CN107755668A - The method for preparing enhancing nickel base superalloy composite single crystal blade - Google Patents
The method for preparing enhancing nickel base superalloy composite single crystal blade Download PDFInfo
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- CN107755668A CN107755668A CN201710854816.4A CN201710854816A CN107755668A CN 107755668 A CN107755668 A CN 107755668A CN 201710854816 A CN201710854816 A CN 201710854816A CN 107755668 A CN107755668 A CN 107755668A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/02—Use of electric or magnetic effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
- B22D27/045—Directionally solidified castings
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
Abstract
The present invention relates to the method for preparing enhancing nickel base superalloy composite single crystal blade, main raw material(s) is used as by the use of ultra-fine monocrystalline nickel powder, add reinforcing material, other ultra-fine refractory metal powders are added according to high-temperature alloy material recipe requirements, after shaping, the method recrystallized by electromagnetic field containment induced regions melting directional solidification prepares the nickel base superalloy composite single crystal turbine blade that aircraft engine graphene strengthens.Compared with prior art, the present invention makes full use of the excellent mechanical performance and high-termal conductivity of reinforcing material, suppress the generation and development of internal stress crackle during single crystal blade work, improve the thermal conductivity factor and quick heat radiating performance of single crystal blade, so as to significantly improve the mechanical behavior under high temperature of traditional single crystal blade, operating temperature and fatigue at high temperature service life, and then significantly improve the thrust-weight ratio of aircraft engine.
Description
Technical field
The invention belongs to aerospace material technical field, induces and prepares more particularly, to the electromagnetic field based on extra-fine nickel powder
Strengthen the method for nickel base superalloy composite single crystal blade.
Background technology
Single crystal blade is the cast blade of only one crystal grain.Directional solidification crystallization blade eliminates quick to cavity and crackle
The transverse grain boundaries of sense, make whole crystal boundaries parallel to stress direction of principal axis, so as to improve the applied at elevated temperature performance of alloy.Aviation at present
Engine turbine blade generally uses the single crystal hollow structure of compound film cooling formula, but because its planform is complicated, shaping
Precision is relatively low, percent defective is high, and the industrialization of single crystal blade casting is not implemented, and is more not carried out strengthening by adding the second phase
Material improves the performance of turbo blade.Graphene be it is a kind of completely by conjugation hydridization carbon atom arrangement into honeycomb structure two
Material is tieed up, has proved to be most thin, the most hard nano material in world, it is almost fully transparent.Graphene has
2630m2/ g theoretical specific surface area, for its fracture strength up to 125GPa, tensile strength reaches 130GPa, and Young's modulus is up to
1100GPa, thermal conductivity factor are up to 5300W/mK, and higher than CNT and diamond, and resistivity only has about 1 Ω m, compares copper
It is the minimum material of resistivity, and chemical property is extremely stable or silver is lower.Moreover, carbon is nature fusing point highest material,
Fusing point is up to 3650 DEG C.As can be seen here, graphene has excellent mechanical property and thermal property, is a kind of ideal gold
Belong to solid solution second-phase strength reinforcing material.If by the advantages that graphene high-melting-point, high intensity, high ratio modulus and nickel-base high-temperature
The features such as alloy strength is high, antifatigue creep-resistant property is good combines, and the material for nickel base superalloy single crystal blade is set
Meter and performance boost bring tremendous influence, and are expected to develop the nickel base superalloy of the graphene enhancing with excellent properties
Composite single crystal blade.
Although United States Patent (USP) US2012070303A1, US2012034098A1 and Chinese patent 200510046361.0 propose
A kind of rhenium-containing prepares nickel base superalloy single crystal blade method, and the He of Chinese patent 201510907051.7
201610214707.1 propose a kind of preparation method for the nickel base superalloy for preparing graphene enhancing, and these above-mentioned patents will
It is to prepare single crystal blade using traditional directional solidification technique, otherwise it is to prepare Ni-based height using traditional composite technology
Temperature alloy composite, still can not solve the problems, such as to improve turbo blade performance.
The content of the invention
The purpose of the present invention is exactly in order to which the nickel base superalloy single crystal blade for overcoming prior art to produce does not add stone
Black alkene reinforcing material, mechanical property is low, the shortcomings of fatigue at high temperature short life and a kind of electricity based on ultra-fine monocrystalline nickel powder for proposing
The method that induced by magnetic field prepares enhancing nickel base superalloy composite single crystal blade, by making full use of graphene reinforcing material
Excellent mechanical performance and high-termal conductivity, suppress single crystal blade work when internal stress crackle generation and development, improve monocrystalline
The thermal conductivity factor of blade, to spread out the heat of blade in itself rapidly during applied at elevated temperature, so as to improve turbine
Mechanical property of the blade in applied at elevated temperature, fatigue at high temperature life-span and the operating temperature for especially improving turbo blade.
