CN109161773A - A kind of preparation method of high-entropy alloy bonding phase cemented carbide - Google Patents
A kind of preparation method of high-entropy alloy bonding phase cemented carbide Download PDFInfo
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- CN109161773A CN109161773A CN201811107242.5A CN201811107242A CN109161773A CN 109161773 A CN109161773 A CN 109161773A CN 201811107242 A CN201811107242 A CN 201811107242A CN 109161773 A CN109161773 A CN 109161773A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 105
- 239000000956 alloy Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000009792 diffusion process Methods 0.000 claims abstract description 10
- 238000003801 milling Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 43
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000003701 mechanical milling Methods 0.000 claims description 4
- 239000012856 weighed raw material Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002159 abnormal effect Effects 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910009043 WC-Co Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- -1 WC as hard phase Chemical class 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000009768 microwave sintering Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention discloses a kind of preparation methods of high-entropy alloy bonding phase cemented carbide, it is characterized in that preparing Fe:Co:Ni:Cu:Cr=1:1:1:(0.4~0.6 using intermittent planetary ball mill first): amorphous high-entropy alloy Binder Phase powder of (0.4~0.6)；Then amorphous high-entropy alloy Binder Phase powder is carried out roller milling with hard phase powder to mix, the mixture prepared still is amorphous state；SPS sintering is finally carried out at 1400~1450 DEG C makes amorphous high-entropy alloy Binder Phase recurring structure relaxation in hard alloy complete crystallization, amorphous state makes the dissolution in the opposite Binder Phase of hard be inhibited to the sluggish elements diffusion effect of process and high-entropy alloy itself that crystalline state changes, its Binder Phase is the high-entropy alloy of single-phase face-centred cubic structure, to prepare high-entropy alloy bonding phase cemented carbide.The present invention overcomes when the preparation of existing high-entropy alloy bonding phase cemented carbide, hard phase dissolves in Binder Phase and relative amount reduction occurs, hard phase crystal grain is easy to appear abnormal growth, eventually leads to the problem of hard alloy mechanical property deficiency, can be used for the fields such as cutting tool, wear part.
Description
Technical field
The present invention relates to a kind of preparation method of cemented carbide material, in particular to high-entropy alloy bonding phase cemented carbide
Preparation method belongs to field of compound material.
Background technique
Hard alloy is using refractory carbides such as WC as hard phase, and the transition metal such as Co are Binder Phase, using powder
The composite material that metallurgical method is prepared into.Hard alloy has the mechanical properties such as excellent hardness, wearability, is widely used in cutting
Cutting knife tool, wear-resisting property, miner tool etc..In order to further increase the performance of hard alloy, hard phase is carried out both at home and abroad
The research such as fine and carbide addition；In terms of Binder Phase, mainly by addition Fe, Ni, other metals such as rare earth element come
Realize the reinforcing to Binder Phase.But current Binder Phase design does not break through the ingredient design limitation of traditional single pivot.
And the high-entropy alloy that last century end occurs is by 5~13 kinds of essential elements according to equal atomic ratios or close to equal atomic ratio alloys
The multi-principal elements alloy of formation forms, and the molar content of every kind of element is between 5%~35%.High-entropy alloy is with higher strong
Degree, good wearability, high processing hardening, the conventional alloys such as high temperature resistant softening, pyro-oxidation resistance are incomparable a little,
Its performance can be effectively improved if for the Binder Phase of hard alloy.
CN102796933A discloses a kind of nitrogenous hard alloy and preparation method thereof based on high-entropy alloy Binder Phase, high
Entropy alloy bonding is mutually made of at least four in iron, cobalt, nickel, chromium, aluminium, vanadium, titanium, copper, zirconium, molybdenum, manganese, and this method is by WC
Powder, high-entropy alloy Binder Phase and carbonitride solid solution powder carry out ball milling mixing after weighing by predetermined formulation together, finally exist
0.5-1.5 hours completion low pressure sinterings of 1400 DEG C -1480 DEG C (1-3 DEG C of heating rate/min) heat preservations.CN1827817A is disclosed
A kind of hard alloy and preparation method thereof of high-entropy alloy binder and double carbide sintering, it is characterized in that Binder Phase is using more
First high-entropy alloy, the main metal element contained by the Binder Phase include iron, cobalt, nickel, chromium, aluminium, titanium, vanadium, copper, zirconium, molybdenum, manganese,
The metal powder of double carbide and Binder Phase is mixed in ball grinding cylinder when preparation, ball grinding cylinder is then put into ball mill
The interior high-energy ball milling for carrying out at least 10 hours, is finally sintered at 1350 DEG C -1500 DEG C under vacuum conditions.
