of described punching block: 400-600Mpa, cold isostatic compaction: 250-400Mpa.
Described sintering carries out in vacuum oven or feeds protective atmosphere, and sintering temperature: 500-1000 ℃, sintering time 3-8 hour, vacuum sintering required vacuum tightness to be about 10
-6-10
-4Pa, protective atmosphere adopts argon gas or hydrogen.
Described raw material be the granularity of pure metal powder, pure non-metal powder (as silicon, boron etc.) or powdered alloy less than 100 microns, purity requirement〉99%.
Al
31Sn
26Cu
17Ni
10Ti
10Zn
6High-entropy alloy, the composition of this alloy be by weight percentage: 31% aluminium powder, 26% glass putty, 17% copper powder, 10% nickel powder, 10% titanium valve, 6% zinc powder.
Zr
21W
16Cr
14Nb
13Mo
13Fe
10Hf
7Cu
6High-entropy alloy, the composition of this alloy be by weight percentage: 21% zirconium, 16% tungsten powder, 14% chromium powder, 13% niobium powder, 13% molybdenum powder, 10% iron powder, 7% hafnium powder, 6% copper powder.
Pb
21Sn
20Ag
17Nb
16Mg
14Mn
6B
6High-entropy alloy, the composition of this alloy be by weight percentage: the accurate alloy powder of 41% slicker solder, 17% silver powder, 16% niobium powder, 14% magnesium powder, 6% manganese powder, 6% boron powder.
Compare advantage and the positively effect that is had with known technology:
The previous research work of this research team shows, the method for preparing high-entropy alloy of the non-miscible system of processing of present patent application is a kind of high-entropy alloy preparation method at the unmixing alloying element that report is not arranged as yet, its principal feature is to realize dissolving each other between the arbitrary element, add the element that alloy only limits to form sosoloid thereby solved, for the preparation of the high-entropy alloy of new special composition provides possibility, beat the nature and extent of having expanded high-entropy alloy greatly.The alloy material that the characteristics of this patent are to adopt the mechanical alloying method of high-energy ball milling can be formed arbitrarily in principle, material is by constantly collision in the high-energy ball milling process, cold welding, grind, recrystallize etc. make the continuous refinement of particle, can obtain multiple elementary composition high-entropy alloy material, owing to itself do not dissolve each other between the element that adds, the alloy that forms is actually the miscible complex construction of a kind of standard, normally simple face-centered cubic or body-centered cubic, what obtain is non-equilibrium phase or the tissue that does not have on the equilibrium phase diagram.Because high-energy ball milling method can make all even grain refining of high-entropy alloy material structure of many pivots, thereby make high entropy material have high high-temp stability, solidity to corrosion, high strength, high rigidity, high anti-oxidation character, excellent magnetic electricity performance etc., and alloy compositions can in very large range be adjusted, start a wide prospect for metallic substance, become a kind of type material that has development potentiality.
The alloy material that this patent adopts the mechanical alloying method of high-energy ball milling to be formed arbitrarily, material is by constantly collision in the high-energy ball milling process, cold welding, grind, recrystallize etc. make the continuous refinement of particle, can obtain nano bulk material, owing to itself do not dissolve each other between the element that adds, the alloy that forms is actually the miscible complex construction of a kind of standard, what obtain is non-equilibrium phase or the tissue that does not have on the equilibrium phase diagram, its normally simple body-centered cubic or face-centred cubic structure are the novel non-equilibrium alloy phases that does not have on a kind of phasor.
The high-entropy alloy preparation method that this patent is mentioned, can satisfy dissolving each other between the arbitrary element, add the element that alloy only limits to form sosoloid thereby solved,, expanded the nature and extent of high-entropy alloy greatly for the high-entropy alloy preparation of new special composition provides possibility.The method of present patent application is applied to the novel non-equilibrium alloy phase that the exploitation of accurate miscible system material can obtain not having on the phasor, thus the type material of research difference and conventional alloys.