The purpose of the present invention can be achieved through the following technical solutions:
The method for preparing enhancing nickel base superalloy composite single crystal blade, using following steps:
(1) using ultra-fine monocrystalline or polycrystalline nickel powder particle as main raw material(s), added according to high-temperature alloy material recipe requirements
Other ultra-fine refractory metal powders;
(2) it is reinforcing material to add graphene, CNT or carbon fiber, and ball milling mixing is uniform;
(3) the well mixed powder added with reinforcing material is molded by mould or 3D printing is into blade blank;
(4) obtained blade blank is completed into Alloying Treatment by zone refining and directional solidification realizes recrystallization, profit
There is the characteristics of superparamagnetism more than Curie temperature with ultra-fine monocrystalline nickel powder, apply electromagnetic field before smelting area, force also
The monocrystalline or the small domains magnetic moment of polycrystalline nickel powder particle not melted are aligned by the direction of growth of single crystal blade, while molten
Refining also applies electromagnetic field behind region, constrains and induce blade large single crystal magnetic domain magnetic not solidified, in high temperature re-crystallization process
Square aligns growth by the direction of growth of single crystal blade, and slowly solidification and crystallization forms all atomic arrangements one and touches the same list
Crystal, so as to make to obtain the nickel-base composite material single crystal blade of graphene, CNT or fibre reinforced.
As preferred embodiment, ultra-fine monocrystalline or polycrystalline nickel powder particle is spherical or spherical crystal in step (1),
Particle diameter is micron, sub-micron or nano-particle, and addition is more than 50wt%, and particle diameter is 20nm~1mm;It is it is further preferred that ultra-fine
1~10 μm, 50~100wt% of addition of the particle size range of monocrystalline or polycrystalline nickel powder particle, then it is further preferred that addition is 65
~85wt%.
As preferred embodiment, other submicron metals include tungsten, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium in step (1)
Or the one or more in tantalum, powder are micron, sub-micron or nano-particle, pattern is spherical or spherical, can be crystal,
Can also be noncrystal.
As preferred embodiment, the addition of the reinforcing material described in step (2) is 0.01~10wt%, preferably
Addition is 0.1~1wt%.
As preferred embodiment, the reinforcing material added needs have good powder dispersity, and electrical conductivity is high,
Thermal conductivity is good, the characteristics such as impurity element is few.The graphene added is individual layer or few layer, and lamella is less than 10 layers, and phosphorus content is more than
99%, specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m.The CNT added is single wall or double wall carbon nano-tubes
Pipe, diameter are less than 4 μm, and length is less than 30 μm, and purity is more than 95%, and specific surface area is more than 400m2/ g, electrical conductivity are more than 150S/
m.The carbon fiber added is the carbon fiber powder of high heat conduction, and diameter is less than 50 μm, and length is less than 500 μm, and phosphorus content is more than 99%,
Specific surface area is more than 0.4m2/ g, electrical conductivity are more than 1000S/m, and thermal conductivity factor is more than 400W/mK.Using dry ball milling or wet method
Ball milling is mixed.
As more preferred embodiment, reinforcing material is preferably graphene.The graphene added is individual layer or few
Layer, lamella are less than 10 layers, and phosphorus content is more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m.
As preferred embodiment, at 1000~1600 DEG C, temperature is terraced for the smelting temperature control of step (4) smelting area
Degree>50K/cm, hauling speed 0.5-150mm/min, empty gas and water or liquid metal can be used to cool down;In unfused melting
Apply pre-treatment external electromagnetic field before region, the external electromagnetic field magnetic moment direction and the angle of spoon of blade axial direction control all the time
In the range of 10 degree;In the after-applied post processing external electromagnetic field of not solidified smelting area, the external electromagnetic field magnetic moment side
Controlled all the time in the range of less than 10 degree to the angle with spoon of blade axial direction.
As more preferred embodiment, the magnetic strength of processing external electromagnetic field before applying before unfused smelting area
Intensity is answered to be controlled in 0.1~100 tesla, external magnetic-field direction and the axial of blade at 0~5 °.In not solidified smelting area
The magnetic induction intensity of after-applied post processing external electromagnetic field is in 0.1~100 tesla, the axial direction control of external magnetic-field direction and blade
System is at 0~5 °.
It is solid vane or hollow blade to make obtained composite single crystal blade, can be monocrystalline leaf from material
Piece, column crystal blade, the directional solidification blade of equiax crystal blade or grain refining.
In addition to blade, it can also make to obtain composite machine casket and the turbine disk by the above method.
