CN106435323B - A kind of oxide dispersion intensifying ODS high-entropy alloys and preparation method thereof - Google Patents
A kind of oxide dispersion intensifying ODS high-entropy alloys and preparation method thereof Download PDFInfo
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- CN106435323B CN106435323B CN201610711659.7A CN201610711659A CN106435323B CN 106435323 B CN106435323 B CN 106435323B CN 201610711659 A CN201610711659 A CN 201610711659A CN 106435323 B CN106435323 B CN 106435323B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
A kind of oxide dispersion intensifying ODS high-entropy alloys and preparation method thereof, belong to structural metallic materials field.The present invention will prepare ODS high-entropy alloy powders after the oxide particle mixing of the pure metal powder of certain ingredients proportioning and certain content by Mechanical Alloying；Then final ODS high-entropy alloys are obtained using the method for discharge plasma sintering (SPS).The ODS high-entropy alloys being prepared mainly are made up of the nano-oxide particles of solid solution phase (more than 95%) and a small amount of even dispersion distribution；And there is excellent comprehensive mechanical property and good heat endurance, the compression strength for the FeCoNiCrAl base ODS high-entropy alloys being wherein made up of face-centred cubic structure (FCC)+body-centered cubic structure (BCC) solid solution phase is more than 3500MPa, and compression strain is up to 10%.High-entropy alloy of the present invention has high intensity, high rigidity, high anti-corrosion and wearability, excellent heat endurance and radiation-resistant property, has potential application prospect in fields such as Aero-Space, chemical metallurgy, electric power energies.
Description
Technical field
The invention belongs to structural metallic materials field, there is provided a kind of oxide dispersion intensifying (ODS) high-entropy alloy and its
Preparation method.
Background technology
Oxide dispersion intensifying (ODS) alloy typically will have heat endurance and chemistry steady using PM technique at present
Qualitatively fine oxide is uniformly added into alloy substrate.What these oxide particles can fail in solution strengthening and precipitation strength
Under high temperature, as dispersion-strengtherning Pinning dislocation and crystal boundary, dislocation movement and the generation of recrystallization process are hindered, so as to have
Effect improves the mechanical behavior under high temperature and anti-radiation performance of material.Conventional oxide is Y2O3、Al2O3、ThO2Deng.At present, ODS is closed
The research of the structure property, processing technology etc. of gold is as one of the study hotspot in investigation of materials field.ODS alloys are
Be widely used in field of aerospace thermal protection structure and engine thermal end pieces, nuclear reactor the first wall involucrum and its
His thermal structure part field.
ODS steel is due to excellent Properties of High Temperature Creep and anti-radiation performance, it is considered to be most develops at present
The core containment structure material of prospect.However, due in ODS steel grain boundaries contain the oxide particle of higher volume fraction so that
The plasticity and impact flexibility of material are poor, simultaneously because serious tissue and property anisotropy in cold working be present, to alloy
Preparation brings great difficulty, and this limits its application in engineering to a certain extent.It is therefore desirable to develop to have height concurrently
The new ODS alloy materials of intensity, high tenacity and good processability.
High-entropy alloy is a kind of new metallic material that latest developments are got up, and it has broken conventional alloys with one or two
Metallic element is the designing axiom of pivot, be it is a kind of comprise at least four kinds between constituent element, constituent element for etc. atomic ratio or approximation etc.
Atomic ratio, and novel alloy system of every kind of constituent element content between 5%~35%.Although constituent element is more, it is prepared
The structure of high-entropy alloy is fairly simple, generally simple face-centered cubic (FCC), body-centered cubic (BCC) or close-packed hexagonal
(HCP) solid solution.Due to its unique composition and architectural feature, high-entropy alloy has a series of excellent performances, as high intensity,
The performances such as high tenacity, high corrosion-resistant and good heat endurance.Further, since the complexity of its chemical composition causes high-entropy alloy
Inside has serious distortion of lattice, and this greatly limits effective diffusion rate of atom in alloy.This slowly diffusion effect
Should have beneficial to the diffusional resistance of caused room and interstitial atom in increase irradiation process, reduce secondary defect such as dislocation ring, layer
Wrong tetrahedron, the formation speed in cavity.Therefore, high-entropy alloy also has good anti-radiation performance.The high intensity of high-entropy alloy,
High tenacity, good heat endurance, anti-radiation performance and corrosion resistance make it be expected to turn into nuclear reactor structure material of new generation
Material.But there is also obvious deficiency for single-phase high-entropy alloy：The high-entropy alloy toughness of FCC solid solution structure is very well but yield strength
It is too low；And the high-entropy alloy intensity height but plasticity of BCC solid solution structures are poor.Therefore, how to improve its comprehensive mechanical property is
The task of top priority that can high-entropy alloy be used widely.