But in existing high-entropy alloy bonding phase cemented carbide preparation process, the high entropy of more pivots is mostly first prepared
Alloy bonding phase constituent, then these starting powders are mixed together with the other compositions of hard alloy, therefore, various bondings
Phase constituent powder is random to be distributed between hard phase powder particle, and cannot be guaranteed these polynary bonding phase constituents in mixing ball
Solid solution reaction formation and the consistent high-entropy alloy of design object ingredient occur for phase counterdiffusion in mill and sintering process.On the other hand,
Heating rate is slower in sintering process, and soaking time is longer, and hard phase constituent can be to bonding phase constituent dissolution, even if foring height
The Binder Phase of entropy alloying component, ingredient are also difficult to keep；This cannot not only obtain real high-entropy alloy Binder Phase, but also
Will appear hard phase relative amount reduces the case where growing up with crystal grain.Therefore, it is necessary to which it is hard to develop new high-entropy alloy Binder Phase
Matter alloy preparation method.
Summary of the invention
The present invention is at present in such a way that Binder Phase powder directly mixes with hard phase powder and to carry out vacuum-sintering again
The problem of being difficult to obtain real high-entropy alloy Binder Phase, and hard phase content is caused to reduce, proposes and prepares the high entropy of amorphous
Alloy powder, then carry out the technical solution of Fast Sintering preparation.The present invention is prepared using intermittent planetary ball mill first
The amorphous high-entropy alloy Binder Phase powder of FeCoNiCuCr；Then by amorphous high-entropy alloy Binder Phase powder and hard phase
Powder carries out roller milling mixing, and the mixture prepared still is amorphous state；Finally using be rapidly heated, isothermal treatment for short time
SPS sintering process make amorphous high-entropy alloy Binder Phase recurring structure relaxation in hard alloy complete crystallization, amorphous state to
The process of crystalline state transformation and the sluggish elements diffusion effect of high-entropy alloy itself obtain the dissolution in the opposite Binder Phase of hard
Inhibit, Binder Phase is real high-entropy alloy, to prepare high-entropy alloy bonding phase cemented carbide.
The preparation method of high-entropy alloy bonding phase cemented carbide of the invention, it is characterised in that successively comprise the steps of:
(1) prepared by amorphous state high-entropy alloy powder: various raw material powders are weighed, by atomic percent Fe:Co:Ni:Cu:Cr=1:
1:1:(0.4~0.6): the weighed raw material powder of institute is carried out planetary ball mill, 300~400r/ of rotational speed of ball-mill by (0.4~0.6)
The ratio of grinding media to material of min, ball milling are 10:1, use diameter for the WC-6Co abrading-ball of 5mm, between 72~120h of Ball-milling Time, 4~6h of ball milling
Have a rest 20min, by filtering, dry, sieving after ball milling, is prepared into amorphous state high-entropy alloy Binder Phase powder；
(2) hard phase-amorphous state high-entropy alloy Binder Phase mixture preparation: carbide is weighed by weight percentage and amorphous state is high
Entropy alloy powder, WC, which accounts for 49~97%, TiC and accounts for 0~15%, TaC and account for 0~8%, NbC, accounts for 0~8%, and amorphous state high-entropy alloy is viscous
Knot phase powder accounts for 3~20%；The weighed mixed-powder of institute is subjected to a roller milling mixing, rotational speed of ball-mill 52r/min, ball milling
Ratio of grinding media to material is 4:1, uses diameter for the WC-6Co abrading-ball of 8mm, 24~72h of Ball-milling Time, by filtering, drying, sieving, preparation
At hard phase-amorphous state high-entropy alloy Binder Phase mixture；
(3) prepared by high-entropy alloy bonding phase cemented carbide: hard phase-amorphous state high-entropy alloy Binder Phase mixture is put into mold
Middle progress SPS sintering, heating rate are 100~150 DEG C/min, are heated to 1400~1450 DEG C, sintering pressure is 40~
50MPa, keeps the temperature 5min, and cooling prepares high-entropy alloy bonding phase cemented carbide after coming out of the stove；Hard alloy in sintering process
Binder Phase is crystalline state from amorphous state, and the diffusion in the opposite Binder Phase of hard is inhibited, and Binder Phase is single-phase face-centered cubic
Structure high-entropy alloy.
