CN107747019B - A kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system and preparation method thereof - Google Patents
A kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system and preparation method thereof Download PDFInfo
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- 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
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- 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
- C22C1/02—Making non-ferrous alloys by melting
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- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Abstract
A kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system and preparation method thereof, belongs to high-entropy alloy field.The chemical component of alloy is NiaCobCrcAldWeTafMogRx, wherein R Re, one or both of Ru.The present invention removes the surface scale of raw metal using the method mechanically and chemically combined, and cleans raw metal using industrial alcohol ultrasonic oscillation；Vacuum arc furnace melting alloy is reused, when vacuum degree reaches 5 × 10‑2After Pa, it is filled with technical argon；After the abundant melting of master alloy is uniform, using vacuum casting or inhale casting machine, by alloy inject water cooled copper mould in, obtain high-entropy alloy bar, 1250 DEG C solution treatment 2~6 hours, then 900 DEG C and 950 DEG C aging strengthening model 4~50 hours.Alloy of the present invention has excellent room temperature and elevated temperature strength, excellent resistance to high temperature oxidation, excellent creep resistant and anti-fatigue performance and chronic tissue stability, is suitable for manufacture aero-engine and gas turbine hot-end component, such as blade and the turbine disk；For engineering machinery, special vehicle, coal, mine, railway etc..
Description
Technical field
The invention belongs to high-entropy alloy field, be related to a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system and its
Preparation method.
Background technique
High-entropy alloy (or multi-principal elements alloy) is a kind of new alloy material developed in recent years.The characteristics of this alloy
Be: comprising 5 kinds or 5 kinds or more of constituent element, and each constituent element content is between 5% to 35%.Recently, the ingredient model of high-entropy alloy
It encloses and has been further expanded to the constituent element comprising 4 kinds or 4 kinds or more, and each constituent element content is between 5% to 50%, such as
Constituent content in the FeMnCoCr high-entropy alloy (9June 2016, Vol 534, Nature:227) of Ziming Li et al. report
Range has been expanded to 50%.Numerous intermetallic compound phase is not formed after high-entropy alloy solidification, but shape
At the institutional framework based on simple FCC, BCC or HCP solid solution.The formation of solid solution matrix makes high-entropy alloy overcome gold
Compound and the intrinsic brittleness of amorphous alloy between category, so promising to be very much a kind of advanced structural timber.
In recent years, the development of high-entropy alloy is approximately along both direction, first is that the alloy system that development is new.
CN201410386446.2 disclosure of the invention a kind of high-entropy alloy, the alloy are made of aluminium, chromium, iron, nickel, copper, molybdenum, wherein each
The molar ratio of component is (1~1.1): (1~1.05): (1~1.05): (1~1.05): (1~1.05): (1~1.05).
A kind of high tough Ultra-fine Grained high-entropy alloy of CN201410545199.6 disclosure of the invention and preparation method thereof.The height is tough ultra-fine
Brilliant high-entropy alloy is made of the element of following atomic percent: Ni 20%~25%, Fe 18%~20%, Co 18%~
22%, Cr 18%~20%, Al 20%~24%, microstructure are unordered solid with the body-centered cubic rich in Ni, Al element
Solution is mutually matrix phase, with the face-centered cubic random solid solution containing rich Fe, Cr element mutually for reinforced phase.CN201410448734.6
A kind of AlCoCuFeNiSi high-entropy alloy of disclosure of the invention and preparation method thereof, it is therefore an objective to solve existing structure steel heat resistance
