CN109095471A - A kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide with core-shell structure - Google Patents

A kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide with core-shell structure Download PDF

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CN109095471A
CN109095471A CN201811267200.8A CN201811267200A CN109095471A CN 109095471 A CN109095471 A CN 109095471A CN 201811267200 A CN201811267200 A CN 201811267200A CN 109095471 A CN109095471 A CN 109095471A
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rare earth
sintering
core
earth oxide
shell structure
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程继贵
李剑峰
陈鹏起
陈闻超
魏邦争
卫陈龙
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

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Abstract

The invention discloses a kind of, and the WC with core-shell structure coats the preparation method of rare earth oxide non-bond cemented carbide, it is using ammonium metatungstate and soluble rare-earth salt as raw material, utilize the principle of substep forming core and chemical combination in situ, the WC with core-shell structure is gradually made and coats rare earth oxide composite granule, shaped again and sintering densification, that is, obtaining, there is the WC of core-shell structure to coat rare earth oxide non-bond cemented carbide material.The powder application of the method for the present invention preparation is in preparing in non-bond cemented carbide, high compactedness material can be obtained under relatively lower temp, and since the rare earth oxide of doping is distributed in inside WC grain, the crystal grain of WC during the sintering process can be inhibited to grow up, pinning dislocation is mobile simultaneously, so that the hard alloy of preparation has good comprehensive performance.