The preparation method of high-entropy alloy bonding phase cemented carbide of the invention, further characterized in that:
(1) when prepared by amorphous state high-entropy alloy Binder Phase powder, ball-milling medium is dehydrated alcohol, and dosage is that Binder Phase powder is total
The 15~20% of weight are filled with 0.03MPa argon gas in mechanical milling process and are protected, and 400 mesh net filtrations are used after ball milling,
And it is dried at 90~110 DEG C, and be sieved by 100 mesh；
(2) when hard phase-amorphous state high-entropy alloy Binder Phase mixture preparation, ball-milling medium is dehydrated alcohol, and dosage is mixed
The 25% of feed powder end gross weight is closed, uses 400 mesh net filtrations after ball milling, and be dried at 90~110 DEG C, and pass through
The sieving of 60 mesh；
(3) when prepared by high-entropy alloy bonding phase cemented carbide, starting vacuum degree is 2~5Pa, furnace cooling after heat preservation.
The present invention has the advantages that (1) may insure to be pre-formed amorphous state high-entropy alloy using intermittent planetary ball mill
Binder Phase, and traditional technique has only carried out ingredient design by high-entropy alloy definition, by various Binder Phases and hard phase raw material
Powder ball milling together, will lead to the formation that high-entropy alloy is dispersed and be unable to ensure to various composition, therefore complete in sintering process
The Diversity Binder Phase that is usually formed after rather than real high-entropy alloy.(2) preformed high-entropy alloy Binder Phase is in
Existing amorphous state is that crystallization occurs in it in order to make it in sintering stage, can inhibit hard phase element to viscous using this crystallization process
Tie the diffusion of phase.(3) high-entropy alloy itself has a sluggish elements diffusion effect, and hard phase element is to Binder Phase when Fast Sintering
Diffusion is difficult to carry out.(4) heating rate of SPS sintering process is fast, and soaking time is short, can inhibit hard phase element to Binder Phase
Diffusion, be conducive to keep Binder Phase high-entropy alloy ingredient and structure, be also beneficial to keep hard alloy in hard phase it is opposite
Content inhibits hard phase crystal grain to grow up.Hard phase content is consistent with design object, and Binder Phase is high-entropy alloy, is conducive to
Obtain high performance hard alloy.