Not high problem.The high-entropy alloy of invention preparation has simple body-centered cubic structure and face-centred cubic structure, yield strength
Up to 1781.6MPa, breaking strength are up to 1895.2MPa.The high-entropy alloy of the invention can be as structural material applications in power station
Bearing structure in the heat-resisting field such as boiler.CN201510788841.8 disclosure of the invention is a kind of with shape memory effect
The chemical component of NxMy high-entropy alloy and preparation method thereof, alloy is as follows: 45≤x≤55,45≤y≤55, N be Ti, Zr, Hf,
V, any two in Nb, Ta, Mo and W or two kinds or more, and the content of every kind of element is more than or equal to 5%, is less than or equal to 35%；
M be in V, Mn, Fe, Co, Ni, Cu, Cr and Zn any two or it is a variety of, and the content of every kind of element be more than or equal to 5%, be less than
Equal to 35%.The alloy that the invention is related to has shape memory effect in wide temperature range, while having high-entropy alloy
Characteristic.CN201410132963.7 discloses a kind of preparation method of high rigidity BCC high entropy alloy coating, according to
The component ratio of Al1.5CoCrFeNiTi chooses the metal powder of respective element.It is melted using powder plasma spray welding apparatus
It covers, has prepared the high entropy alloy coating that hardness reaches 700HV.201610090111.5 disclosure of the invention is a kind of to be used for 3D printing
High-entropy alloy amorphous powder and preparation method, belong to metal powder preparation technical field.Its equal atomic percents composition is as follows:
Cu 15.5~18%, Mn 15~18%, Ti 16~18%, Mo 15~18%, Cr 15~18%, Fe 15~18%, always
Percentage is 100%.In addition, present invention applicant also discloses four kinds of high-entropy alloys with BCC structure, it is respectively: (1) one
Kind ingredient is TiZrNbHfOxHigh-entropy alloy, wherein x be molar ratio and value range be x=0~0.1 (patent authorization number:
201310690502.7).Compared with conventional crystal material, high-entropy alloy of the invention shows high-yield strength and fracture is strong
Degree, compared with other high-intensitive body-centred structure high-entropy alloys, high-entropy alloy of the invention has high plastic deformation and low processing
Hardening ratio.(2) a kind of high-strength low-modulus TiZrNbHf high-entropy alloy and preparation method thereof (patent authorization number:
201310593871.4).(3) a kind of TiZrNbVMox high-entropy alloy and preparation method thereof (patent authorization number:
201310530812.2), which shows excellent elevated temperature strength and high-temperature stability.(4) a kind of with hyperelastic
TiZrHfNbAl high-entropy alloy and preparation method thereof.
Another developing direction of high-entropy alloy is new alloy preparation method.CN201410386446.2 discloses a kind of high
The preparation method of entropy alloy.This method is formed by powder materials pressing mold, and vacuum-sintering obtains the large volume high-entropy alloy of high-quality.Benefit
There is preferable hardness, higher compressive strength and corrosion resistance outstanding, Neng Gouman with high-entropy alloy prepared by this method
The certain environment with particular/special requirement of foot.CN201410621549.2 discloses a kind of preparation method of high-entropy alloy enhancing.Its
Method is by AlCrFeNiCo, AlCrFeNiCoTi, and AlCrFeNiCoCu high-entropy alloy particle and Al alloy powder put into ball milling
In tank and seal, mixed 5~25h of powder obtains mixed material, and mixed material is put into jacket, apply at room temperature pressure be 5~
Mixed material in jacket is compacted into blank, the blank after compacting is put into Hot Extrusion Equipment by 15MPa, and preheated charge is extremely
400~480 DEG C, for preheated mold to 200~400 DEG C, then it is 5 in squeeze pressure that blank and mold, which keep the temperature 1~3h preheating and complete,
~15MPa, extrusion ratio are hot extrusion molding under conditions of 4~25, obtain the aluminum matrix composite of high-entropy alloy enhancing.