Current research is mostly to lift high-entropy alloy mechanical property by interior raw precipitation strength and solution strengthening, and right
It is also few in the research of external ODS high-entropy alloys.Therefore, the present invention is with General Promotion high-entropy alloy mechanical property, heat endurance
For the purpose of anti-radiation performance, oxide dispersion intensifying technology is applied in high-entropy alloy.Compared to ODS steel, ODS high-entropy alloys
Plasticity and impact flexibility it is stronger.Compared to pure solid solution high-entropy alloy, the compression strength of ODS high-entropy alloys significantly improves.
Therefore, the ODS high-entropy alloys that the present invention obtains all have latent in high-tech areas such as Aero-Space, chemical metallurgy, electric power energies
Application prospect.
The content of the invention
The present invention develops a kind of oxide dispersion intensifying (ODS) high-entropy alloy and preparation method thereof, passes through micro-oxidation
The addition of composition granule, on the premise of alloy plasticity is not damaged, the intensity of alloy is significantly improved.
The present invention is to be achieved through the following technical solutions：Rare earth oxide is realized by mechanical alloying in preparation process
Y2O3Solid solution in alloy substrate, then separated out again in sintering process and to form highly dispersed, yardstick is nano level disperse oxygen
Compound hardening constituent, so that the mechanical property through ODS high-entropy alloys made from this inventive method is more excellent.Further,
In order to make Y as far as possible2O3More stable nanocluster is formed in mechanical milling process, in addition Y2O3While, addition trace Ti,
A kind of element in Zr or Hf.
Described oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that ODS high-entropy alloy phase compositions are by more than 95%
Solid solution phase and Dispersed precipitate less than 5% nano-oxide particles composition.
High-entropy alloy matrix comprises at least 4 kinds of elements, and its atomic percent expression formula is FeaCobNicCrdLe(atomic molar
Than), and each component：0 ＜ a≤35,0 ＜ b≤35,0 ＜ c≤35,0 ＜ d≤35,0≤e≤35 and a+b+c+d+e=100.Its
In, L is one or both of Al and Mn.
Further ODS high-entropy alloys are FeCoNiCr bases, FCC configuration solid solution phase that phase composition is more than 95% and small
In the nano-oxide particles of 5% Dispersed precipitate；Its compression yield strength more than 930MPa, compression strain reach 50% with
On.
Further ODS high-entropy alloys are FeCoNiCrAl bases, and phase composition is more than 95% FCC+BCC structure solid solution
The nano-oxide particles of Dispersed precipitate mutually and less than 5%, its compression strength is more than 3500MPa, and compression strain is up to 10%.
It is a further object of the present invention to provide the preparation method of above-mentioned alloy, following steps are specifically included：
(1) dispensing：According to target component, mass ratio is converted into according to the atomic percent of above-mentioned expression formula, is weighed each
Pantogen feed powder, it is well mixed；
(2) ball milling：After step (1) is mixed, using comprehensive planetary ball mill, mechanical alloy is carried out under argon gas protection
Change.Ratio of grinding media to material is 10:1~25:1, rotational speed of ball-mill is 200~300rpm, and Ball-milling Time is 50~80h；
(3) sinter：Powder after step (2) ball milling is subjected to discharge plasma sintering, sintering temperature is 900~1100
DEG C, using graphite jig, sintering pressure is 40~50MPa, and soaking time is 5~10min.
Elemental metalpowder material purity is above 99wt%, and particle size is 200~325 mesh；The oxide added
Y2O3The size of particle is between 20~40nm.
