CN109594002A - A kind of more pivot medium entropy alloys and preparation method thereof - Google Patents

A kind of more pivot medium entropy alloys and preparation method thereof Download PDF

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CN109594002A
CN109594002A CN201811465459.3A CN201811465459A CN109594002A CN 109594002 A CN109594002 A CN 109594002A CN 201811465459 A CN201811465459 A CN 201811465459A CN 109594002 A CN109594002 A CN 109594002A
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pivot
medium entropy
ingredient
entropy alloys
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CN109594002B (en
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刘宁
范佳承
陈晨
彭振
杜文栋
王小京
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Jiangsu University of Science and Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C1/02—Making non-ferrous alloys by melting

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Abstract

The present invention relates to a kind of more pivot medium entropy alloys and preparation method thereof, the ingredient of more pivot medium entropy alloys is Fe by atomic percent25Ni25Co50‑xMox(0≤x≤50)；Ingredient is Fe25Ni25Co25Mo25Medium entropy alloy have optimal comprehensive mechanical property: hardness 411HV, yield strength 1520MPa, compression strength reaches 2056MPa, while plasticity reaches 31%.Medium entropy alloy of the invention is prepared using arc melting method, and the preparation method technique simplifies, and difficulty is lower, so that cost is relatively low.

Description

A kind of more pivot medium entropy alloys and preparation method thereof
Technical field
The present invention relates to metal material and its preparation fields, in particular to a kind of more pivot medium entropy alloys and its preparation Method.
Technical background
In thermodynamics, entropy represents the confusion degree of system, and entropy is bigger, and the confusion degree of system is bigger, when entropy reaches When to maximum value, system tends towards stability, and reaches balance.Novel more pivot metal materials are with higher system △ SmixValue is different from Conventional alloys, for conventional alloys based on a kind of element, the entropy of mixing is less than 0.693R, and (R is gas constant R=8.314J/ MolK) belong to low entropy alloy, the alloy being made of 2~4 kinds of elements, the entropy of mixing between 0.693R~1.61R, referred to as in Entropy alloy.The alloy of 5 kinds and above element composition, the entropy of mixing is on 1.61R, referred to as high-entropy alloy.
The high entropy of mixing can be effectively reduced the Gibbs free energy (△ G=△ H-T △ S) of system, to make alloy System is more stable.Generally, although having more constituent element, multi-principal elements alloy tends to form simple phase in phase composition Structure, this is conducive to the raising of alloy property.High-entropy alloy is easy to obtain because having high entropy and atom to be not easy the characteristic spread Thermal stability high solid solution phase and nanostructure or even non crystalline structure are obtained, while having some conventional alloys institutes incomparable Excellent properties, such as high intensity, hardness, wearability, preferable plasticity and toughness, good structure stability and corrosion resistance etc..
AlCoCrCuFeMoxIn Ni system high-entropy alloy, as Mo content increases, the intensity of alloy is significantly improved, but simultaneously Along with the severe exacerbation of alloy plasticity；AlCoCrCuFeMo0.6The compression strength of Ni alloy reaches peak 2820MPa, and strains Value is only 1.1%.This seminar previous experiments result of study shows to wait atomic percents CoCrFeMoNi multi-principal high-entropy alloy Compression strength reach 2427MPa, yield strength 1250MPa, while plastic strain is 33%.Patent (CN 201610759867.4 with CN 201610758896.9) conjunction of TiCuAlCrMoNi and TiCuAlCrMoNb high entropy is disclosed respectively Gold, two kinds of alloys all have higher yield strength, tensile strength and certain elongation percentage, while fine corrosion resistance, but Above-mentioned high-entropy alloy includes a variety of refractory metals there are a common problem, i.e. alloy, and smelting technology is complicated, at high cost.
Therefore, on the basis of guaranteeing preferable strong plasticity cooperation, technology difficulty is reduced as much as possible, is saved cost, is Middle and high entropy Alloyapplication problems faced.
Summary of the invention
One of the objects of the present invention is to provide a kind of more pivot medium entropy alloys.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of more pivot medium entropy alloys, it is characterised in that: its ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 0≤x≤50。
Further preferably, ingredient is Fe by atomic percent25Ni25Co25Mo25。
Further preferably, ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 0≤x < 25.
Further preferably, ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 25 x≤50 <.
Further preferably, ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 0≤x < 15.