201410583314.9 a kind of high-entropy alloy turbogenerator hot-end component for being based on precinct laser fusion (SLM) of disclosure of the invention
Manufacturing method, this method chosen from eight kinds of tungsten, titanium, zirconium, hafnium, vanadium, niobium, tantalum and molybdenum refractory metal powder any five kinds or
Five kinds of person or more powder, uniformly mix according to certain mol proportion, and high-entropy alloy powder is made；Establish turbogenerator hot-end component
Three-dimensional entity model, slicing delamination is carried out by software, obtains the outline data in each section, these data are imported fast rapid-result
Shape equipment；Go out turbogenerator hot-end component green body by SLM technology Quick-forming；Green body is heat-treated, is finished, is obtained
To the good high-entropy alloy turbogenerator hot-end component of high-temperature behavior.The turbogenerator hot-end component that the present invention shapes has
High consistency and superior high-temperature behavior, while forming accuracy with higher and surface accuracy, can be realized high-performance whirlpool
The quick accurate manufacture of turbine hot-end component.CN201710155516.7, which is disclosed, a kind of prepares Al0.5CoCrFeNi high
The method of entropy alloy, this method significantly reduce low melting point element Al waving in fusion process using intermediate alloy as raw material
Hair.The ingredient of ingot casting is made using electromagnetic agitation effect possessed by induction heating equipment using vacuum induction heating equipment simultaneously
Uniformity is guaranteed.The fusing point that the present invention is reduced indirectly between minimum fusing point metal Al and peak melting point metal Cr is poor, keeps away
Excessive volatilization problems of the low melting point Al simple substance in fusion process are exempted from, have been made using electromagnetic agitation effect present in induction heating
The homogeneity of ingredients of multi-principal high-entropy alloy is guaranteed.It is pre- by the atmosphere in reasonable design fusion process, air pressure, mold
The parameters such as hot temperature, smelting temperature, soaking time, casting rate successfully prepare the conjunction of large volume Al0.5CoCrFeNi high entropy
Golden ingot casting.A kind of Argon arc cladding high entropy alloy coating of CN201710108364.5 disclosure of the invention and preparation method thereof, with Q235
Steel is matrix, and Fe, Al, Cr, Cu, Co and Ti element are composition high-entropy alloy element, is prepared for height using the method for Argon arc cladding
Entropy alloy coat.In the high entropy alloy coating being prepared, FexAlCrCuCoTi0.4 (x=0,1) is in high entropy alloy coating
Institutional framework by single BCC phase composition, between Fe1AlCrCuCoTi0.4 high entropy alloy coating and matrix be in metallurgical bonding,
Microhardness, abrasive wear and the erosion-wear-resisting performance of coating improve a lot both with respect to matrix, meet actual production need
It wants, and promotes extensive use of the high-entropy alloy on the surface of the material in engineering.201610090111.5 a kind of use of disclosure of the invention
It is as follows in the atomic percent composition of the high-entropy alloy amorphous powder and preparation method of 3D printing, alloy: Cu 15.5~18%,
Mn 15~18%, Ti 16~18%, Mo 15~18%, Cr 15~18%, Fe 15~18%, percent of total 100%.
Using the method for symmetrical liquid drop impulse jet；Load weighted each raw material metal is put into crucible, circulated inert gas is filled with
Protection carries out melting, monitor system 10KW, electric current 28A, and time 40min is aided with electromagnetic agitation and alloy is sufficiently mutually melted；Using
Symmetrical liquid drop pulse jet technique generates the gas pulses of corresponding frequencies and pressure by impulse generator, controls cooling rate,
The high-entropy alloy amorphous powder of high sphericity of the average grain diameter less than 50 μm is prepared, microhardness reaches 1200HV.It is main to use
In the consumptive material of 3D printing.A kind of preparation of Self- propagating Sintering Synthetic founding high-entropy alloy of CN201710207927.6 disclosure of the invention
Method, this method add aluminium oxide work using aluminium powder, iron oxide, cobalt oxide, nickel protoxide, chromium oxide, manganese oxide as raw material
For reaction diluent, relative density prefabricated section is obtained；Graphite crucible and graphite casting mould are assembled, and casting plaster is perfused, gypsum
After type vacuumizes degasification, it is placed in mould drying in Muffle furnace, the prefabricated section of acquisition is placed in the gypsum mould of acquisition, by pre-
The heating coil that clamp dog surface is placed heats prefabricated section surface quickly to light prefabricated section, and high entropy is obtained during combustion heat release
Aluminium alloy.By vacuumizing in gypsum mould bottom, aluminium alloy is cooling in graphite casting mould to obtain high-entropy alloy.