X and Y2O3Proportioning be in order that Y2O3Nanocluster, this nanocluster fine uniform are formed in mechanical milling process
And Dispersed precipitate, be advantageous to improve alloy mechanical performance.
In the mechanical milling process of the step (2), using normal heptane as process control agent, addition is the 1 of metal dust
~3wt%.
The elemental metalpowder material purity is above 99wt%, and particle size is 200~325 mesh；The oxygen added
Compound Y2O3The size of particle is between 20~40nm.
Ф 10mm and Ф 8mm stainless steel balls are used in the mechanical milling process of the step (2).
After oxide particle is added, intensity is significantly improved the high-entropy alloy of the present invention.Wherein, FeCoNiCr bases
The compression yield strength of ODS high-entropy alloys is more than 930MPa, and compression plasticity is more than 100%；FeCoNiCrAl base ODS high-entropy alloys
Compression strength more than 3500MPa, and the elongation percentage of alloy still can reach 10%.In addition, effectively spread in high-entropy alloy
Speed is low, can increase the diffusional resistance of caused room and interstitial atom in irradiation process.Therefore, the high-entropy alloy is expected to making
For the cladding materials of nuclear reactor.
The advantage of the invention is that：
1st, a series of ODS high-entropy alloys composition ranges involved in the present invention are wide, and preparation condition is also very extensive, can be low
Prepared under vacuum, cost is low, is advantageous to mass produce.
2nd, the essential element of ODS high entropy alloy materials provided by the invention is common simple metal raw material and ceramic raw material, valency
Lattice are cheap, and convenient with preparing, and technique is simple, it is safe to use the advantages that.
3rd, it is significantly improved compared to conventional high-entropy alloy, ODS high-entropy alloys comprehensive mechanical property provided by the present invention：
The strength of materials is significantly improved, while does not drop low-alloyed plasticity also.
Brief description of the drawings
Fig. 1 is that ODS height is made in ball milling after FeCoNiCr additions 0.5wt% composite oxide powers in the embodiment of the present invention 1
The XRD of entropy alloy powder.
Fig. 2 is the XRD after FeCoNiCr base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 1.
Fig. 3 is the room temperature compressive stress strain curve of FeCoNiCr base ODS high-entropy alloys prepared by the embodiment of the present invention 1.
Fig. 4 is that ODS is made in ball milling after FeCoNiCrAl additions 0.5wt% composite oxide powers in the embodiment of the present invention 2
The XRD of high-entropy alloy powder.
Fig. 5 is the XRD after FeCoNiCrAl base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 2.
Fig. 6 is that room temperature compression stress-strain of FeCoNiCrAl base ODS high-entropy alloys prepared by the embodiment of the present invention 2 is bent
Line.
Fig. 7 is that the high entropys of ODS are made in ball milling after FeCoNiCr additions 1wt% composite oxide powers in the embodiment of the present invention 3
The XRD of alloy powder.
Fig. 8 is the XRD after FeCoNiCr base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 3.
Fig. 9 is the room temperature compressive stress strain curve of FeCoNiCr base ODS high-entropy alloys prepared by the embodiment of the present invention 3.
Figure 10 is that ODS height is made in ball milling after FeCoNiCrAl additions 1wt% composite oxide powers in the embodiment of the present invention 4
The XRD of entropy alloy powder.
Figure 11 is the XRD after FeCoNiCrAl base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 4.
Figure 12 is that room temperature compression stress-strain of FeCoNiCrAl base ODS high-entropy alloys prepared by the embodiment of the present invention 4 is bent
Line.
Figure 13 is the transmission electron microscope photo of FeCoNiCrAl base ODS high-entropy alloys prepared by the embodiment of the present invention 4.
Figure 14 is the XRD after FeCoNiCr base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 5.
Figure 15 is that room temperature compression stress-strain of FeCoNiCr base ODS high-entropy alloys prepared by the embodiment of the present invention 5 is bent
Line.
Figure 16 is the XRD after FeCoNiCrAl base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 6.
Figure 17 is that room temperature compression stress-strain of FeCoNiCrAl base ODS high-entropy alloys prepared by the embodiment of the present invention 6 is bent
Line.
Figure 18 is the XRD after FeCoNiCr base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 7.