The accurate miscible high-entropy alloy material that this patent is mentioned has been broken through traditional restriction, it is a kind of composition that can in wide range, adjust alloy material, solved the solid solution problem between the unmixing element, thereby obtained the new property of material, it forms Stability Analysis of Structures the alloy of preparation, over-all properties is good, has the magnetic electricity performance of high high-temp stability, solidity to corrosion, high strength, high rigidity, high anti-oxidation character, excellence etc., especially can be applicable to special functional materials and structured material field.The more present known alloy material of its production cost is low, the simple and control easily of entire production process, pollution-free or less contamination, can form production in enormous quantities.The high-entropy alloy material of preparation can adopt metal or non-metallic element arbitrarily according to the demand of character fully, make the research range and the use value of novel alloy material improve greatly, pertinent literature is looked into newly and is shown, the preparation method of the difficult miscible high-entropy alloy of solution mentioned in this article is not at international and domestic open report, related science and technical study field still lack at present, worldwide and find no related application.
Description of drawings
Further specify flesh and blood of the present invention with example below, but content of the present invention is not limited to this.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Fig. 1 is a process flow sheet of the present invention.Preparation 5-10 kind pure metal or powdered alloy; raw material calculates the stoichiometric ratio of each alloying element by particular requirement; with the material further refinement in high energy ball mill that makes; the process argon shield of mechanical alloying; the high-entropy alloy powder of preparation is handled in vacuum glove box; the suitable mould of under vacuum or protective atmosphere, powder being packed into; adopt the two-way compacting of punching block; and, put into sintering oven and carrying out the sample sintering under argon gas or the reducing atmosphere or under the vacuum condition with the further compression moulding of cold isostatic press.The strict control of sintering process associated process conditions makes alloying constituent even, makes alloying element solid solution or be uniformly dispersed fully, makes the miscible structure of corresponding standard, takes out and promptly gets the high-entropy alloy block materials.
Concrete implementing process and method:
One, material composition, granularity and shared weight percent thereof
1, base-material:
Pure metal powder, pure non-metal powder (as silicon, boron etc.), or powdered alloy; Powder size is less than 100 microns.
Purity requirement:〉99%,
The element of shared weight percent and adding requires to adjust according to predetermined alloy material.
Two, technical qualification
1. pure metal powder or alloy powder need be avoided oxidation in operating process, need anneal under hydrogen or other reducing atmosphere before the operation that experimentizes, and guarantee the purity of powder;
2. in high energy ball mill, carry out mechanical alloying: will screen good powder and put into planetary high-energy ball mill, abrading-ball and mill jar employing corundum or agate material preparation, milling atmosphere adopts argon shield, rotating speed 800-1200rad/min, 10-60 hour ball milling time;
3. operate in glove box: the powder for preparing is inserted particular mold, and the entire treatment process is carried out under vacuum environment, prevents the powder oxidation;
4. biscuit compacting pressure
The two-way compacting of punching block: 400-600MPa;
Cold isostatic compaction: 250-400MPa;
5. sintering temperature: 500-1000 ℃, time 3-8 hour; Carry out in vacuum oven, perhaps feed protective atmosphere, vacuum sintering requires vacuum tightness to be about 10
-6-10
-4Pa; Protective atmosphere adopts argon gas or hydrogen.
Embodiment 1
Al
31Sn
26Cu
17Ni
10Ti
10Zn
6The high-entropy alloy preparation:
31% aluminium (Al) powder (constituent content per-cent mentioned in this article specify all unify to refer to weight percent), 26% glass putty (Sn) by weight percentage, 17% copper powder (Cu), 10% nickel powder (Ni), 10% titanium valve (Ti), 6% zinc powder (Zn), the alloyage powder, wherein aluminium and tin element belong to solid-state immiscible system.Through hydrogen annealing 4 hours in the reducing atmosphere stove, insert in the ball grinder of corundum material, vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 800rad/min, 15 hours ball milling time, the accurate miscible powdered alloy of the ultra-fine high entropy of collecting is taken out in glove box, insert in the preprepared mould, two-way compacting in punching block, compression moulding pressure 350MPa, and further suppress with isostatic cool pressing equipment, compression moulding pressure 300MPa, sample is put into the sintering oven sintering, 650 ℃ of sintering temperatures, sintering time 4 hours, it is even that taking-up obtains grain size distribution, and alloy structure is single body-centered cubic structure mutually.The alloy of preparation has certain ductility and plasticity after testing, and toughness can be carried out to a certain degree extrusion processing and rolling deformation, can be used for the related industries field.