Compared with prior art, the present invention introduces graphene etc. and is used as reinforcing material in the material, with ultra-fine monocrystalline or more
Brilliant nickel powder is main raw material(s), while the double inductive constraint Directional Recrystallizations of external electromagnetic field, fully profit are introduced in technical process
With the excellent mechanical performance and high-termal conductivity of reinforcing material, suppress the generation of internal stress crackle and hair during single crystal blade work
Exhibition, the thermal conductivity factor and quick heat radiating performance of single crystal blade are improved, so as to significantly improve the high-temperature mechanics of traditional single crystal blade
Energy, operating temperature and fatigue at high temperature service life, and then the thrust-weight ratio of aircraft engine is significantly improved, it can obtain following beneficial
Effect:
(1) graphene is added in raw material, the generation and development of internal stress crackle during single crystal blade work can be suppressed, improved
The thermal conductivity factor of single crystal blade, to spread out the heat of blade in itself rapidly during applied at elevated temperature, so as to improve
Mechanical property of the turbo blade in applied at elevated temperature, especially improve the fatigue at high temperature life-span and improve the work temperature of turbo blade
Degree.
(2) raw material uses submicron metal, can reduce sintering, crystallization temperature, crystal grain is more refined;
(3) because using submicron metal, sintering driving force is stronger, and diffusion of alloy elements is more easy, diffusion length
It is short, it is easier to alloying, while gross segregation can be reduced;
(4) extra-fine nickel powder is used, in more than 357.6 DEG C of nickel curie point, extra-fine nickel powder has superparamagnetism, before thawing
Under additional confining magnetic field regulation and control, the orientation of monocrystalline magnetic domain can be easily adjusted, constrains and control, constraint powder granule melts
Change, sintering.
(5) due to sintering without the domain structure for destroying monocrystalline nickel powder, in recrystallization process, monocrystalline can easily be made
Grain magnetic domain aligns, and completes recrystallization process.
(6) powder metallurgy, it is formulated by changing, is easily adjusted and controls single crystal alloy composition and ratio;
(7) melted using electromagnetic field containment, constraint induced coagulation recrystallization;
(8) sintering process is substantially alloying, recrystallization process, and sintering temperature can be less than 1453 DEG C of nickel fusing point, without
Powder all melts, and surface, which is melted, completes sintering, eliminates single crystal grain crystal boundary, completes alloying, eventually form big alloy list
Brilliant process.
(9) the double constraints of rotating excitation field, it can control monocrystal magnetic domain, the arrangement of atomic magnetic moment direction consistent, it can be ensured that crystallization
Direction axially controls all the time with spoon of blade<5 °, thus improve monocrystalline quality and yield rate;
(10) without putamina, the type heart, the pollution of formwork composition, deformation effect is reduced, reduces cost;
(11) 3D printing or molding are preforming, accurately control blade dimensions and shape, easily prepare hollow blade blank;
(12) powder metallurgyization is once completed with sintering, crystallization;
(13) zone sintering, bigger thermograde can be established, is easily controlled longitudinal heat flux direction and transverse temperature distribution,
Fast Sintering and solidification, it is not necessary to vacuum sintering furnace;
(14) without seeding, choosing crystalline substance, changeover portion waste material.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
Using 2 microns of spherical super fine monocrystalline nickel powder, 0.3wt% graphene powder is added, the graphene added is
Individual layer, phosphorus content are more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity is more than 1000S/m, while according to material prescription, presses
Tungsten of the ratio addition less than 5 microns, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, the ball milling in alcohol solvent
It is well mixed, blade blank is formed using 3D printing technique, zone refining alloying then is carried out to blank, while in melting
Region forms big thermograde and is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces nothing
The small nickel powder monocrystalline magnetic domain of sequence aligns, the oriented growth of constraint induction nickel-base alloy monocrystalline, while it is additional to rotate adjustment
The direction in magnetic field, the small domains magnetic moment for constraining ultra-fine monocrystalline nickel powder align direction and axially retained all the time with turbo blade
In the angle less than 5 degree.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan,
The advantages that operating temperature is high.
Embodiment 2
Using 2 microns of spherical super fine polycrystalline nickel powder, 0.3wt% carbon nanotube dust, the carbon nanometer added are added
Manage and be less than 4 μm for single-walled carbon nanotube, diameter, length is less than 30 μm, and purity is more than 95%, and specific surface area is more than 400m2/ g, electricity
Conductance is more than 150S/m, while according to material prescription, adds tungsten, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, the tantalum less than 5 microns in proportion
Equal sphere submicron metal, ball milling mixing is uniform in alcohol solvent, forms blade blank using powder molding technique, then
Zone refining alloying is carried out to blank, while forms big thermograde in smelting area and is oriented solidification, close
The front and rear of smelting area applies external electromagnetic field, forces unordered small nickel powder monocrystalline magnetic domain to align, constraint induction nickel
The oriented growth of based alloy monocrystalline, while the direction of adjustment externally-applied magnetic field is rotated, constrain the small domains magnetic of ultra-fine monocrystalline nickel powder
Square aligns the angle that is axially retained at less than 5 degree of the direction all the time with turbo blade.Obtained graphene strengthens composite wood
Expect single crystal blade mechanical property is good, fatigue at high temperature long lifespan, the advantages that operating temperature is high.