Further preferably, ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 15≤x≤50.
The second object of the present invention is to provide the preparation method of more pivot medium entropy alloys.Concrete scheme is as follows:
A kind of preparation method of more pivot medium entropy alloys, comprising the following steps:
Step 1: be converted into mass percentage according to atomic percentage content, and by the metal former material of purity >=99.95% Material is matched according to mass percentage accurate weighing, is used for molten alloy；
Step 2: melting uses non-consumable arc furnace, the load weighted simple substance raw material of step 1 is put into vacuum arc In water cooled copper mould melting pond in furnace, oxygen uptake titanium is placed among crucible, then fire door is closed, tightens knob；
Step 3: by electric arc stove evacuation, when vacuum degree reaches 5 × 10-3Purity >=99.99wt% is filled with after Pa into furnace Argon gas to normal pressure, so carry out " vacuumizing-applying argon gas " 1~3 time, then carry out melting, melting is overturn after founding ingot, such as This melt back is to uniform, furnace cooling ingot.
Further preferably, melting electric current described in step 3 is 350~450A.
Beneficial effects of the present invention:
Compared with conventional alloys, more pivot medium entropy alloys intensity with higher of the invention and preferably plasticity；With property CoCrFeMoNi high-entropy alloy that can be close compares, and the preparation method technique of medium entropy alloy of the invention simplifies, due to infusibility gold Melting is uniform less and more easily for category, and cost is relatively low, is conducive to produce.
Detailed description of the invention
Due to Fe and Ni ingredient it is known that for the sake of simplifying, the ingredient of Co and Mo is only shown in attached drawing.
Fig. 1 is the Fe of embodiment25Ni25Co50-xMoxThe XRD spectrum of medium entropy alloy, wherein Fig. 1 a is Fe25Ni25Co50-xMox (when 25 < x≤50, x is respectively 30,35,40,45,50) XRD diagram of medium entropy alloy, and Fig. 1 b is Fe25Ni25Co50-xMox(0≤x When≤25, x is respectively 0,5,10,15,20,25) XRD diagram of medium entropy alloy.
Fig. 2 is the Fe of embodiment25Ni25Co50-xMoxThe solidified structure photo of medium entropy alloy, wherein Fig. 2 a~Fig. 2 k be Fe25Ni25Co50-xMoxSEM figure of the medium entropy alloy when x is respectively 0,5,10,15,20,25,30,35,40,45,50.
Fig. 3 is the Fe of embodiment25Ni25Co50-xMoxThe compressive stress strain curve and hardness of medium entropy alloy, wherein Fig. 3 a For Fe25Ni25Co50-xMox(when 25 < x≤50, x is respectively 30,35,40,45,50) compression stress-strain of medium entropy alloy is bent Line chart, Fig. 3 b are Fe25Ni25Co50-xMox(when 25≤x≤50, x is respectively 25,30,35,40,45,50) Vickers of medium entropy alloy Hardness figure, Fig. 3 c are Fe25Ni25Co50-xMox(when 0≤x≤25, x is respectively 0,5,10,15,20,25) compression of medium entropy alloy Stress-strain curve, Fig. 3 d are Fe25Ni25Co50-xMox(when 0≤x≤25, x is respectively 0,5,10,15,20,25) medium entropy conjunction The Vickers hardness figure of gold.
Specific embodiment
The present invention is described in detail below by way of specific embodiment, but this embodiment is merely illustrative, It does not form any restrictions to the present invention.
Embodiment
1. Fe of the invention25Ni25Co50-xMoxThe preparation process of medium entropy alloy is as follows:
Step 1: accurately calculating high pure metal raw material (>=99.95%) and weigh according to mass percentage, for molten Alloy is refined to use；
Step 2: WK type non-consumable arc furnace is used, load weighted simple substance raw material is put into vacuum arc furnace ignition In water cooled copper mould melting pond, oxygen uptake titanium is placed among crucible, then fire door is closed, tightens knob；
Step 3: by electric arc stove evacuation, when vacuum degree reaches 5 × 10-399.99wt% purity is filled with after Pa into furnace Argon gas reduces volatilization to normal pressure when being to keep alloy not oxidized and alloy melting in this way.It carries out " vacuumizing-filling in this way Argon gas " three times, can melting.Melting about 30 seconds, alloy is overturn under 400A electric current, repeatedly founding 5 times it is uniform to ingredient, After the completion of melting, furnace cooling obtains the uniform Fe of ingredient25Ni25Co50-xMoxAlloy pig.
2. the institutional framework and performance of alloy
1) X-ray diffraction (XRD) test and crystal species analysis
Sample is cut with Metallographic Specimen Cutting Machine, then with #600 silicon carbide paper ground on levigator one it is smooth flat Whole plane is to do XRD analysis, and 2 θ range of scanning angle is 30-80 °, and scanning speed is 6 °/min.