Description

A kind of WC cladding rare earth oxide non-bond cemented carbide with core-shell structure Preparation method
Technical field
The invention belongs to powder body material preparation field, in particular to a kind of WC with core-shell structure coats rare earth The technology of preparing of oxide hard alloy.
Background technique
Since in terms of chemical property, Binder Phase is poor compared to hard phase, it is easy in the use process of hard alloy Corrosion and oxidation occurs.To overcome the above disadvantages, a kind of novel non-bond cemented carbide (Binderless Carbide) be developed, in alloy without or with the metal adhesives such as minimal amount of Co, Ni, Fe (mass fraction < 0.5%).This series hard alloy has higher hardness, wearability, corrosion resistance, inoxidizability and polishability.It is thus common Wearing piece etc. is slidingly sealed in Electronic Packaging, the mold of optical element, the pipeline of high-temperature corrosion resistance, blast nozzle and heavy duty. But due to lacking lower melting-point metallic binding phase in non-bond cemented carbide, during the preparation process compared to traditional (1370-1490 DEG C) of hard alloy needs very high sintering densification temperature (1800-2000 DEG C), and is difficult to obtain high cause The cemented carbide material of density.Sintering temperature high simultaneously often also results in growing up for WC grain, influences the performance of alloy.Separately Outside, since metallic binding phase is less or is not present, though the hard alloy of preparation has higher hardness, its strength and toughness compared with Difference, thus limit its scope of application.
In order to further improve the mechanical performance of non-bond cemented carbide material, expand its application, attempt to use second Phase particle is doping to for research hotspot in recent years.Wherein carbide (TiC, Mo2C, ZrC, SiC etc.), ceramic oxide (ZrO2、Al2O3Deng) and rare earth oxide (La2O3、Y2O3) adulterated particle as main second phase and refine soap-free emulsion polymeization WC grain degree in phase cemented carbide, and improve the obdurability of material.However, the second phase particles of addition are largely present in WC grain Boundary, especially rare earth oxide its can be only present in WC grain boundary.And be present in WC grain boundary second phase particles its Crystallite dimension is relatively larger than the particle being present in inside WC grain, and its continuity for destroying material structure, leads to alloy The decline of intensity.And when material is by external force, coarse second phase particles can generate bigger stress and concentrate, thus second It is cracked at phase particle, weaken the intensity of material and leads to the Cracking Failure of material.Ding X.Y. et al. exists 《Preparation of TiC/W core-shell structured powders by one-step activation And chemical reduction process " TiC composite granule is coated by preparing core-shell structure W in document mixes TiC It is miscellaneous enter W intra-die, the problems such as generation and Second Phase Particle for not only avoiding local stress are roughened, while also acting nail The effect that dislocation hinders it to move is pricked, thus strengthening material performance.It, also can be by the second phase thus for soap-free emulsion polymeization hard alloy Grain is doped to the performance inside WC grain with reinforced alloys, but not yet has been reported that at present and rare earth oxide can be doped to WC grain Internal method.
Summary of the invention
In order to solve above-mentioned deficiency of the prior art, the WC cladding with core-shell structure that the present invention provides a kind of The preparation method of rare earth oxide non-bond cemented carbide material, problem to solve is that: it is realized by technology controlling and process Product middle rare earth is largely distributed in inside WC grain, and makes non-binding phase cemented carbide obtained than common rare earth Adulterating hard alloy has higher hardness and toughness.
In order to solve the technical problem, the present invention adopts the following technical scheme:
It is a kind of with core-shell structure WC cladding rare earth oxide non-bond cemented carbide material preparation method, be by Following steps carry out:
A, using ammonium metatungstate and soluble rare-earth salt as raw material；Soluble rare-earth salt is dissolved in deionized water, stirring is extremely It is completely dissolved, obtains homogeneous solution A；
B, ammonium hydroxide is added dropwise into homogeneous solution A obtained, so that the pH value of solution is reached alkalinity, by diffusion-precipitation in solution The rare earth salts particle of distribution, is dispersed in solution, obtains aaerosol solution B；
C, ammonium metatungstate is dissolved in deionized water, stirring obtains homogeneous solution C to being completely dissolved；
D, homogeneous solution C is added dropwise into aaerosol solution B, while ammonium hydroxide is added dropwise, the pH for controlling mixed solution maintains alkalinity；
E, after being added dropwise to complete, gained mixed solution is heated, until moisture volatilizees completely, obtaining has core-shell structure Tungsten salt cladding rare-earth salts presoma powder；