Detailed description of the invention
Fig. 1 the method for the present invention prepares the process schematic representation of high-entropy alloy bonding phase cemented carbide
Specific embodiment
Example 1: the new bonding phase cemented carbide of high-performance is prepared according to the following steps:
(1) prepared by amorphous state high-entropy alloy Binder Phase powder: various raw material powders are weighed, by atomic percent Fe:Co:Ni:Cu:
Cr=1:1:1:0.4:0.4；The weighed raw material powder of institute is subjected to planetary ball mill, rotational speed of ball-mill 500r/min, the ball material of ball milling
Than using diameter for the WC-Co abrading-ball of 4mm for 5:1, ball-milling medium is dehydrated alcohol, and dosage is Binder Phase powder gross weight
17%, 0.03MPa argon gas, which is filled with, in mechanical milling process is protected, Ball-milling Time 4h, ball milling 1h interval 12min, after ball milling
It is dried using 400 mesh net filtrations, and at 90 DEG C, is sieved by 100 mesh, be prepared into amorphous state high-entropy alloy bonding
Phase powder；
(2) prepared by carbide-amorphous state high-entropy alloy powder mixture: weighing raw material powder by weight percentage, WC is accounted for
90%, amorphous state high-entropy alloy Binder Phase powder accounts for 10%；The weighed mixed-powder of institute is subjected to roller milling mixing, ball milling
The ratio of grinding media to material of revolving speed 56r/min, ball milling are 3:1, use diameter for the WC-Co abrading-ball of 10mm, and ball-milling medium is dehydrated alcohol,
Dosage is the 20% of powder gross weight, and Ball-milling Time 36h, mixed-powder total weight 2% is added into ball grinder by 4h before ball milling terminates
Paraffin 400 mesh net filtrations are used after ball milling as forming agent, and be dried at 100 DEG C, and pass through 60 mesh mistakes
Sieve, is prepared into carbide-amorphous state high-entropy alloy powder mixture；
(3) it takes off the preparation of forming agent green compact: carbide-amorphous state high-entropy alloy mixture being pressed into life under 220MPa pressure
Base, green compact are put into low-pressure sintering furnace, and heating rate is 5 DEG C/min, are heated to 300 DEG C of heat preservation 2h, are passed through stream in insulating process
Amount is the N of 40L/h2, N after heat preservation end is closed2De- forming agent green compact are prepared in furnace cooling, and still Binder Phase still keeps amorphous
State；
(4) prepared by high-entropy alloy bonding phase cemented carbide: green compact being carried out microwave sintering, starting vacuum degree is 3Pa, heating rate
For 40 DEG C/min, 1420 DEG C of heat preservation 20min are heated to, the Ar air cooling that flow is 50L/h is passed through after sintering；Sintering process
In the Binder Phase of hard alloy from amorphous state be crystalline state, the diffusion in the opposite Binder Phase of hard is inhibited, Binder Phase
For single-phase face-centred cubic structure high-entropy alloy.
Example 2: the new bonding phase cemented carbide of high-performance is prepared according to the following steps:
(1) prepared by amorphous state high-entropy alloy Binder Phase powder: various raw material powders are weighed, by atomic percent Fe:Co:Ni:Cu:
Cr=1:1:1:0.4:0.6；The weighed raw material powder of institute is subjected to planetary ball mill, rotational speed of ball-mill 550r/min, the ball material of ball milling
Than using diameter for the WC-Co abrading-ball of 4mm for 5:1, ball-milling medium is dehydrated alcohol, and dosage is Binder Phase powder gross weight
19%, 0.03MPa argon gas, which is filled with, in mechanical milling process is protected, Ball-milling Time 6h, ball milling 1h interval 15min, after ball milling
It is dried using 400 mesh net filtrations, and at 95 DEG C, and is sieved by 100 mesh, be prepared into amorphous state high-entropy alloy bonding
Phase powder；
(2) prepared by carbide-amorphous state high-entropy alloy powder mixture: weighing raw material powder by weight percentage, WC is accounted for
84%, TiC, which account for 5%, TaC and account for 2%, NbC, accounts for 2%, and amorphous state high-entropy alloy Binder Phase powder accounts for 7%；By the weighed mixing of institute
Powder carries out roller milling mixing, and the ratio of grinding media to material of rotational speed of ball-mill 56r/min, ball milling are 3:1, uses diameter for the WC- of 10mm
Co abrading-ball, ball-milling medium are dehydrated alcohol, and dosage is the 24% of powder gross weight, Ball-milling Time 64h, and 4h is to ball before ball milling terminates
The paraffin that mixed-powder total weight 2% is added in grinding jar is used as forming agent, using 400 mesh net filtrations after ball milling, and
It is dried at 105 DEG C, and is sieved by 60 mesh, be prepared into carbide-amorphous state high-entropy alloy powder mixture；
(3) it takes off the preparation of forming agent green compact: carbide-amorphous state high-entropy alloy mixture being pressed into life under 280MPa pressure
Base, green compact are put into low-pressure sintering furnace, and heating rate is 5 DEG C/min, and being passed through flow in 400 DEG C of heat preservation 2h, insulating process is
The N of 50L/h2, N after heat preservation end is closed2De- forming agent green compact are prepared in furnace cooling, and still Binder Phase still keeps amorphous state；
(4) prepared by high-entropy alloy bonding phase cemented carbide: green compact being carried out microwave sintering, starting vacuum degree is 5Pa, heating rate
The Ar air cooling that flow is 60L/h is passed through after sintering in 1440 DEG C of heat preservation 25min for 45 DEG C/min；In sintering process
The Binder Phase of hard alloy is crystalline state from amorphous state, and the diffusion in the opposite Binder Phase of hard is inhibited, and Binder Phase is single
Phase face-centred cubic structure high-entropy alloy.