Fig. 1 is Fe25Ni25Co50-xMoxThe XRD analysis map of medium entropy alloy, wherein Fig. 1 a is Fe25Ni25Co50-xMox(25 When < x≤50, x is respectively 30,35,40,45,50) XRD diagram of medium entropy alloy, and Fig. 1 b is Fe25Ni25Co50-xMox(0≤x≤25 When, x is respectively 0,5,10,15,20,25) XRD diagram of medium entropy alloy.In conjunction with Fig. 1 a and Fig. 1 b it is found that with Mo constituent content Increase, the reduction of Co constituent content, Fe25Ni25Co50-xMoxIt is the phase structure of multi-principal elements alloy by the single opposite FCC+ of FCC BCC+ topology solid matter phase or the transformation of MoNi phase heterogeneous structure.
Equal atomic percents Fe25Ni25Co25Mo25The crystal structure of alloy is mainly by simple face-centered cubic phase FCC Xiang Yutuo Flutter solid matter phase (including μ phase and σ phase) composition.Wherein FCC is similar is similar to Fe0.64Ni0.36 phase, and dot-pattern space group is Fm3m, Lattice constant is a=b=c=3.592.Due to the presence of systematic extinction law in X-ray diffraction spectrum, only when indices of crystallographic plane H, K, when L is all odd number or even number, face-centered cubic lattice just has diffraction phenomena, so diffraction corresponding to simple face-centered cubic phase Peak is respectively (111), (200), (220) and (311) crystal face.μ phase is the complicated ordered phase similar to Co7Mo6 phase, and point type is empty Between group be R-3m, lattice constant a=b=4.672, c=25.617.σ phase is the complicated ordered phase similar to Co2Mo3 phase, Dot-pattern space group is P42/mnm, lattice constant a=b=9.229, c=4.827.
2) scanning electron microscope (SEM) structure observation and analysis
The advanced line of alloy is cut into the pole of certain length, then it is inlayed, 180# is utilized after inlaying, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper carry out water mill and polish.Then corroded using chloroazotic acid, the examination after corrosion Sample carries out solidified structure shooting using scanning electron microscope.
Fig. 2 is Fe25Ni25Co50-xMoxThe solidified structure photo of medium entropy alloy, wherein Fig. 2 a~Fig. 2 k be in order Fe25Ni25Co50-xMoxSEM figure of the medium entropy alloy when x is respectively 0,5,10,15,20,25,30,35,40,45,50.It can send out It is existing, Fe25Ni25Co50-xMoxMedium entropy Solidification Structure is mainly made of primary dendrite and interdendritic Eutectic Layer lamellar structure. From Fig. 2 a~Fig. 2 c as can be seen that as x < 15%, Solidification Structure is simple dendrite；It can be with from Fig. 2 d~Fig. 2 k Find out, as x >=15%, Fe25Ni25Co50-xMoxMulti-principal elements alloy solidified structure dendrite and interdendritic eutectic structure.
3) alloy compression experiment
By the advanced line cutting of sample, being prepared into diameter is 5mm, is highly the standard compression test rod of 10mm, utilizes water Dry sanding paper polishes smooth both ends smooth.If both ends are not horizontal, error will be generated in compression process, influences test result. Room temperature compression experiment is carried out on universal testing machine.And compressive stress strain curve is drawn with Origin software.
4) alloy rigidity is tested
The advanced line of alloy is cut into the pole of certain length, then it is inlayed, 180# is utilized after inlaying, 400#, 800#, 1000#, 1500#, 2000# silicon carbide paper carry out water mill and polish.Then corroded using chloroazotic acid, the examination after corrosion Sample measures the hardness of alloy using micro Vickers.The load chosen in this experiment be 25K, load retention time 10s, Hardness number is read after unloading.It measures 7 groups of hardness numbers and records, calculate average value.
Fig. 3 show Fe25Ni25Co50-xMoxThe mechanical property of more pivot medium entropy alloys, wherein Fig. 3 a is Fe25Ni25Co50- xMox(when 25 < x≤50, x is respectively 30,35,40,45,50) the compressive stress strain curve figure of medium entropy alloy, and Fig. 3 b is Fe25Ni25Co50-xMox(when 25≤x≤50, x is respectively 25,30,35,40,45,50) the Vickers hardness figure of medium entropy alloy, Fig. 3 c For Fe25Ni25Co50-xMox(when 0≤x≤25, x is respectively 0,5,10,15,20,25) compression stress-strain of medium entropy alloy is bent Line chart, Fig. 3 d are Fe25Ni25Co50-xMox(when 0≤x≤25, x is respectively 0,5,10,15,20,25) Vickers of medium entropy alloy is hard Degree figure.It can be seen that the increase with Mo constituent content, the reduction of Co constituent content, Fe from Fig. 3 b and Fig. 3 d25Ni25Co50- xMoxThe hardness of multi-principal elements alloy increases to 953.53HV from 137.28HV.It can be seen that from Fig. 3 a and Fig. 3 c Fe25Ni25Co25Mo25Alloy and Fe25Ni25Mo50Alloy obtains maximum compression strength (2056MPa) and yield strength respectively (1928MPa)；According to Fig. 1 a and Fig. 1 b: the alloy of single-phase FCC configuration has excellent plasticity but intensity lower, and FCC+ BCC+ topology solid matter phase/MoNi phase heterogeneous structure alloy intensity with higher, but plasticity is lower with the raising of intensity.
As can be seen that Fe25Ni25Co25Mo25 alloy has preferably strong plasticity cooperation, resistance to compression from Fig. 3 a- Fig. 3 d Intensity is 2056MPa, yield strength 1520MPa, while being able to maintain 31% plastic strain.