Embodiment 3
Using 2 microns of spherical super fine polycrystalline nickel powder, 0.3wt% carbon fiber powder is added, the carbon fiber added is
The carbon fiber powder of high heat conduction, diameter are less than 50 μm, and length is less than 500 μm, and phosphorus content is more than 99%, and specific surface area is more than 0.4m2/
G, electrical conductivity are more than 1000S/m, and thermal conductivity factor is more than 400W/mK, while is less than 5 microns according to material prescription, in proportion addition
Tungsten, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, ball milling mixing is uniform in alcohol solvent, utilizes powder
Mould pressing process forms blade blank, then carries out zone refining alloying to blank, while big temperature is formed in smelting area
Degree gradient is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces unordered small nickel powder list
Brilliant magnetic domain aligns, the oriented growth of constraint induction nickel-base alloy monocrystalline, while rotates the direction of adjustment externally-applied magnetic field, constraint
The small domains magnetic moment of ultra-fine monocrystalline nickel powder aligns the folder that is axially retained at less than 5 degree of the direction all the time with turbo blade
Angle.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan, operating temperature height etc. are excellent
Point.
Embodiment 4
Using 500 nanometers of spherical super fine monocrystalline nickel powder, 0.3wt% graphene powder, the graphene added are added
For 5 layers, phosphorus content is more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity is more than 1000S/m, while according to material prescription, presses
Tungsten of the ratio addition less than 5 microns, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, the ball milling in alcohol solvent
It is well mixed, blade blank is formed using 3D printing technique, zone refining alloying then is carried out to blank, while in melting
Region forms big thermograde and is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces nothing
The small nickel powder monocrystalline magnetic domain of sequence aligns, the oriented growth of constraint induction nickel-base alloy monocrystalline, while it is additional to rotate adjustment
The direction in magnetic field, the small domains magnetic moment for constraining ultra-fine monocrystalline nickel powder align direction and axially retained all the time with turbo blade
In the angle less than 5 degree.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan,
The advantages that operating temperature is high.
Embodiment 5
Using 50 nanometers of spherical super fine monocrystalline nickel powder, 0.3wt% graphene powder is added, the graphene added is
8 layers, phosphorus content is more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m, while according to material prescription, by than
Tungsten of the example addition less than 5 microns, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, ball milling mixes in alcohol solvent
Close uniformly, form blade blank using 3D printing technique, zone refining alloying then is carried out to blank, while in smelting zone
Domain forms big thermograde and is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces unordered
Small nickel powder monocrystalline magnetic domain align, the oriented growth of constraint induction nickel-base alloy monocrystalline, while rotate the additional magnetic of adjustment
Direction, the small domains magnetic moment for constraining ultra-fine monocrystalline nickel powder aligns direction and is axially retained at all the time with turbo blade
Angle less than 5 degree.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan, work
Make the advantages that temperature is high.
Embodiment 6
Using 2 microns of spherical super fine monocrystalline nickel powder, 0.1wt% graphene powder is added, the graphene added is 2
Layer, phosphorus content are more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m, while according to material prescription, by than
Tungsten of the example addition less than 5 microns, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, ball milling mixes in alcohol solvent
Close uniformly, form blade blank using 3D printing technique, zone refining alloying then is carried out to blank, while in smelting zone
Domain forms big thermograde and is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces unordered
Small nickel powder monocrystalline magnetic domain align, the oriented growth of constraint induction nickel-base alloy monocrystalline, while rotate the additional magnetic of adjustment
Direction, the small domains magnetic moment for constraining ultra-fine monocrystalline nickel powder aligns direction and is axially retained at all the time with turbo blade
Angle less than 5 degree.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan, work
Make the advantages that temperature is high.
Embodiment 7
Using 2 microns of spherical super fine monocrystalline nickel powder, 1wt% graphene powder is added, the graphene added is 5
Layer, phosphorus content are more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m, while according to material prescription, by than
Tungsten of the example addition less than 5 microns, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium, tantalum equal sphere submicron metal, ball milling mixes in alcohol solvent
Close uniformly, form blade blank using 3D printing technique, zone refining alloying then is carried out to blank, while in smelting zone
Domain forms big thermograde and is oriented solidification, applies external electromagnetic field in the front and rear close to smelting area, forces unordered
Small nickel powder monocrystalline magnetic domain align, the oriented growth of constraint induction nickel-base alloy monocrystalline, while rotate the additional magnetic of adjustment
Direction, the small domains magnetic moment for constraining ultra-fine monocrystalline nickel powder aligns direction and is axially retained at all the time with turbo blade
Angle less than 5 degree.The mechanical property of obtained graphene enhancing composite single crystal blade is good, fatigue at high temperature long lifespan, work
Make the advantages that temperature is high.