Claims (2)
1. a kind of preparation method of high-entropy alloy bonding phase cemented carbide, it is characterised in that successively comprise the steps of:
(1) prepared by amorphous state high-entropy alloy powder: various raw material powders are weighed, by atomic percent Fe:Co:Ni:Cu:Cr=1:
1:1:(0.4~0.6): the weighed raw material powder of institute is carried out planetary ball mill, 300~400r/ of rotational speed of ball-mill by (0.4~0.6)
The ratio of grinding media to material of min, ball milling are 10:1, use diameter for the WC-6Co abrading-ball of 5mm, between 72~120h of Ball-milling Time, 4~6h of ball milling
Have a rest 20min, by filtering, dry, sieving after ball milling, is prepared into amorphous state high-entropy alloy Binder Phase powder；
(2) hard phase-amorphous state high-entropy alloy Binder Phase mixture preparation: carbide is weighed by weight percentage and amorphous state is high
Entropy alloy powder, WC, which accounts for 49~97%, TiC and accounts for 0~15%, TaC and account for 0~8%, NbC, accounts for 0~8%, and amorphous state high-entropy alloy is viscous
Knot phase powder accounts for 3~20%；The weighed mixed-powder of institute is subjected to a roller milling mixing, rotational speed of ball-mill 52r/min, ball milling
Ratio of grinding media to material is 4:1, uses diameter for the WC-6Co abrading-ball of 8mm, 24~72h of Ball-milling Time, by filtering, drying, sieving, preparation
At hard phase-amorphous state high-entropy alloy Binder Phase mixture；
(3) prepared by high-entropy alloy bonding phase cemented carbide: hard phase-amorphous state high-entropy alloy Binder Phase mixture is put into mold
Middle progress SPS sintering, heating rate are 100~150 DEG C/min, are heated to 1400~1450 DEG C, sintering pressure is 40~
50MPa, keeps the temperature 5min, and cooling prepares high-entropy alloy bonding phase cemented carbide after coming out of the stove；Hard alloy in sintering process
Binder Phase is crystalline state from amorphous state, and the diffusion in the opposite Binder Phase of hard is inhibited, and Binder Phase is single-phase face-centered cubic
Structure high-entropy alloy.
2. the preparation method of high-entropy alloy bonding phase cemented carbide according to claim 1, further characterized in that:
(1) when prepared by amorphous state high-entropy alloy Binder Phase powder, ball-milling medium is dehydrated alcohol, and dosage is that Binder Phase powder is total
The 15~20% of weight are filled with 0.03MPa argon gas in mechanical milling process and are protected, and 400 mesh net filtrations are used after ball milling,
And it is dried at 90~110 DEG C, and be sieved by 100 mesh；
(2) when hard phase-amorphous state high-entropy alloy Binder Phase mixture preparation, ball-milling medium is dehydrated alcohol, and dosage is mixed
The 25% of feed powder end gross weight is closed, uses 400 mesh net filtrations after ball milling, and be dried at 90~110 DEG C, and pass through
The sieving of 60 mesh；
(3) when prepared by high-entropy alloy bonding phase cemented carbide, starting vacuum degree is 2~5Pa, furnace cooling after heat preservation.
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