Advanced high-temperature structural material is the foundation stone of the fields such as aerospace and electricity power development, Development of Novel high temperature alloy
Material has important theoretical and practical values.For the demanding room temperature of high temperature alloy and elevated temperature strength, excellent resistant to high temperatures
Oxidation, excellent creep resistant and anti-fatigue performance and chronic tissue stability feature, the present invention devise one kind and contain Ni, Co,
The high entropy high temperature alloy of the elements such as Cr, Al, W, Re, Ta, Mo, the alloy are that a kind of new concept proposed based on high entropy effect is closed
Gold belongs to high-entropy alloy field scope.
Summary of the invention
The present invention is devised with Ni, Co, Cr, Al, W, Ta, based on Mo, adds Re or Ru element according to special requirement
High entropy high temperature alloy, the main function of each element in the present invention are summarized as follows:
Ni is the infrastructure elements of alloy of the present invention, and main function is the matrix to form face-centered cubic crystal structure, simultaneously
The elements such as Ni and Al, Ti form the γ ' phase of L12 structure, this is mutually the key point that alloy obtains excellent high temperature mechanical property.
Co is alloying element important in high temperature alloy.Studies have shown that Co can significantly improve high temperature alloy corrosion and heat resistant
Performance.In terms of mechanical property, Co can play solution strengthening effect, to improve the creep rupture strength and creep resistance of alloy.
Co also makes the quantity that can increase γ ' hardening constituent simultaneously, improves the solid solubility temperature of γ ' phase.The addition of Co also can be reduced carbide and exist
Precipitation on crystal boundary improves the hot-working character, plasticity and impact flexibility of nickel-base alloy.
Cr has good antioxygenic property and hot corrosion resistance, is indispensable important in nickel base superalloy
Element, too low Cr will lead to the inoxidizability of alloy and hot corrosion resistance weakens significantly, again can be strong but Cr is excessively added
The strong precipitation for promoting TCP phase, to damage the mechanical property of alloy.In the forth generation single crystal super alloy containing Ru, Cr's adds
γ ' phase volume fraction and γ-γ ' mismatch can also be increased by adding, to play the role of improving Creep Properties.
Most basic alloying element in Al nickel-base alloy is to form the mutually most important essential element of γ '.High Al content is advantageous
In the high temperature oxidation resistance for improving alloy.The high-temperature behavior of nickel-base alloy depends primarily on the total amount and Ti/Al ratio of Al and Ti.
After identical heat treatment, as Al and Ti content increases, the size of γ ' phase is gradually increased, and γ ' phase morphology is from spherical shape to vertical
Square shape changes to irregular shape again.Therefore the control of Al content is needed to be optimized according to alloying component.
Ta is refinement crystal grain and boundary-strengthening element.Studies have shown that Ta element generally all enters γ ' phase, promote γ ' phase
It is precipitated, delays the agglomeration of γ ' phase, to improve the elevated temperature strength of alloy.Ta element can also increase between γ-γ ' phase
Mismatch, strengthen γ ' mutually with improve γ ' phase high-temperature stability.
W, Mo and Re are common elements in high temperature alloy, wherein Re is the spy of the second generation and third generation single crystal super alloy
Element is levied, is played the role of to the high-temperature behavior for improving alloy vital.There is quite high solubility in γ ' phase, especially
It is that W is added to the increase that will lead to γ ' phase amount after high temperature alloy.Due to the atomic radius of these three elements differ with Ni compared with
Greatly, no matter mutually there is very strong solid solution strengthening effect to γ or γ ', while they also improve the recrystallization temperature and diffusion of alloy
Activation energy increases γ-γ ' mismatch, to play the role of improving the temperature capability of high temperature alloy.But when Mo too high levels
It is easy that μ phase is precipitated in γ matrix, can seriously damage the enduring quality of high temperature alloy.With the increase of Re content, after heat treatment
Tissue in γ ' phase size reduce, a cube degree for γ ' phase morphology obviously increases.
Ru is the characteristic element of forth generation single crystal super alloy.Studies have shown that the addition of Ru, which can be played, postpones TCP phase shape
Core reduces TCP phase Enhancing Nucleation Density and volume fraction, to reach the precipitation effect with inhibition TCP phase, Ru can also change alloy
The distribution behavior of element improves the solubility of refractory element in the base, to improve the effect of Creep Properties.