Embodiment 8
The method that electromagnetic field induction based on extra-fine nickel powder prepares enhancing nickel base superalloy composite single crystal blade, is adopted
Use following steps:
(1) using ultra-fine monocrystalline nickel powder particle as main raw material(s), the ultra-fine monocrystalline nickel powder particle that is used in the present embodiment for
It is spherical, particle diameter 20nm, addition 50wt%, other superfine metals can also be added according to high-temperature alloy material recipe requirements
Powder, the submicron metal added in the present embodiment is tungsten, molybdenum, and powder is nano-particle, and pattern is sphaerocrystal, then is carried out
Dry ball milling mixes;
(2) CNT is added as reinforcing material, and the CNT added is double-walled carbon nano-tube, and diameter is less than 4 μ
M, length are less than 30 μm, and purity is more than 95%, and specific surface area is more than 400m2/ g, electrical conductivity are more than 150S/m, and addition is above-mentioned
The 0.01wt% of material, is then well mixed using dry ball milling;
(3) well mixed submicron metal is molded into blade blank by mould;
(4) obtained blade blank is completed into Alloying Treatment by smelting area and directional solidification realizes recrystallization, melted
The smelting temperature control in region is refined at 1100 DEG C, thermograde>50K/cm, hauling speed 0.5mm/min, use during directional solidification
Air carries out cooling treatment.Apply magnetic field before and after smelting area, force the monocrystalline not melted also or polycrystalline nickel powder particle
Small domains by the direction of growth of single crystal blade aligned and constrained and induce the monocrystalline magnetic in high temperature re-crystallization process
Square is aligned by the direction of growth of single crystal blade, wherein, the magnetic induction of processing external electromagnetic field before applying before smelting area
Intensity is 0.1 tesla, and magnetic moment direction and the angle of spoon of blade axial direction control in the range of less than 10 degree all the time, in melting
The after-applied post processing external electromagnetic field in region, the magnetic induction intensity of the external electromagnetic field is 0.1 tesla, magnetic moment direction and blade
The angle of curved surface axial direction controls in the range of less than 10 degree all the time, and making obtains single crystal blade, and its structure is solid.
Embodiment 9
The method that electromagnetic field induction based on extra-fine nickel powder prepares enhancing nickel base superalloy composite single crystal blade, is adopted
Use following steps:
(1) using ultra-fine monocrystalline nickel powder particle as main raw material(s), the ultra-fine monocrystalline nickel powder particle that is used in the present embodiment for
Spherical, particle diameter is 1 μm, addition 65wt%, and other ultra-fine gold can also be added according to high-temperature alloy material recipe requirements
Belonging to powder, the submicron metal added in the present embodiment is tungsten, molybdenum, and powder is submicron particle, and pattern is sphaerocrystal, then
Carry out dry ball milling mixing;
(2) CNT is added as reinforcing material, and the CNT added is double-walled carbon nano-tube, and diameter is less than 4 μ
M, length are less than 30 μm, and purity is more than 95%, and specific surface area is more than 400m2/ g, electrical conductivity are more than 150S/m, and addition is above-mentioned
The 0.1wt% of material, is then well mixed using dry ball milling;
(3) well mixed submicron metal is molded into blade blank by mould;
(4) obtained blade blank is completed into Alloying Treatment by smelting area and directional solidification realizes recrystallization, melted
The smelting temperature control in region is refined at 1200 DEG C, thermograde>50K/cm, hauling speed 10mm/min, use during directional solidification
Air carries out cooling treatment.Apply magnetic field before and after smelting area, force the monocrystalline not melted also or polycrystalline nickel powder particle
Small domains by the direction of growth of single crystal blade aligned and constrained and induce the monocrystalline magnetic in high temperature re-crystallization process
Square is aligned by the direction of growth of single crystal blade, wherein, the magnetic induction of processing external electromagnetic field before applying before smelting area
Intensity is 1 tesla, and magnetic moment direction and the angle of spoon of blade axial direction are controlled at 5 degree, located after smelting area is after-applied all the time
External electromagnetic field is managed, the magnetic induction intensity of the external electromagnetic field is 1 tesla, and magnetic moment direction and the angle of spoon of blade axial direction begin
At 5 degree, making obtains hollow column crystal blade for control eventually.