Embodiment 2
Pb
21Sn
20Ag
17Nb
16Mg
14Mn
6B
6The high-entropy alloy preparation:
The accurate alloy powder of 41% lead (Pb) tin (Sn) by weight percentage, 17% silver powder (Ag), 16% niobium powder (Nb), 14% magnesium powder (Mg), 6% manganese powder (Mn), 6% boron powder (B), the alloyage powder, wherein lead and tin and boron belong to solid-state immiscible system each other.Through hydrogen annealing 3 hours in the reducing atmosphere stove, insert in the ball grinder of corundum material, vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 1000rad/min, 25 hours ball milling time, the accurate miscible powdered alloy of the ultra-fine high entropy of collecting is taken out in glove box, insert in the preprepared mould, two-way compacting in punching block, compression moulding pressure 300MPa, and further suppress with isostatic cool pressing equipment, compression moulding pressure 250MPa, sample is put into the sintering oven sintering, 550 ℃ of sintering temperatures, sintering time 5 hours, it is even that taking-up obtains grain size distribution, and alloy structure is single face-centred cubic structure mutually.The alloy of preparation has certain ductility and plasticity after testing, and toughness can be carried out to a certain degree extrusion processing and rolling deformation, and is totally different with known conventional alloys performance, but the fundamental characteristics with known alloys can be used for the related industries field.
Embodiment 3
Zr
21W
16Cr
14Nb
13Mo
13Fe
10Hf
7Cu
6The high-entropy alloy preparation:
21% zirconium (Zr) powder, 16% tungsten powder (W) by weight percentage, 14% chromium powder (Cr), 13% niobium powder (Nb), 13% molybdenum powder (Mo), 10% iron powder (Fe), 7% hafnium powder (Hf), 6% copper powder (Cu), the alloyage powder, wherein copper and chromium element belong to the solid-state difficulty system of dissolving each other.Through hydrogen annealing 8 hours in the reducing atmosphere stove, insert in the ball grinder of corundum material, vacuumize, charge into argon gas, under argon shield atmosphere, carry out mechanical alloying.Planetary high-energy ball mill rotating speed 1200rad/min, 45 hours ball milling time, the accurate miscible powdered alloy of the ultra-fine high entropy of collecting is taken out in glove box, insert in the preprepared mould, two-way compacting in punching block, compression moulding pressure 350MPa, and further suppress with isostatic cool pressing equipment, compression moulding pressure 300MPa, sample is put into the sintering oven sintering, 850 ℃ of sintering temperatures, sintering time 4 hours, it is even that taking-up obtains grain size distribution, and alloy structure is single face-centred cubic structure mutually.The alloy of preparation has higher hardness and wear resistance after testing, can be used for the related industries field.