The chemical component of the high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system of the invention is represented by by atomic ratio
NiaCobCrcAldWeTafMogRx, wherein R Re, one or both of Ru.The chemical composition of each element is 31≤a≤40,
31≤b≤39,5≤c≤20,10≤d≤18,5≤e≤12,0.1≤f≤5,0.1≤g≤5,0≤x≤5, a+b+c+d+e+f
+ g+x=100.
For save the cost, which can be free of precious metal Re and Ru, and above-mentioned composition of alloy can be reduced to
NiaCobCrcAldWeTafMog, composition range be expressed as 31≤a≤40,31≤b≤39,5≤c≤20,10≤d≤18,5≤
E≤12,0.1≤f≤5,0.5≤g≤5, a+b+c+d+e+f+g=100.
In order to effectively control harmful phase TCP phase in alloy, in above-mentioned NiaCobCrcAldWeTafMogIn alloy, improve into one
Step improves the content of Ni and Co, reduces Cr, W, Ta, and the content of Mo, alloy component range can be more preferably 32≤a≤40,
32≤b≤39,5≤c≤18,10.5≤d≤15,5≤e≤10,0.1≤f≤2,0.1≤g≤3, a+b+c+d+e+f+g=
100。
When more harsh to TCP content requirement, in above-mentioned alloy component range, then further improve Ni's and Co
Content reduces the content of Cr and W, and by preferred alloy ingredient, composition range is expressed as 34.5≤a≤40, and 34.5≤b≤
39,5≤c≤17,10.5≤d≤15,5≤e≤7,0.1≤f≤2,0.5≤g≤2, a+b+c+d+e+f+g=100.
In order to obtain more excellent mechanical behavior under high temperature, added on the basis of Ni-Co-Cr-Al-W-Ta-Mo alloy
Re element obtains Ni by optimizing componentsaCobCrcAldWeTafMogRexComposition range be 32≤a≤40,32≤b≤39,5≤
C≤18,10≤d≤18,5≤e≤10,0.1≤f≤3,0.1≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
In order to effectively control NiaCobCrcAldWeTafMogRexTCP phase in alloy, further preferred alloying component, after optimization
Composition range be expressed as 34.5≤a≤40,34.5≤b≤39,5≤c≤17,10≤d≤15,5≤e≤7,0.1≤f≤2,
0.5≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
By adding Ru element on the basis of Ni-Co-Cr-Al-W-Ta-Mo alloy, it can obtain and compare Ni-Co-Cr-
The more excellent mechanical behavior under high temperature of Al-W-Ta-Mo-Re alloy obtains Ni by optimizing componentsaCobCrcAldWeTafMogRux
Composition range be 32≤a≤40,32≤b≤39,5≤c≤18,10≤d≤18,5≤e≤10,0.1≤f≤3,0.1≤g≤
2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
In order in NiaCobCrcAldWeTafMogRuxIn effectively control TCP phase, further preferred alloying component, after optimization
Composition range is expressed as 34.5≤a≤40,34.5≤b≤39,5≤c≤17,10≤d≤15,5≤e≤7,0.1≤f≤2,
0.5≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
The technical solution adopted in the present invention the following steps are included: (1) use 99.5% or more purity Ni, Co, Cr,
Al, W, Ta, Mo, Re, Ru element carry out weighing proportion according to molar ratio, use for preparing alloy；(2) using mechanically and chemically
The method combined removes raw metal Ni, Co, Cr, Al, W, Ta, Mo, the surface scale of Re, Ru, and uses industrial alcohol
Ultrasonic oscillation cleans raw metal；(3) vacuum arc furnace melting alloy is used, sample room is vacuumized, when vacuum degree reaches 5
×10-2After Pa, technical argon is filled with until furnace pressure reaches half of atmospheric pressure；(4) after the abundant melting of master alloy is uniform, make
With vacuum casting or casting machine is inhaled, alloy is injected in water cooled copper mould, high-entropy alloy bar is obtained.(5) high-entropy alloy obtained
Bar 1250 DEG C solution treatment 2~6 hours, then 900 DEG C and 950 DEG C aging strengthening model 4~50 hours.