Embodiment 10
The method that electromagnetic field induction based on extra-fine nickel powder prepares enhancing nickel base superalloy composite single crystal blade, is adopted
Use following steps:
(1) using ultra-fine polycrystalline nickel powder particle as main raw material(s), the ultra-fine polycrystalline nickel powder particle that is used in the present embodiment for
Spherical, particle diameter is 10 μm, addition 85wt%, and other ultra-fine gold can also be added according to high-temperature alloy material recipe requirements
Belong to powder, the submicron metal added in the present embodiment is cobalt, rhenium, ruthenium, and powder is micro particles, and pattern is spherical amorphous
Body, then carry out wet ball grinding mixing;
(2) carbon fiber is added as reinforcing material, and the carbon fiber added is the carbon fiber powder of high heat conduction, and diameter is less than 50
μm, length is less than 500 μm, and phosphorus content is more than 99%, and specific surface area is more than 0.4m2/ g, electrical conductivity are more than 1000S/m, heat conduction system
Number is more than 400W/mK, and addition is the 1wt% of above-mentioned material, is then well mixed using wet ball grinding;
(3) by well mixed submicron metal by 3D printing into blade blank;
(4) obtained blade blank is completed into Alloying Treatment by smelting area and directional solidification realizes recrystallization, melted
The smelting temperature control in region is refined at 1400 DEG C, thermograde>50K/cm, hauling speed 80mm/min, use during directional solidification
Air carries out cooling treatment.Apply magnetic field before and after smelting area, force the monocrystalline not melted also or polycrystalline nickel powder particle
Small domains by the direction of growth of single crystal blade aligned and constrained and induce the monocrystalline magnetic in high temperature re-crystallization process
Square is aligned by the direction of growth of single crystal blade, wherein, the magnetic induction of processing external electromagnetic field before applying before smelting area
Intensity is 10 teslas, and magnetic moment direction and the angle of spoon of blade axial direction are controlled at 2 degree, located after smelting area is after-applied all the time
External electromagnetic field is managed, the magnetic induction intensity of the external electromagnetic field is 10 teslas, magnetic moment direction and the angle of spoon of blade axial direction
All the time control at 2 degree, making obtains hollow equiax crystal blade.
Embodiment 11
The method that electromagnetic field induction based on extra-fine nickel powder prepares enhancing nickel base superalloy composite single crystal blade, is adopted
Use following steps:
(1) using ultra-fine polycrystalline nickel powder particle as main raw material(s), the ultra-fine polycrystalline nickel powder particle that is used in the present embodiment for
It is spherical, particle diameter 1mm, addition 95wt%, other ultra-fine gold can also be added according to high-temperature alloy material recipe requirements
Belong to powder, the submicron metal added in the present embodiment is cobalt, rhenium, ruthenium, and powder is micro particles, and pattern is spherical amorphous
Body, then carry out wet ball grinding mixing;
(2) carbon fiber is added as reinforcing material, and the carbon fiber added is the carbon fiber powder of high heat conduction, and diameter is less than 50
μm, length is less than 500 μm, and phosphorus content is more than 99%, and specific surface area is more than 0.4m2/ g, electrical conductivity are more than 1000S/m, heat conduction system
Number is more than 400W/mK, and addition is the 10wt% of above-mentioned material, is then well mixed using wet ball grinding;
(3) by well mixed submicron metal by 3D printing into blade blank;
(4) obtained blade blank is completed into Alloying Treatment by smelting area and directional solidification realizes recrystallization, melted
The smelting temperature control in region is refined at 1600 DEG C, thermograde>50K/cm, hauling speed 150mm/min, use during directional solidification
Air carries out cooling treatment.Apply magnetic field before and after smelting area, force the monocrystalline not melted also or polycrystalline nickel powder particle
Small domains by the direction of growth of single crystal blade aligned and constrained and induce the monocrystalline magnetic in high temperature re-crystallization process
Square is aligned by the direction of growth of single crystal blade, wherein, the magnetic induction of processing external electromagnetic field before applying before smelting area
Intensity is 10 teslas, and magnetic moment direction and the angle of spoon of blade axial direction are controlled at 0 degree, located after smelting area is after-applied all the time
External electromagnetic field is managed, the magnetic induction intensity of the external electromagnetic field is 10 teslas, magnetic moment direction and the angle of spoon of blade axial direction
All the time control at 0 degree, making obtains hollow equiax crystal blade.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (14)
1. prepare the method for enhancing nickel base superalloy composite single crystal blade, it is characterised in that this method uses following step
Suddenly:
(1) using ultra-fine monocrystalline or polycrystalline nickel powder particle as main raw material(s), added according to high-temperature alloy material recipe requirements other
Ultra-fine refractory metal powder;
(2) one or more added in graphene, CNT or carbon fiber are uniform as reinforcing material, ball milling mixing;
(3) the well mixed powder added with reinforcing material is molded by mould or 3D printing is into blade blank;
(4) obtained blade blank is completed into Alloying Treatment by zone refining and directional solidification realizes recrystallization, in melting
Apply electromagnetic field before region and force life of the small domains magnetic moment of the monocrystalline not melted also or polycrystalline nickel powder particle by single crystal blade
Length direction aligns, and in the after-applied electromagnetic field of smelting area, constrains and induces and be not solidified, in high temperature re-crystallization process
Blade large single crystal magnetic domain magnetic moment aligns growth solidification and crystallization by the direction of growth of single crystal blade and forms all atomic arrangements
Consistent monocrystal, make the nickel-base composite material single crystal blade strengthened.
2. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In ultra-fine monocrystalline or polycrystalline the nickel powder particle described in step (1) is spherical or spherical crystal, and particle diameter is micron, sub-micron
Or nano-particle, addition are more than 50wt%.
3. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In the particle diameter of ultra-fine monocrystalline or polycrystalline the nickel powder particle described in step (1) is 20nm~1mm, the μ of preferable particle size scope 1~10
M, 50~100wt% of addition, 65~85wt% of the amount of being preferably added to.
4. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In, other submicron metals described in step (1) include the one or more in tungsten, molybdenum, chromium, cobalt, rhenium, ruthenium, aluminium or tantalum,
Powder is micron, sub-micron or nano-particle, and pattern is spherical or spherical, can be crystal or noncrystal.
5. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In, the addition of the reinforcing material described in step (2) is 0.01~10wt%, and the amount of being preferably added to is 0.1~1wt%,
Described graphene is individual layer or few layer, and lamella is less than 10 layers, and phosphorus content is more than 99%, and specific surface area is more than 80m2/ g, electricity
Conductance is more than 1000S/m,
Described CNT is single wall or double-walled carbon nano-tube, and diameter is less than 4 μm, and length is less than 30 μm, and purity is more than 95%,
Specific surface area is more than 400m2/ g, electrical conductivity are more than 150S/m,
Described carbon fiber is the carbon fiber powder of high heat conduction, and diameter is less than 50 μm, and length is less than 500 μm, and phosphorus content is more than 99%,
Specific surface area is more than 0.4m2/ g, electrical conductivity are more than 1000S/m, and thermal conductivity factor is more than 400W/mK.
6. the method for enhancing nickel base superalloy composite single crystal blade, its feature are prepared according to claim 1 or 5
It is, the reinforcing material described in step (2) is preferably graphene.The graphene added is that individual layer or few layer, lamella are less than
10 layers, phosphorus content is more than 99%, and specific surface area is more than 80m2/ g, electrical conductivity are more than 1000S/m.
7. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In step (2) is mixed using dry ball milling or wet ball grinding.
8. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In, the smelting area described in step (4) smelting temperature control at 1000~1600 DEG C, thermograde>50K/cm, hauling speed
0.5-150mm/min, empty gas and water or liquid metal can be used to cool down.
9. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In processing external electromagnetic field, the external electromagnetic field magnetic moment direction and blade before step (4) applies before unfused smelting area
The angle of curved surface axial direction controls in the range of less than 10 degree all the time.
10. the method according to claim 9 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In, external electromagnetic field magnetic induction intensity in 0.1~100 tesla, the axial direction control of external magnetic-field direction and blade 0~
5°。
11. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In step (4) is in the after-applied post processing external electromagnetic field of not solidified smelting area, the external electromagnetic field magnetic moment direction and blade
The angle of curved surface axial direction controls in the range of less than 10 degree all the time.
12. the method according to claim 11 for preparing enhancing nickel base superalloy composite single crystal blade, its feature
Be, the magnetic induction intensity of external electromagnetic field in 0.1~100 tesla, the axial direction control of external magnetic-field direction and blade 0~
5°。
13. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In the composite single crystal blade for making to obtain is solid vane or hollow blade.