Claims (7)
1. method for preparing high-entropy alloy that contains immiscible element, it is characterized in that: adopt the pure metal powder, pure non-metal powder or powdered alloy, the element of shared weight percent and adding requires to adjust according to predetermined alloy material, raw material calculates the stoichiometric ratio of each alloying element by particular requirement, will be through the further refinement in high energy ball mill of the material after the batching, the process argon shield of mechanical alloying, the high-entropy alloy powder of preparation is handled in a vacuum, the mould of under vacuum or protective atmosphere, powder being packed into, adopt the two-way compacting of punching block, and, put into sintering oven and carrying out the sample sintering under argon gas or the reducing atmosphere or under the vacuum condition with the further compression moulding of cold isostatic press;
Al wherein
31Sn
26Cu
17Ni
10Ti
10Zn
6The composition of high-entropy alloy series is by weight percentage: 31% aluminium powder, 26% glass putty, 17% copper powder, 10% nickel powder, 10% titanium valve, 6% zinc powder;
Zr wherein
21W
16Cr
14Nb
13Mo
13Fe
10Hf
7Cu
6The composition of high-entropy alloy series is by weight percentage: 21% zirconium, 16% tungsten powder, 14% chromium powder, 13% niobium powder, 13% molybdenum powder, 10% iron powder, 7% hafnium powder, 6% copper powder;
Pb wherein
21Sn
20Ag
17Nb
16Mg
14Mn
6B
6The composition of high-entropy alloy series is by weight percentage: the accurate alloy powder of 41% slicker solder, 17% silver powder, 16% niobium powder, 14% magnesium powder, 6% manganese powder, 6% boron powder.
2. the method for preparing high-entropy alloy that contains immiscible element according to claim 1, it is characterized in that: described high-entropy alloy is the alloy that contains multiple element, wherein each principal element all has high atomic percent, the principal element number is more than or equal to 5, but its atomic percent all is no more than 35%.
3. the method for preparing high-entropy alloy that contains immiscible element according to claim 1, it is characterized in that: described pure metal powder or alloy powder need be avoided oxidation in operating process, before the operation that experimentizes, need under hydrogen or other reducing atmosphere, anneal, guarantee the purity of powder.
4. the method for preparing high-entropy alloy that contains immiscible element according to claim 1; it is characterized in that: described to carry out mechanical alloying in high energy ball mill be that the powder that screening is good is put into planetary high-energy ball mill; abrading-ball and mill jar employing corundum or agate material preparation; milling atmosphere adopts argon shield; rotating speed 800-1200rad/min, 10-60 hour ball milling time.
5. the method for preparing high-entropy alloy that contains immiscible element according to claim 1 is characterized in that: the two-way compacting of described punching block: 400-600MPa, cold isostatic compaction: 250-400MPa.
6. the method for preparing high-entropy alloy that contains immiscible element according to claim 1; it is characterized in that: described sintering carries out in vacuum oven or feeds protective atmosphere; sintering temperature: 500-1000 ℃, sintering time 3-8 hour, it was 10 that vacuum sintering requires vacuum tightness
-6-10
-4Pa, protective atmosphere adopts argon gas or hydrogen.
7. the method for preparing high-entropy alloy that contains immiscible element according to claim 1 is characterized in that: described raw material be the granularity of pure metal powder, pure non-metal powder or powdered alloy less than 100 microns, purity requirement＞99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102334779A CN101386928B (en) | 2008-10-24 | 2008-10-24 | Method for preparing high-entropy alloy containing immiscible element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102334779A CN101386928B (en) | 2008-10-24 | 2008-10-24 | Method for preparing high-entropy alloy containing immiscible element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101386928A CN101386928A (en) | 2009-03-18 |