The advantages of high entropy high temperature alloy of the invention has both high-entropy alloy and high temperature alloy has excellent room temperature and high temperature
Intensity, excellent resistance to high temperature oxidation, excellent creep resistant and anti-fatigue performance and chronic tissue stability are suitable for manufacture aviation
Engine and gas turbine hot-end component, such as blade and the turbine disk；It is also suitable for manufacture naval vessel, marine engineering equipment engine turbine
Blade；Apply also for engineering machinery, special type (military) vehicle, coal, mine, railway etc..
Detailed description of the invention
Fig. 1 is that the XRD of as cast condition Ni35Co30Cr17Al10W7Re1 and Ni40Co25Cr17Al10W7Re1 of the invention are bent
Line.
Fig. 2 is of the invention 1250 DEG C of Ni32Co32Cr18Al10W7Re1 and Ni32Co32Cr18Al10W7Ta1 alloy solid
XRD curve after molten 6 hours+900 DEG C of timeliness 50 hours.
Fig. 3 is the SEM image of as cast condition Ni40Co25Cr17Al10W7Re1 of the invention.
Fig. 4 is the DSC curve of as cast condition Ni32.5Co32.5Cr18Al10W7 and Ni35Co35Cr13Al10W7 of the invention.
Fig. 5 as cast condition Ni32.5Co32.5Cr18Al10W7 Alloy At Room Temperature stress strain curve
Fig. 6 is as cast condition Ni32Co32Cr18Al10W7Re1 Alloy At Room Temperature stress strain curve of the invention
Fig. 7 is as cast condition Ni35Co30Cr17Al10W7Re1 Alloy At Room Temperature stress strain curve of the invention
Fig. 8 is as cast condition Ni35Co34Cr15Al10W5Re1 Alloy At Room Temperature stress strain curve of the invention
Fig. 9 is that Ni35Co34Cr15Al10W5Re1 alloy solid solution of the invention closes room temperature stress strain curve after ageing treatment
Figure 10 is as cast condition Ni40Co25Cr17Al10W7Re1 Alloy At Room Temperature stress strain curve of the invention
Specific embodiment
It is specific in terms of ingredient design, alloy preparation and performance test three below to introduce the present invention.
1, ingredient designs
Design the Ni of 10 kinds of heterogeneitiesaCobCrcAldWeTafMogRex, wherein the composition range of each element be 31≤a≤
40,31≤b≤35,10≤c≤18, d=10,5≤e≤10,0≤f≤1,0≤g≤1,0≤x≤1, a+b+c+d+e+f+g+x
=100.The specific ingredient of 10 kinds of alloys is as shown in Table 1.The purpose of this 10 kinds of design of alloy is primarily to study each member
Element is to the affecting laws of alloy mechanical property, and in addition to Ni, Co, Cr, Al, W outside Ta, Mo, select Re and Ru as further increasing
The addition element of elevated temperature strength.
The composition proportion (atomic percent) of one 10 kinds of table high entropy high temperature alloys
| Serial number | Ni | Co | Cr | Al | W | Mo | Ta | Re | Ru |
| NC1 | 31.5 | 31.5 | 18 | 10 | 7 | 0 | 1 | 1 | 0 |
| NC2 | 32 | 32 | 18 | 10 | 7 | 0 | 1 | 0 | 0 |
| NC3 | 32 | 32 | 18 | 10 | 7 | 0 | 0 | 1 | 0 |
| NC4 | 32.5 | 32.5 | 18 | 10 | 7 | 0 | 0 | 0 | 0 |
| NC5 | 35 | 35 | 10 | 10 | 10 | 0 | 0 | 0 | 0 |
| NC6 | 35 | 35 | 13 | 10 | 7 | 0.5 | 0 | 0 | 0 |
| NC7 | 35 | 30 | 17 | 10 | 7 | 0.5 | 0 | 1 | 0 |
| NC8 | 35 | 34 | 15 | 10 | 5 | 0.5 | 0 | 1 | 0 |
| NC9 | 40 | 25 | 17 | 10 | 7 | 0.5 | 0 | 1 | 0 |
| NC10 | 40 | 25 | 17 | 10 | 7 | 0.5 | 0 | 0 | 1 |
2. prepared by alloy
1) ingredient: using the Ni of 99.5% or more purity, Co, Cr, Al, W, Ta, Mo, Re, Ru element utilizes mechanical and changes
It learns the method combined and removes raw metal Ni, Co, Cr, Al, W, Ta, Mo, the surface scale of Re, Ru, and use industrial second
Alcohol ultrasonic oscillation cleans raw metal, carries out accurate weighing according to molar ratio and matches raw material.