F, the precursor powder is calcined in air, obtains tungsten oxide cladding rare earth oxide composite powder Body；
G, tungsten oxide obtained cladding rare earth oxide composite granule is carbonized, so that being coated on rare-earth oxidation The tungsten oxide in-situ reducing chemical combination of beyond the region of objective existence layer is transformed into WC, so that obtaining has the WC cladding rare earth oxide of core-shell structure multiple Close powder；
H, WC cladding rare earth oxide composite granule is formed and sintering densification, acquisition has core-shell structure WC coat rare earth oxide non-bond cemented carbide material.
Further, soluble rare-earth salt described in step a is rare earth nitrades, rare earth sulfate or rare earth-iron-boron Salt, the rare earth element in the soluble rare-earth salt is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
Further, the quality proportioning of ammonium metatungstate and soluble rare-earth salt is with required WC and rare-earth oxidation in target product The quality proportioning of object, which calculates, to be obtained, and target product middle rare earth quality accounts for the 0.01-20% of material gross mass.
Further, the pH value of alkaline condition described in step b and step d is 7.5-10.
Further, heating temperature described in step e is 60-150 DEG C.
Further, the temperature of calcining described in step f be 400-1500 DEG C, time 1min-5h.
Further, the mode of carbonization described in step g is mode one or mode two:
Mode one: carbon black is added into the composite granule of tungsten oxide cladding rare earth oxide, then ball milling or stirs Mix uniformly mixed, then be carbonized in the atmosphere of nitrogen, hydrogen or nitrogen and hydrogen mixture, carburizing temperature is 600-1500 DEG C, when Between be 1min-10h；Carbon black additional amount presses the molar ratio of itself and the wolfram element in tungsten oxide cladding rare earth oxide composite granule (i.e. C:W=1:1-4:1) is added in 1:1-4:1.
Mode two: by the composite granule of tungsten oxide cladding rare earth oxide, in CH4Gas, CH4/H2Gaseous mixture or CO2Atmosphere carbonization is carried out in/CO gaseous mixture, carburizing temperature is 600-1500 DEG C, time 1min-10h；Wherein, CH4/H2Mixing CH in gas4And H2Volume ratio be 1-99:1, CO2CO in/CO gaseous mixture2Volume ratio with CO is 1:1-99.
Further, the mode of forming and sintering densification described in step h is mode one or mode two:
Mode one, first compression moulding re-sinter densification
Compression moulding is that (binder can be polyethylene glycol, paraffin with binder by WC cladding rare earth oxide composite granule Or synthetic rubber) mixing after, the compression moulding at 50-300MPa, pressure maintaining 5s-5min；
The method of sintering densification is vacuum-sintering, gas pressure sintering or microwave sintering: when vacuum-sintering, initial depression is small In 10Pa, sintering temperature is 1600 DEG C -1800 DEG C, keeps the temperature 1h-5h；When gas pressure sintering, the pressure under sintering temperature is 1- 10Mpa, keeps the temperature 1h-5h by 1600-1700 DEG C of sintering temperature；When microwave sintering, sintering temperature is 1600 DEG C -1800 DEG C, heat preservation 10min-1h；
Mode two, forming and sintering densification carry out simultaneously
Be sintered for hot pressed sintering or discharge plasma: when hot pressed sintering, the pressure under sintering temperature is 20-100Mpa, 1500-1700 DEG C of sintering temperature, keep the temperature 30min-5h；When discharge plasma is sintered, the pressure under sintering temperature is 20- 50Mpa, sintering temperature are 1400 DEG C -1600 DEG C, keep the temperature 1min-10min.
There is gained of the invention the WC cladding rare earth oxide composite granule of core-shell structure can be obtained relatively by low-temperature sintering Density is higher than 99%, hardness and is higher than 95HRA, fracture toughness higher than 6MPam1/2Non-bond cemented carbide material
Compared with prior art, the beneficial effects of the present invention are embodied in:
The present invention is to prepare the WC cladding rare-earth oxidation with core-shell structure by substep forming core and growth in situ principle Object composite granule.For the particle size of the composite granule of this method preparation up to ultra-fine even nanoscale, impurity content is few.The party Preparation equipment used in method is simple, and process costs are lower, can be produced in enormous quantities.The powder application of this method preparation is in preparation In non-bond cemented carbide, high compactedness material can be obtained under relatively lower temp.And it is dilute due to what is largely adulterated Native oxide is distributed in inside WC grain, the crystal grain of WC during the sintering process can be inhibited to grow up, while pinning dislocation is mobile, So that the hard alloy of preparation has good comprehensive performance.
Detailed description of the invention
Fig. 1 is the work that there is the WC of core-shell structure to coat rare earth oxide non-bond cemented carbide material for present invention preparation Skill flow chart；
Fig. 2 is WO prepared by the embodiment of the present invention 13Coat La2O3The TEM photo (Fig. 2 (a)) and Fig. 2 (a) of composite granule The corresponding EDS energy spectrum diagram (Fig. 2 (b)) of middle arrow meaning particle；