Claims (8)

1. a kind of more pivot medium entropy alloys, it is characterised in that: its ingredient is Fe by atomic percent25Ni25Co50-xMox, wherein 0 ≤x≤50。
2. more pivot medium entropy alloys according to claim 1, which is characterized in that its ingredient is by atomic percent Fe25Ni25Co25Mo25。
3. more pivot medium entropy alloys according to claim 1, which is characterized in that its ingredient is by atomic percent Fe25Ni25Co50-xMox, wherein 0≤x < 25.
4. more pivot medium entropy alloys according to claim 1, which is characterized in that its ingredient is by atomic percent Fe25Ni25Co50-xMox, wherein 25 x≤50 <.
5. more pivot medium entropy alloys according to claim 1, which is characterized in that its ingredient is by atomic percent Fe25Ni25Co50-xMox, wherein 0≤x < 15.
6. more pivot medium entropy alloys according to claim 1, which is characterized in that its ingredient is by atomic percent Fe25Ni25Co50-xMox, wherein 15≤x≤50.
7. a kind of preparation method of any one of claim 1~6 more pivot medium entropy alloys, which is characterized in that including following Step:
Step 1: being converted into mass percentage according to atomic percentage content, and the raw material metal of purity >=99.95% is pressed It weighs and matches according to mass percentage, used for molten alloy；
Step 2: melting uses non-consumable arc furnace, the load weighted simple substance raw material of step 1 is put into vacuum arc furnace ignition Water cooled copper mould melting pond in, oxygen uptake titanium is placed among crucible, then fire door is closed, tightens knob；
Step 3: by electric arc stove evacuation, when vacuum degree reaches 5 × 10-3Purity >=99.99wt% argon is filled with after Pa into furnace Gas so carries out " vacuumizing-applying argon gas " 1~3 time, then carries out melting, overturn melting after founding ingot, so instead to normal pressure Remelt is refined to uniform, furnace cooling ingot.
8. wanting the preparation method of 7 more pivot medium entropy alloys according to right, which is characterized in that the electricity of melting described in step 3 Stream is 350~450A.
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CN112643003A (en) * 2020-12-01 2021-04-13 中南大学 Method for preparing aluminum-based medium-entropy alloy through electromagnetic stirring casting
CN113234986A (en) * 2021-06-03 2021-08-10 哈尔滨工程大学 Low-activation refractory medium-entropy alloy and preparation method thereof
CN113878220A (en) * 2021-08-27 2022-01-04 合肥工业大学 Tungsten and steel layered metal composite material and diffusion bonding method thereof
CN116005150A (en) * 2022-12-07 2023-04-25 哈尔滨工业大学 High-temperature friction wear resistant high-entropy alloy coating and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN111676411A (en) * 2020-06-30 2020-09-18 江苏鑫信润科技股份有限公司 Microalloyed high-toughness dynamic sealing material and preparation method thereof
CN111676412A (en) * 2020-06-30 2020-09-18 江苏鑫信润科技股份有限公司 Oxidation-resistant corrosion-resistant dynamic sealing material and preparation method thereof
CN112643003A (en) * 2020-12-01 2021-04-13 中南大学 Method for preparing aluminum-based medium-entropy alloy through electromagnetic stirring casting
CN113234986A (en) * 2021-06-03 2021-08-10 哈尔滨工程大学 Low-activation refractory medium-entropy alloy and preparation method thereof
CN113878220A (en) * 2021-08-27 2022-01-04 合肥工业大学 Tungsten and steel layered metal composite material and diffusion bonding method thereof
CN116103556A (en) * 2022-09-29 2023-05-12 西北工业大学 Face-centered cubic structure high-entropy alloy with excellent room temperature wear resistance and preparation method thereof
CN116005150A (en) * 2022-12-07 2023-04-25 哈尔滨工业大学 High-temperature friction wear resistant high-entropy alloy coating and preparation method thereof
CN116005150B (en) * 2022-12-07 2023-09-19 哈尔滨工业大学 High-temperature friction wear resistant high-entropy alloy coating and preparation method thereof

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