2) the rodlike sample preparation of alloy: vacuum arc furnace melting alloy is used, sample room is vacuumized, when vacuum degree reaches
5×10-2After Pa, technical argon is filled with until furnace pressure reaches half of atmospheric pressure；After the abundant melting of master alloy is uniform, use
Vacuum casting inhales casting machine, and alloy is injected in water cooled copper mould, the high-entropy alloy bar of 10 × 10 × 70mm is obtained.
3) be heat-treated: the high-entropy alloy bar of acquisition at 2~6 hours, then 900 DEG C and 950 DEG C of aging strengthening models 4~
50 hours.
3. alloy structure performance test
1) X-ray diffraction (XRD) is tested
Crystal species analysis is carried out to sample using X-ray diffractometer, for convenience of testing, the sample of different-diameter is using different
Test equipment, the sample of diameter 2mm or more tested using Cu target XRD equipment, scanning step 0.02s-1, scanning angle
The range of 2 θ is from 10 ° to 90 °.Fig. 1 be as cast condition Ni35Co30Cr17Al10W7Re1 of the invention and
The XRD curve of Ni40Co25Cr17Al10W7Re1.It can be seen that alloy is single-phase FCC configuration.Fig. 2 is of the invention
1250 DEG C of Ni32Co32Cr18Al10W7Re1 and Ni32Co32Cr18Al10W7Ta1 alloy solid solutions, 6 hours+900 DEG C of timeliness 50 are small
When after XRD curve part γ ' phase has been precipitated in alloy other than original FCC phase.
2) scanning electron microscopic observation
The microscopic structure of alloy is observed using scanning electron microscope, Fig. 3 is as cast condition of the invention
The SEM image of Ni40Co25Cr17Al10W7Re1, it is seen then that under as-cast condition, the tissue of alloy is single-phase γ dendrite group
It knits.
3) differential scanning calorimetry (DSC) is analyzed
Using differential scanning calorimeter to amorphous alloy sample carry out Thermodynamic Analysis, heating rate 20K/min,
Temperature elevating range is 300K~1600K.Fig. 4 be as cast condition Ni32.5Co32.5Cr18Al10W7 of the invention and
The DSC curve of Ni35Co35Cr13Al10W7.For high temperature alloy, fusion temperature is very important adjustment temperature, alloy
Temperature capability and fusion temperature height it is closely related.From the curve, the fusion temperature of available alloy is two kinds of conjunctions
The fusion temperature of gold is respectively 1383 DEG C and 1400 DEG C.Illustrate that the fusion temperature of high entropy high temperature alloy is more molten than general high temperature alloy
Change temperature and wants high.
4) by the rodlike of preparation, being machined into standard size is 1mm × 5mm × 10mm plaques, in CMT
Room temperature tensile test is carried out on 4305 type universal electrical testing machines, rate of extension is 1 × 10-3s-1, every kind of alloying component at least selects
3 samples are taken to be tested.Table two is the room-temperature mechanical property of N1~NC10 alloy, wherein N1~NC9 alloy is experiment test
As a result, the performance of NC10 be based on Re and Ru it is having the same effect and by the Performance inference of NC9 alloy come.Exemplary alloy room
Warm stress strain curve is as shown in Fig. 6~10.