Figure 19 is that room temperature compression stress-strain of FeCoNiCr base ODS high-entropy alloys prepared by the embodiment of the present invention 7 is bent
Line.
Figure 20 is the XRD after FeCoNiCrAl base ODS high-entropy alloys SPS prepared by the embodiment of the present invention 8.
Figure 21 is that room temperature compression stress-strain of FeCoNiCrAl base ODS high-entropy alloys prepared by the embodiment of the present invention 8 is bent
Line.
Embodiment
Technical scheme is described further with reference to specific embodiment.
Embodiment 1:
FeCoNiCr addition 0.5wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCr) and titanium valve and nanometer Y to test raw materials used2O3
Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3Powder
Average grain diameter be 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to quality hundred
It is 99.5 (FeCoNiCr) -0.33Ti-0.17Y to divide ratio2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
280rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 15 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Fig. 1 spreads out for the XRD rays of powder sample after ball milling different time
Collection of illustrative plates is penetrated, after ball milling 60 shown in figure hour, phase structure of alloy is mainly by FCC solid solution phase composition.Fig. 2 is sample after sintering
XRD x ray diffraction collection of illustrative plates, shown in figure sinter after sample be FCC solid solution structure.Fig. 3 is the room temperature compression of sample after sintering
Load-deformation curve, the yield strength of sample shown in figure is 725MPa, and the yield strength of pure FeCoNiCr high-entropy alloys exists
280MPa or so.And the toughness of this ODS high-entropy alloy sample is very good, and sample is not broken in whole compression process.
Embodiment 2:
FeCoNiCrAl addition 0.5wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCrAl) and titanium valve and nanometer to test raw materials used
Y2O3Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3
The average grain diameter of powder is 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to matter
Amount percentage is (FeCoNiCrAl) -0.33Ti-0.17Y2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
280rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 15 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Fig. 4 spreads out for the XRD rays of powder sample after ball milling different time
Collection of illustrative plates is penetrated, after ball milling 60 shown in figure hour, phase structure of alloy is mainly made up of BCC solid solution phases.Fig. 5 is sample after sintering
XRD x ray diffraction collection of illustrative plates, shown in figure sinter after sample be BCC+FCC solid solution structures.Fig. 6 is the room temperature of sample after sintering
Compressive stress strain curve, the yield strength of sample shown in figure are 2150MPa, compression strength 3138MPa, compression strain
For 9.3%.Compression strength than pure FeCoNiCrAl high-entropy alloys improves 1130MPa, and compression strain is 9.3%, is embodied
Good compression plasticity.
Embodiment 3：FeCoNiCr addition 1wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCr) and titanium valve and nanometer Y to test raw materials used2O3
Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3Powder
Average grain diameter be 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to quality hundred
It is (FeCoNiCr) -0.67Ti-0.33Y to divide ratio2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
280rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 15 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Fig. 7 spreads out for the XRD rays of powder sample after ball milling different time
Collection of illustrative plates is penetrated, after ball milling 60 shown in figure hour, phase structure of alloy is mainly by FCC solid solution phase composition.Fig. 8 is sample after sintering
XRD x ray diffraction collection of illustrative plates, shown in figure sinter after sample be FCC solid solution structure.Fig. 9 is the room temperature compression of sample after sintering
Load-deformation curve, the yield strength of sample shown in figure is 932MPa, and the yield strength of pure FeCoNiCr high-entropy alloys exists
280MPa or so.And the toughness of this ODS high-entropy alloy sample is very good, and sample is not broken in whole compression process.
Embodiment 4:
FeCoNiCrAl addition 1wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCrAl) and titanium valve and nanometer to test raw materials used
Y2O3Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3
The average grain diameter of powder is 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to matter
Amount percentage is (FeCoNiCrAl) -0.67Ti-0.33Y2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
280rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 15 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Figure 10 is the XRD rays of powder sample after ball milling different time
Diffracting spectrum, after ball milling 60 shown in figure hour, phase structure of alloy is mainly made up of BCC solid solution phases.After Figure 11 is sintering
The XRD x ray diffraction collection of illustrative plates of sample, it can be seen that sample is BCC+FCC solid solution structures after sintering.Figure 12 is sample after sintering
Room temperature compressive stress strain curve, the yield strength of sample shown in figure is 2087MPa, compression strength σmaxFor 3550MPa,
Compression strength than as cast condition FeCoNiCrAl high-entropy alloys improves 1550MPa.And the compression strain of sample is 9.7%, is embodied
Good compression plasticity.Figure 13 is the images of transmissive electron microscope of this sample, it can be seen that the nano-scale oxide of Dispersed precipitate, grain
Footpath is 10~40nm.