| CN101386928B true CN101386928B (en) | 2011-04-06 |
Family
ID=40476597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102334779A Expired - Fee Related CN101386928B (en) | 2008-10-24 | 2008-10-24 | Method for preparing high-entropy alloy containing immiscible element |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101386928B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039127B (en) * | 2010-12-20 | 2013-03-06 | 昆明理工大学 | Method for preparing catalyst of alpha/gamma-Al2O3-loaded nano-precious metal particles |
| CN102828139A (en) * | 2012-09-28 | 2012-12-19 | 安徽工业大学 | High-entropy alloy powder used for spraying |
| CN103056352B (en) * | 2012-12-04 | 2015-09-09 | 中国人民解放军装甲兵工程学院 | For the high-entropy alloy powder material and preparation method thereof of supersonic spray coating |
| CN104141127B (en) * | 2013-10-10 | 2017-02-08 | 天津大学 | Preparation method of high-entropy alloy powder and cladding layer and application |
| CN104388817A (en) * | 2014-11-28 | 2015-03-04 | 西安交通大学 | High-strength-toughness sintered iron nickel alloy and preparation method thereof |
| CN105463443B (en) * | 2015-12-04 | 2018-06-12 | 山东开泰抛丸机械股份有限公司 | A kind of marine drilling platform corrosion resistant coating production |
| CN105562680B (en) * | 2016-01-05 | 2017-12-05 | 济南大学 | The method that a kind of high-entropy alloy powder and hot pressed sintering prepare high-entropy alloy coating |
| CN106222517B (en) * | 2016-08-30 | 2017-11-24 | 中国船舶重工集团公司第七二五研究所 | A kind of TiCuAlCrMoNb high-entropy alloys and preparation method thereof |
| CN106244889B (en) * | 2016-08-30 | 2017-11-24 | 中国船舶重工集团公司第七二五研究所 | A kind of TiCuAlCrMoNi high-entropy alloys and preparation method thereof |
| CN106825588B (en) * | 2016-12-30 | 2018-09-28 | 西安交通大学青岛研究院 | A kind of mechanical alloying preparation method of nickel aluminium powder |
| CN107661978B (en) * | 2017-10-10 | 2019-07-09 | 安徽工业大学 | Two-phase is containing Mg high entropy semi-hard magnetic alloy powder and preparation method thereof |
| CN107671278B (en) * | 2017-10-10 | 2019-08-02 | 安徽工业大学 | It is single-phase to contain Mg high entropy corrosion resisting alloy powder and preparation method thereof |
| CN108998716B (en) * | 2018-07-26 | 2020-01-03 | 江苏理工学院 | Arc deposited cored wire and preparation method of high-entropy alloy coating thereof |
| CN109161774A (en) * | 2018-11-23 | 2019-01-08 | 西安工业大学 | Haystellite and preparation method thereof by high-entropy alloy as binder |
| EP3663019A1 (en) * | 2018-12-07 | 2020-06-10 | The Swatch Group Research and Development Ltd | Method of manufacturing precious metal alloys and precious metal alloys thus obtained |
| CN109867525A (en) * | 2019-01-28 | 2019-06-11 | 广东工业大学 | A kind of high-entropy alloy boride ceramics and its preparation method and application |
| CN110230056B (en) * | 2019-07-17 | 2021-06-11 | 哈尔滨工程大学 | Low-melting-point high-entropy alloy powder for magnesium-lithium alloy laser surface modification and preparation method and application thereof |
| CN110541104B (en) * | 2019-09-05 | 2021-02-19 | 华南理工大学 | Low-density two-phase high-entropy alloy material and preparation method thereof |
| CN110976888B (en) * | 2019-12-24 | 2022-08-26 | 郑州大学 | Complete solid solution molybdenum-niobium alloy powder and preparation method and application thereof |
| CN111058076B (en) * | 2019-12-30 | 2020-11-20 | 安徽工业大学 | Zr-based high-entropy alloy material and method for synthesizing porous spherical structure on surface of Zr-based high-entropy alloy |
| CN111172446B (en) * | 2020-01-15 | 2021-04-27 | 东南大学 | Strong corrosion-resistant non-equal atomic ratio high-entropy alloy and preparation method thereof |
| CN111519079B (en) * | 2020-04-15 | 2021-09-10 | 燕山大学 | CoCrNiCuFeMnAl high-entropy alloy and preparation method thereof |
| CN111893357B (en) * | 2020-08-06 | 2021-07-16 | 天津工业大学 | Self-supporting three-dimensional nano hierarchical pore high-entropy alloy electrolytic water material and preparation method thereof |