Fig. 3 is that WC prepared by invention the present embodiment 1 coats La2O3XRD analysis figure (Fig. 3 (a)), the TEM figure of composite granule (Fig. 3 (b)) and corresponding EDS Surface scan spectrogram (Fig. 3 (c) and Fig. 3 (d)).
Specific embodiment
It elaborates below with reference to embodiment to the present invention, following embodiments are under the premise of the technical scheme of the present invention Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following Embodiment.
Embodiment 1
As shown in Figure 1, the present embodiment prepares WC cladding La as follows2O3Non-bond cemented carbide material:
0.53g lanthanum nitrate hexahydrate is dissolved in 40mL deionized water, solution A is configured to, it is 25% that concentration, which is then added, Ammonium hydroxide, control solution ph are 8.5, and the rare earth salts particle being distributed by diffusion-precipitation in solution is dispersed in solution, obtains Obtain aaerosol solution B.Then 25.01g ammonium metatungstate is dissolved in 100mL deionized water, is configured to solution C.Solution C is slowly dripped It is added in solution B, and the ammonium hydroxide that concentration is 25% is added dropwise into solution B, keeping solution ph is 8.5.Again to mixed solution into Row is heated to 80 DEG C and continuous heating until moisture volatilizees completely, obtains precursor powder.Gained presoma powder is put into horse Not in furnace, 60min is calcined in 800 DEG C of heat preservations in air atmosphere, obtains WO3Coat La2O3Composite granule.Then by composite granule Ball milling mixing is carried out with 4.86g carbon black, ball-milling medium is 100mL alcohol, Ball-milling Time 6h, rotational speed of ball-mill 400r/min, ball Material is sintered carbide ball than 3:1, ball.Drying to constant weight in 80 DEG C of baking oven for mixed powder after ball milling.Finally mixed powder is put Enter graphite and burn boat, be carbonized in vacuum carbon tube furnace, carburizing temperature is 1300 DEG C, keeps the temperature 2h, obtains having core-shell structure WC coats La2O3Composite granule.La in obtained composite granule2O3Mass percent be 1%.
WC prepared by the present embodiment with core-shell structure is coated into La2O3Composite granule through 1600 DEG C electric discharge etc. from Daughter sintering, pressure is 50MPa when being sintered, and keeps the temperature 2min.Obtaining, there is the WC of core-shell structure to coat La2O3Soap-free emulsion polymeization is mutually hard Matter alloy material, sintered body relative density are 99.3%, and hardness reaches 96HRA, and fracture toughness reaches 6.35MPam1/2。
Fig. 2 is WO manufactured in the present embodiment3Coat La2O3Arrow in the TEM photo (Fig. 2 (a)) and Fig. 2 (a) of composite granule The corresponding EDS energy spectrum diagram (Fig. 2 (b)) of signified particle, it can be seen from the figure that nanoscale La after calcining2O3Distribution of particles in WO3In particle, core-shell structure is formd.
Fig. 3 is that WC manufactured in the present embodiment coats La2O3XRD analysis figure (Fig. 3 (a)), the TEM of composite granule scheme (Fig. 3 (b)) and corresponding EDS Surface scan spectrogram (Fig. 3 (c) and Fig. 3 (d)), from XRD diagram as can be seen that after being carbonized WO3Powder Body is fully converted to WC, without other object phases.It can be seen that WC from TEM figure and corresponding EDS Surface scan spectrogram and be coated on and receive Meter level La2O3Particle outer layer forms core-shell structure.
Embodiment 2
As shown in Figure 1, the present embodiment prepares WC cladding CeO as follows2Non-bond cemented carbide material:
Tetra- water cerous sulfate of 0.24g is dissolved in 40mL deionized water, solution A is configured to, it is 25% that concentration, which is then added, Ammonium hydroxide, control solution ph are 9, and the rare earth salts particle being distributed by diffusion-precipitation in solution is dispersed in solution, are obtained Aaerosol solution B；Then 25.14g ammonium metatungstate is dissolved in 100mL deionized water, is configured to solution C.C solution is slowly added dropwise Enter in solution B, and the ammonium hydroxide that concentration is 25% is added dropwise into solution B, keeping solution ph is 9.Mixed solution is added again Heat is to 100 DEG C and continuous heating is until moisture volatilizees completely.Gained presoma powder is put into Muffle furnace, is forged in 700 DEG C of heat preservations 60min is burnt, the composite granule of tungsten oxide cladding lanthana is obtained.Finally, putting it into graphite burns boat, carbon is carried out in pipe furnace Change, carburizing atmosphere CH4/H2(its volume ratio CH4:H2=90:10, flow 250mL/min), carburizing temperature be 900 DEG C, protect Warm 2h obtains the WC cladding CeO with core-shell structure2Composite granule.CeO in obtained composite granule2Mass percent be 0.5%.
By composite granule prepared by the present embodiment through 1700 DEG C of hot pressed sinterings, hot pressing pressure 40MPa keeps the temperature 1h.It obtains There must be the WC cladding CeO of core-shell structure2Non-bond cemented carbide, sintered body relative density are 98.5%, and hardness reaches 95.3HRA, fracture toughness reach 6.51MPam1/2。