Embodiment 5:
FeCoNiCr addition 1.5wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCr) and titanium valve and nanometer Y to test raw materials used2O3
Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3Powder
Average grain diameter be 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to quality hundred
It is (FeCoNiCr) -1.0Ti-0.5Y to divide ratio2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
300rpm, Ball-milling Time 60h.In mixing and ball milling, per 20h, addition 25 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 60h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1000 DEG C, sintering pressure 50MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Figure 14 is the XRD x ray diffraction collection of illustrative plates of sample after sintering, in figure
Sample is FCC solid solution structure after shown sintering.Figure 15 is the room temperature compressive stress strain curve of sample after sintering, institute in figure
The yield strength of sample product is 1274MPa, compression strength σmaxFor 2579MPa, and the yield strength of pure FeCoNiCr high-entropy alloys
In 280MPa or so.And the toughness of this ODS high-entropy alloy sample is good, elongation percentage ε is compressedfFor 40.6%.
Embodiment 6:
FeCoNiCrAl addition 1.5wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCrAl) and titanium valve and nanometer to test raw materials used
Y2O3Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3
The average grain diameter of powder is 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to matter
Amount percentage is (FeCoNiCrAl) -0.1Ti-0.5Y2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
300rpm, Ball-milling Time 60h.In mixing and ball milling, per 20h, addition 25 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 60h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1000 DEG C, sintering pressure 50MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Figure 16 is the XRD x ray diffraction collection of illustrative plates of sample after sintering, in figure
Sample is BCC+FCC solid solution structures after shown sintering.Figure 17 is the room temperature compressive stress strain curve of sample after sintering, is schemed
Shown in the yield strength of sample be 1717MPa, compression strength 2535MPa, it is more anti-than as cast condition FeCoNiCrAl high-entropy alloys
Compressive Strength improves 530MPa, and the compression strain of sample is 7.5%.
Embodiment 7:
FeCoNiCr addition 2.0wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCr) and titanium valve and nanometer Y to test raw materials used2O3
Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3Powder
Average grain diameter be 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to quality hundred
It is (FeCoNiCr) -1.33Ti-0.67Y to divide ratio2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
300rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 10 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Figure 18 is the XRD x ray diffraction collection of illustrative plates of sample after sintering, in figure
Sample is FCC solid solution structure after shown sintering.Figure 19 is the room temperature compressive stress strain curve of sample after sintering, institute in figure
The yield strength of sample product is 583MPa, and the yield strength of pure FeCoNiCr high-entropy alloys is in 280MPa or so.And this ODS
The toughness of high-entropy alloy sample is very good, and sample is not broken during whole compression test.
Embodiment 8:
FeCoNiCrAl addition 2.0wt% (Ti, Y2O3) high-entropy alloy preparation and performance
(1) composition proportion：It is matrix element powder (composition FeCoNiCrAl) and titanium valve and nanometer to test raw materials used
Y2O3Powder, purity are above 99.9wt%.The wherein particle size of matrix element powder and titanium valve is 200~325 mesh, Y2O3
The average grain diameter of powder is 30nm.The high-entropy alloy component for waiting atomic ratio dispensing is converted into mass percent, then according to matter
Amount percentage is (FeCoNiCrAl) -1.33Ti-0.67Y2O3Weigh and mix respectively.
(2) high-energy ball milling：Powder is loaded into vacuum ball grinder together with 300g stainless steel steel balls, in the vacuum of argon gas atmosphere
Glove box is operated.Using comprehensive planetary ball mill ball milling, mechanical milling process is carried out under argon gas protection, and rotational speed of ball-mill is
300rpm, Ball-milling Time 80h.In mixing and ball milling, per 10h, addition 10 drips normal heptane as process control agent in addition.