| CN112725679B (en) * | 2021-01-25 | 2022-03-25 | 重庆大学 | Light high-entropy alloy material with high specific strength and preparation method thereof |
| CN113410131B (en) * | 2021-06-18 | 2023-11-28 | 北京科技大学 | Method for screening high-entropy alloy components |
| CN113549780B (en) * | 2021-07-12 | 2022-05-27 | 中国工程物理研究院材料研究所 | Powder metallurgy refractory multi-principal-element high-entropy alloy and preparation method thereof |
| CN114657436B (en) * | 2022-03-25 | 2022-09-23 | 北京航空航天大学 | TiAlMoNbW high-entropy alloy target and preparation process thereof |
| CN116445792A (en) * | 2023-04-10 | 2023-07-18 | 昆明理工大学 | Wear-resistant refractory high-entropy alloy coating and preparation method thereof |
| CN118186276A (en) * | 2024-05-16 | 2024-06-14 | 湖南大学 | High-entropy alloy and preparation method thereof |
-
2008
- 2008-10-24 CN CN2008102334779A patent/CN101386928B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101386928A (en) | 2009-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101386928B (en) | Method for preparing high-entropy alloy containing immiscible element | |
| CN104674038B (en) | Alloy material with high strength as well as ductility and semi-solid state sintering preparation method and application of alloy material | |
| CN109207829B (en) | High-entropy alloy and multicomponent carbide cocrystallizing type composite material and its in-situ preparation method | |
| CN101818291B (en) | Al-Cu-Mg-Ag powdered metallurgical heat-resisting aluminum alloy and preparation method thereof | |
| CN103205721A (en) | Production method of titanium-aluminum alloy target | |
| CN109022988B (en) | Preparation method of tungsten-based high-specific gravity alloy material | |
| CN111004957B (en) | Non-equal atomic ratio high-entropy alloy and preparation method thereof | |
| CN109778050B (en) | WVTaTiZr refractory high-entropy alloy and preparation method thereof | |
| CN111206174A (en) | Magnetic ultrafine-grain high-strength high-entropy alloy and preparation method thereof | |
| CN103088242A (en) | Preparation method of aluminum-zinc-magnesium-copper-zirconium series high-strength aluminum alloy | |
| CN102719769B (en) | High-strength aluminum-based bulk amorphous composite material | |
| CN114481053B (en) | Magnesium zinc aluminum nickel vanadium alloy target and manufacturing method thereof | |
| CN101942592A (en) | Method for preparing molybdenum-copper alloy through activated sintering | |
| Martínez et al. | Microstructural and mechanical characterization of copper, nickel, and Cu-based alloys obtained by mechanical alloying and hot pressing | |
| CN111118379B (en) | Co-bonded TiZrNbMoTa refractory high-entropy alloy and preparation method thereof | |
| Yusefi et al. | WCu functionally graded material: Low temperature fabrication and mechanical characterization | |
| CN113073274A (en) | Novel method for preparing double-phase ultra-fine grain high-entropy alloy | |
| Lityńska-Dobrzyńska et al. | Microstructure and mechanical properties of aluminium matrix composites reinforced by Al62Cu25. 5Fe12. 5 melt spun ribbon | |
| CN103469119A (en) | Amorphous composite materials, and preparation method and applications thereof | |
| CN108517429B (en) | Ti2Preparation method of AlC reinforced copper-based composite material | |
| CN111519079B (en) | CoCrNiCuFeMnAl high-entropy alloy and preparation method thereof | |
| CN109518037A (en) | A kind of Ti-18Mo-xSi alloy material and preparation method thereof of SPS preparation | |
| Martínez et al. | Microstructure and mechanical properties of copper, nickel and ternary alloys Cu-Ni-Zr obtained by mechanical alloying and hot pressing | |
| CN109482880B (en) | Preparation method that is a kind of while promoting Ni-Mn-In alloy mechanical property and magnetic heating performance | |
| CN110819917A (en) | Method for in-situ synthesis of high-length-diameter ratio whisker reinforced aluminum matrix composite by hot isostatic pressing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110406 Termination date: 20131024 |