Claims (8)

1. a kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide material with core-shell structure, feature It is, carries out as follows:
A, using ammonium metatungstate and soluble rare-earth salt as raw material；Soluble rare-earth salt is dissolved in deionized water, is stirred to complete Dissolution obtains homogeneous solution A；
B, ammonium hydroxide is added dropwise into homogeneous solution A obtained, so that the pH value of solution is reached alkalinity, is distributed by diffusion-precipitation in solution Rare earth salts particle, be dispersed in solution, obtain aaerosol solution B；
C, ammonium metatungstate is dissolved in deionized water, stirring obtains homogeneous solution C to being completely dissolved；
D, homogeneous solution C is added dropwise into aaerosol solution B, while ammonium hydroxide is added dropwise, the pH for controlling mixed solution maintains alkalinity；
E, after being added dropwise to complete, gained mixed solution is heated, until moisture volatilizees completely, obtains the tungsten with core-shell structure The presoma powder of salt cladding rare-earth salts；
F, the precursor powder is calcined in air, obtains tungsten oxide cladding rare earth oxide composite granule；
G, tungsten oxide obtained cladding rare earth oxide composite granule is carbonized, so that being coated on rare-earth oxidation beyond the region of objective existence The tungsten oxide in-situ reducing chemical combination of layer is transformed into WC, so that obtaining, there is the WC of core-shell structure to coat rare earth oxide composite powder Body；
H, WC cladding rare earth oxide composite granule is formed and sintering densification, acquisition has the WC of core-shell structure Coat rare earth oxide non-bond cemented carbide material.
2. the WC cladding rare earth oxide non-bond cemented carbide material according to claim 1 with core-shell structure Preparation method, it is characterised in that: soluble rare-earth salt described in step a is rare earth nitrades, rare earth sulfate or rare earth chlorine Compound salt, the rare earth element in the soluble rare-earth salt is La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc.
3. the WC cladding rare earth oxide non-bond cemented carbide material according to claim 1 with core-shell structure Preparation method, it is characterised in that: the quality proportioning of ammonium metatungstate and soluble rare-earth salt is with required WC and rare earth in target product The quality proportioning of oxide, which calculates, to be obtained, and target product middle rare earth quality accounts for the 0.01-20% of material gross mass.
4. the WC cladding rare earth oxide non-bond cemented carbide material according to claim 1 with core-shell structure Preparation method, it is characterised in that: the pH value of alkaline condition described in step b and step d is 7.5-10.
5. the WC with core-shell structure according to claim 1 coats rare earth oxide non-bond cemented carbide The preparation method of material, it is characterised in that: heating temperature described in step e is 60-150 DEG C.
6. the WC with core-shell structure according to claim 1 coats rare earth oxide non-bond cemented carbide The preparation method of material, it is characterised in that: the temperature of calcining described in step f is 400-1500 DEG C, time 1min-5h.
7. the WC with core-shell structure according to claim 1 coats rare earth oxide non-bond cemented carbide The preparation method of material, which is characterized in that the mode of carbonization described in step g is mode one or mode two:
Mode one: carbon black is added into tungsten oxide cladding rare earth oxide composite granule, then ball milling or is stirred Uniformly, then in the atmosphere of nitrogen, hydrogen or nitrogen and hydrogen mixture it is carbonized, carburizing temperature is 600-1500 DEG C, the time is 1min-10h；Carbon black additional amount is 1 by the molar ratio of itself and the wolfram element in tungsten oxide cladding rare earth oxide composite granule: 1-4:1 is added；
Mode two: by the composite granule of tungsten oxide cladding rare earth oxide, in CH4Gas, CH4/H2Gaseous mixture or CO2/CO Atmosphere carbonization is carried out in gaseous mixture, carburizing temperature is 600-1500 DEG C, time 1min-10h；Wherein, CH4/H2In gaseous mixture CH4And H2Volume ratio be 1-99:1, CO2CO in/CO gaseous mixture2Volume ratio with CO is 1:1-99.
8. the WC cladding rare earth oxide non-bond cemented carbide material according to claim 1 with core-shell structure Preparation method, it is characterised in that: the mode of forming and sintering densification described in step h is mode one or mode two:
Mode one, first compression moulding re-sinter densification
Compression moulding is the compression moulding at 50-300MPa after mixing WC cladding rare earth oxide composite granule with binder, Pressure maintaining 5s-5min；
The method of sintering densification is vacuum-sintering, gas pressure sintering or microwave sintering: when vacuum-sintering, initial depression is less than 10Pa, sintering temperature are 1600 DEG C -1800 DEG C, keep the temperature 1h-5h；When gas pressure sintering, the pressure under sintering temperature is 1-10Mpa, 1600-1700 DEG C of sintering temperature, keep the temperature 1h-5h；When microwave sintering, sintering temperature is 1600 DEG C -1800 DEG C, keeps the temperature 10min- 1h；
Mode two, forming and sintering densification carry out simultaneously
Be sintered for hot pressed sintering or discharge plasma: when hot pressed sintering, the pressure under sintering temperature is 20-100Mpa, sintering 1500-1700 DEG C of temperature, keep the temperature 30min-5h；When discharge plasma is sintered, the pressure under sintering temperature is 20-50Mpa, is burnt Junction temperature is 1400 DEG C -1600 DEG C, keeps the temperature 1min-10min.
CN201811267200.8A 2018-10-29 2018-10-29 A kind of preparation method of the WC cladding rare earth oxide non-bond cemented carbide with core-shell structure Pending CN109095471A (en)

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CN111848168A (en) * 2020-07-29 2020-10-30 台州学院 Method for preparing WC-Y2O3 binderless hard alloy by in-situ reaction hot-pressing sintering
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CN109972018A (en) * 2019-05-10 2019-07-05 赣州有色冶金研究所 A kind of WC-Co-RE composite powder and the preparation method and application thereof
CN111778436A (en) * 2020-07-29 2020-10-16 台州学院 Method for preparing WC-Y2O3 binderless hard alloy by cold pressing-hot pressing sintering
CN111848168A (en) * 2020-07-29 2020-10-30 台州学院 Method for preparing WC-Y2O3 binderless hard alloy by in-situ reaction hot-pressing sintering
CN111848168B (en) * 2020-07-29 2022-03-18 台州学院 Method for preparing WC-Y2O3 binderless hard alloy by in-situ reaction hot-pressing sintering
CN114574726A (en) * 2022-03-01 2022-06-03 合肥工业大学 Preparation method of FeCoCu medium-entropy alloy binding phase hard alloy

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