(3) after the powder after ball milling 80h is taken out, load graphite jig, carry out SPS sintering.Specifically sintering parameter is：Burn
Junction temperature is 1100 DEG C, sintering pressure 40MPa, sintering time 10min.Temperature to be sintered is cooled to room temperature, takes out mould, will
Sample is stripped, that is, obtains prepared ODS high-entropy alloys.
(4) sign of ODS high-entropy alloys and performance test：Figure 20 is the XRD x ray diffraction collection of illustrative plates of sample after sintering, in figure
Sample is BCC+FCC solid solution structures after shown sintering.Figure 21 is the room temperature compressive stress strain curve of sample after sintering, is schemed
Shown in the yield strength of sample be 1489MPa, compression strength 2568MPa, it is more anti-than as cast condition FeCoNiCrAl high-entropy alloys
Compressive Strength improves 560MPa.And the compression strain of sample is 12.3%, embodies good compression plasticity.
Claims (9)
- A kind of 1. oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that using high-entropy alloy as matrix, it with the addition of 0.1~ 2wt% by X and Y2O3The composite oxides nano particle of composition, wherein X are one kind in Ti, Zr or Hf；Above-mentioned ODS high-entropy alloy matrixes, including at least 4 kinds of elements, its atomic percent expression formula is FeaCobNicCrdLe, and Each component：0 ＜ a≤35,0 ＜ b≤35,0 ＜ c≤35,0 ＜ d≤35,0≤e≤35 and a+b+c+d+e=100；Wherein, L is One or both of Al and Mn.
- 2. oxide dispersion intensifying ODS high-entropy alloys according to claim 1, it is characterised in that ODS high-entropy alloy phase groups Nano-oxide particles into the solid solution phase by more than 95% and the Dispersed precipitate less than 5% form.
- 3. oxide dispersion intensifying ODS high-entropy alloys according to claim 1, it is characterised in that ODS high-entropy alloys are The nano-oxide of FeCoNiCr bases, the FCC configuration solid solution phase that phase composition is more than 95% and the Dispersed precipitate less than 5% Grain；Its compression yield strength reaches more than 50% more than 930MPa, compression strain.
- 4. oxide dispersion intensifying ODS high-entropy alloys according to claim 1, it is characterised in that ODS high-entropy alloys are The nano oxygen of FeCoNiCrAl bases, the FCC+BCC structures solid solution phase that phase composition is more than 95% and the Dispersed precipitate less than 5% Compound particle, its compression strength is more than 3500MPa, and compression strain is up to 10%.
- 5. a kind of method for preparing the oxide dispersion intensifying ODS high-entropy alloys as described in any in claim 1-4, its feature It is to specifically include following steps：(1) dispensing：And mass ratio is converted into according to the atomic percent of above-mentioned expression formula, the raw material powder of each element is weighed, is mixed Close uniform；(2) ball milling：Adding procedure controlling agent carries out mechanical alloying, ball milling under inert gas shielding after step (1) is mixed During ratio of grinding media to material be 10:1~25:1, rotational speed of ball-mill is 200~300rpm, and Ball-milling Time is 50~80h；(3) sinter：By after step (2) ball milling powder load mould, carry out discharge plasma sintering, sintering temperature be 900~ 1100 DEG C, using graphite jig, sintering pressure is 40~50MPa, and soaking time is 5~10min.
- 6. the method according to claim 5 for preparing oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that added The elemental metalpowder material purity added is above 99wt%, and particle size is 200~325 mesh；The oxide Y added2O3 The size of grain is between 20~40nm.
- 7. the method according to claim 5 for preparing oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that X and Y2O3Proportioning be in order that Y2O3Nanocluster, this nanocluster fine uniform and Dispersed precipitate are formed in mechanical milling process, Be advantageous to improve the mechanical performance of alloy.
- 8. the method according to claim 5 for preparing oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that described In the mechanical milling process of step (2), using normal heptane as process control agent, addition is 1~3wt% of metal dust.
- 9. the method according to claim 5 for preparing oxide dispersion intensifying ODS high-entropy alloys, it is characterised in that described Ф 10mm and Ф 8mm stainless steel balls are used in the mechanical milling process of step (2).
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