14. the method according to claim 1 for preparing enhancing nickel base superalloy composite single crystal blade, its feature exist
In the composite material blade for making to obtain is the directional solidification leaf of single crystal blade, column crystal blade, equiax crystal blade or grain refining
Piece.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108580881A (en) * | 2018-06-13 | 2018-09-28 | 东莞宜安科技股份有限公司 | A kind of 3D printing metallic composite |
CN109811279A (en) * | 2019-01-21 | 2019-05-28 | 北京科技大学 | A kind of fibre reinforced metal-based high-temperature composite material and preparation method thereof |
CN110821673A (en) * | 2018-08-10 | 2020-02-21 | 劳斯莱斯有限公司 | Turbine arrangement for a gas turbine engine |
CN113737047A (en) * | 2021-09-23 | 2021-12-03 | 河南科技大学 | Metal-based composite material and preparation method thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3890816A (en) * | 1973-09-26 | 1975-06-24 | Gen Electric | Elimination of carbide segregation to prior particle boundaries |
US4060413A (en) * | 1975-12-24 | 1977-11-29 | Westinghouse Canada Limited | Method of forming a composite structure |
US4111606A (en) * | 1976-12-27 | 1978-09-05 | United Technologies Corporation | Composite rotor blade |
US5876659A (en) * | 1993-06-25 | 1999-03-02 | Hitachi, Ltd. | Process for producing fiber reinforced composite |
US20070074601A1 (en) * | 2003-07-25 | 2007-04-05 | Korea Advanced Institute Of Science And Technology | Method of producing metal nanocomposite powder reinforced with carbon nanotubes and the powder prepared thereby |
CN101550523A (en) * | 2009-05-07 | 2009-10-07 | 山东交通学院 | Nickel aluminide intermetal compound-carbon nanotube composite material and preparation thereof |
CN102031465A (en) * | 2009-09-24 | 2011-04-27 | 现代自动车株式会社 | Method of fabricating nano composite powder consisting of carbon nanotube and metal |
CN102719693A (en) * | 2012-06-11 | 2012-10-10 | 上海交通大学 | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof |
CN102864324A (en) * | 2012-09-06 | 2013-01-09 | 东北大学 | Preparation method for carbon nanomaterial enhanced aluminum base composite material |
CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
CN106834807A (en) * | 2016-12-29 | 2017-06-13 | 苏州大学 | A kind of Graphene enhancing two-phase metal aluminide composite and preparation method thereof |
CN107159896A (en) * | 2017-04-17 | 2017-09-15 | 上海交通大学 | The method for preparing single crystal blade based on the double induced orientation recrystallizations in extra-fine nickel powder region |
-
2017
- 2017-09-20 CN CN201710854816.4A patent/CN107755668B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3890816A (en) * | 1973-09-26 | 1975-06-24 | Gen Electric | Elimination of carbide segregation to prior particle boundaries |
US4060413A (en) * | 1975-12-24 | 1977-11-29 | Westinghouse Canada Limited | Method of forming a composite structure |
US4111606A (en) * | 1976-12-27 | 1978-09-05 | United Technologies Corporation | Composite rotor blade |
US5876659A (en) * | 1993-06-25 | 1999-03-02 | Hitachi, Ltd. | Process for producing fiber reinforced composite |
US20070074601A1 (en) * | 2003-07-25 | 2007-04-05 | Korea Advanced Institute Of Science And Technology | Method of producing metal nanocomposite powder reinforced with carbon nanotubes and the powder prepared thereby |
CN101550523A (en) * | 2009-05-07 | 2009-10-07 | 山东交通学院 | Nickel aluminide intermetal compound-carbon nanotube composite material and preparation thereof |
CN102031465A (en) * | 2009-09-24 | 2011-04-27 | 现代自动车株式会社 | Method of fabricating nano composite powder consisting of carbon nanotube and metal |
CN102719693A (en) * | 2012-06-11 | 2012-10-10 | 上海交通大学 | Graphene and carbon nanotube mixed enhanced metal-matrix composite material and preparation method thereof |
CN102864324A (en) * | 2012-09-06 | 2013-01-09 | 东北大学 | Preparation method for carbon nanomaterial enhanced aluminum base composite material |
CN105838913A (en) * | 2016-04-08 | 2016-08-10 | 上海和伍复合材料有限公司 | Graphene/nickel composite material and preparation method thereof |
CN106834807A (en) * | 2016-12-29 | 2017-06-13 | 苏州大学 | A kind of Graphene enhancing two-phase metal aluminide composite and preparation method thereof |
CN107159896A (en) * | 2017-04-17 | 2017-09-15 | 上海交通大学 | The method for preparing single crystal blade based on the double induced orientation recrystallizations in extra-fine nickel powder region |
Non-Patent Citations (3)
Title |
---|
刘宇航: "少层石墨烯增强镍基复合材料的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
吉传波等: "石墨烯增强镍基粉末高温合金复合材料的力学性能", 《材料工程》 * |
魏秉庆: "《碳.索——吴德海先生八十华诞论文集》", 30 June 2014 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108580881A (en) * | 2018-06-13 | 2018-09-28 | 东莞宜安科技股份有限公司 | A kind of 3D printing metallic composite |
CN110821673A (en) * | 2018-08-10 | 2020-02-21 | 劳斯莱斯有限公司 | Turbine arrangement for a gas turbine engine |
CN109811279A (en) * | 2019-01-21 | 2019-05-28 | 北京科技大学 | A kind of fibre reinforced metal-based high-temperature composite material and preparation method thereof |
CN113737047A (en) * | 2021-09-23 | 2021-12-03 | 河南科技大学 | Metal-based composite material and preparation method thereof |
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