Fig. 7 is as cast condition Ni35Co30Cr17Al10W7Re1 Alloy At Room Temperature stress strain curve of the invention, and Fig. 8 is of the invention
As cast condition Ni35Co34Cr15Al10W5Re1 Alloy At Room Temperature stress strain curve, Fig. 9 are Ni35Co34Cr15Al10W5Re1 of the invention
Alloy solid solution closes room temperature stress strain curve after ageing treatment, and Figure 10 is as cast condition Ni40Co25Cr17Al10W7Re1 alloy of the invention
Room temperature tensile curve
The tensile tests at room result of two alloy part of table
It can be seen that in this ten kinds of alloys, as-cast condition lower yield strength and tensile strength it is highest be NC9 alloy, elongation percentage
Highest is NC4 alloy, and highest elasticity modulus is NC2 alloy.Solid solution and ageing treatment to improve alloy yield strength and
Elasticity modulus is significantly increased, but the elongation percentage of alloy can be made to decrease.From the point of view of alloys producing, containing for Ni is improved
Amount helps to improve the intensity and elasticity modulus of alloy.The addition of Ta and Mo improves the intensity of alloy.The addition of Co, W, Re and Ru
Influence to room-temperature property is unobvious, and the effect of both elements is more the influence being embodied in mechanical behavior under high temperature.
Claims (6)
1. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system, it is characterised in that alloy composition is set by atomic ratio
It is calculated as: NiaCobCrcAldWeTafMogRx, composition characteristics are R Re, one or both of Ru；Wherein, 31≤a≤40,
31≤b≤39,5≤c≤20,10≤d≤18,5≤e≤12,0≤f≤5,0≤g≤5,0≤x≤5, a+b+c+d+e+f+g+x
=100；
The preparation method of the high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system the following steps are included:
(1) use 99.5% or more purity Ni, Co, Cr, Al, W, Ta, Mo, Re, Ru element, according to molar ratio carry out weigh match
Than being used for preparing alloy；
(2) raw metal Ni, Co, Cr, Al, W, Ta, Mo, the surface of Re, Ru are removed using the method mechanically and chemically combined
Oxide skin, and raw metal is cleaned using industrial alcohol ultrasonic oscillation；
(3) vacuum arc furnace melting alloy is used, sample room is vacuumized, when vacuum degree reaches 5 × 10-2After Pa, it is filled with industry
Argon gas reaches half of atmospheric pressure until furnace pressure；
(4) after the abundant melting of master alloy is uniform, using vacuum casting or casting machine is inhaled, alloy is injected in water cooled copper mould, is obtained
Obtain high-entropy alloy bar；
(5) obtain high-entropy alloy bar 1250 DEG C solution treatment 2~6 hours, then in 900 DEG C of aging strengthening models 4~50
Hour.
2. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system as described in claim 1, it is characterised in that described
NiaCobCrcAldWeTafMogRxIn, as x=0, the composition of alloy is expressed as NiaCobCrcAldWeTafMog, ingredient model
It encloses and is expressed as 31≤a≤40,31≤b≤39,5≤c≤20,10≤d≤18,5≤e≤12,0.1≤f≤5,0.5≤g≤5, a
+ b+c+d+e+f+g=100.
3. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system as described in claim 1, it is characterised in that described
NiaCobCrcAldWeTafMogRxIn, when R is limited to Re element, the composition of alloy is expressed as 32≤a≤40, and 32≤b≤
39,5≤c≤18,10≤d≤18,5≤e≤10,0.1≤f≤3,0.1≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x
=100.
4. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system as claimed in claim 3, it is characterised in that described
NiaCobCrcAldWeTafMogRexIn, composition range is expressed as 34.5≤a≤40,34.5≤b≤39,5≤c≤17,10≤d
≤ 15,5≤e≤7,0.1≤f≤2,0.5≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
5. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system as described in claim 1, it is characterised in that described
NiaCobCrcAldWeTafMogRxIn, when R is limited to Ru element, the composition of alloy is expressed as
NiaCobCrcAldWeTafMogRux, composition range is expressed as 32≤a≤40,32≤b≤39,5≤c≤18,10≤d≤18,5
≤ e≤10,0.1≤f≤3,0.1≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
6. a kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system as claimed in claim 5, it is characterised in that described
NiaCobCrcAldWeTafMogRuxIn, composition range is expressed as 34.5≤a≤40,34.5≤b≤39,5≤c≤17,10≤d
≤ 15,5≤e≤7,0.1≤f≤2,0.5≤g≤2,0.5≤x≤2, a+b+c+d+e+f+g+x=100.
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