CN109175387A - The method that Amorphous Crystallization prepares nanocrystalline WC-Co hard alloy - Google Patents
The method that Amorphous Crystallization prepares nanocrystalline WC-Co hard alloy Download PDFInfo
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- CN109175387A CN109175387A CN201811233704.8A CN201811233704A CN109175387A CN 109175387 A CN109175387 A CN 109175387A CN 201811233704 A CN201811233704 A CN 201811233704A CN 109175387 A CN109175387 A CN 109175387A
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- 239000000956 alloy Substances 0.000 title claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 56
- 229910009043 WC-Co Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002425 crystallisation Methods 0.000 title claims abstract description 19
- 230000008025 crystallization Effects 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 52
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000000280 densification Methods 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000000159 protein binding assay Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 3
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- 238000003701 mechanical milling Methods 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 1
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- 239000003966 growth inhibitor Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- 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
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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
- C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The method that Amorphous Crystallization prepares nanocrystalline WC-Co hard alloy belongs to cemented carbide material preparation field.Ternary compound Co is prepared first6W6C powder obtains amorphous Co through high-energy ball milling6W6C powder, then under conditions of discharge plasma sintering, make amorphous state Co6W6Crystallization occurs for C powder, and a step generates nano-polycrystalline WC-Co two-phase composite powder, and then is sintered densification, finally obtains the fine and close WC-Co hard alloy block materials of nanometer crystal microstructure.This method may insure amorphous Co6W6C powder complete crystallization, reaction sufficiently obtain pure WC and Co, while obvious crystal grain not occurring and grows up and WC average grain size in block is made to be maintained at nanoscale.
Description
Technical field
The invention belongs to cemented carbide material preparation fields, and in particular to a kind of with ternary compound is that precursor preparation is received
The method of rice WC-Co cemented carbide block materials.
Background technique
WC-Co hard alloy because of the special performances such as its high rigidity and wearability, high bending strength and good fracture toughness,
It is used widely in industrial circles such as cutting element, mold, mine tool and wear-resisting spare parts.When WC grain size is refine to
Ultra-fine or even nanoscale, hard alloy can have higher hardness and strength.Conventional method in WC-Co powder by being added
Refractory carbide (VC, Cr3C2, NbC etc.) be used as grain growth inhibitor, control grain coarsening in sintering process, to
To the hard alloy block material of nanocrystal tissue.However, growing up and obtaining close to theoretical due to being difficult to solve control crystal grain
Contradiction between the densified sintering product of density, the WC average grain size of current domestic and international prepared hard alloy block material
The overwhelming majority is in submicron-scale, and rarely WC average grain size is reduced to 100nm or less truly nanocrystalline hard
The research of matter alloy block material is reported.
Amorphous Crystallization method is a kind of effective ways for the metal or alloy that metal material field is used to prepare nanometer crystal microstructure.
But this method is never applied to ceramic material field or ceramic matric composite field, basic reason are ceramic base
Amorphous state persursor material prepares extremely difficult.Therefore, it there is no so far both at home and abroad and prepare nanocrystalline hard by way of Amorphous Crystallization
The report of alloy.To break through this international technology problem, the present invention selects a kind of special ternary compound using it as before indirect
Body is driven, prepares amorphous microstructure first, then by the synchronous Amorphous Crystallization occurred and reaction in-situ process, obtain nanometer crystal microstructure
WC-Co composite material block.
Summary of the invention
The present invention prepares ternary compound Co in batches first6W6C powder preferably has granted patent skill using applicant
Art (granted patent number: CN201510491451.4)；By the Co of preparation6W6C powder progress high-energy ball milling obtains amorphous
Co6W6C powder recycles the unique conditions of discharge plasma sintering, makes amorphous state Co6W6C powder is synchronous to occur crystallization,
Nano-polycrystalline WC-Co composite powder end is generated, and then is sintered densification, finally obtains the fine and close WC-Co of nanometer crystal microstructure
Hard alloy block material.Present invention be characterized in that comprising the steps of:
(1) the ternary compound Co that average grain diameter is not more than 500nm is prepared in batches6W6C powder (has with applicant and awards
Weigh patented technology (granted patent number: CN201510491451.4)), using it as raw material, hard is added together with sintered carbide ball
Four kinds of hard alloy abrading-balls that diameter is respectively 4mm, 5mm, 8mm and 10mm, mass ratio are packed into alloy ball grinder, in every tank
For 2:2:4:2, using argon gas as protective atmosphere, hard alloy abrading-ball and ternary compound Co6W6The weight ratio of C be (18~
25): 1, Ball-milling Time is 55~70 hours, and rotational speed of ball-mill is 500~600r/min, obtains amorphous Co after ball milling6W6C powder
End；
(2) to the amorphous state Co of preparation6W6C powder carries out carbon content detection, the carbon content and reaction equation of binding assay
Co6W6Corresponding carbon black is added in C+5C=6WC+6Co, so that the carbon element content in mixed-powder is 6.00%~6.90wt%；
(3) hard alloy ball milling is added together with the hard alloy abrading-ball that diameter is 8mm in mixed-powder obtained by step (2)
In tank, ball-milling medium is dehydrated alcohol, and the weight ratio of hard alloy abrading-ball and mixed-powder is (3~5): 1, Ball-milling Time 10
~15 hours, rotational speed of ball-mill was 250~300r/min, this time obtained the evenly dispersed mixed-powder of carbon dust after ball milling；
(4) after mixed-powder obtained by step (3) being dried, a certain amount of be fitted into hot pressing die is taken to carry out precompressed, pressed
Power is 1~2MPa, and then the mold equipped with mixed-powder is put into discharge plasma sintering system and carries out crystallization and burning
Knot densification, wherein pressure is 30~40MPa, and heating rate is 100~140 DEG C/min, and temperature is 870~1000 DEG C/min,
Soaking time is 2~5min, finally obtains the fine and close WC-Co hard alloy block that object is mutually pure, average grain size is less than 100nm
Body material.Technical advantage and effect of the invention is:
(1) mode of ball milling and effect are different from common wet-milling mode in the preparation of previous hard alloy in step (1), this
Method is added without any ball-milling medium, and uses argon gas as protective atmosphere, meanwhile, using higher ratio of grinding media to material.Argon gas conduct
The protective atmosphere of dry milled process can be effectively prevented powder in mechanical milling process and aoxidize.The lesser ball of diameter can be protected in abrading-ball
Card powder obtains abundant ball milling, and the ball being relatively large in diameter provides biggish impact energy in mechanical milling process.The abrading-ball of different-diameter
It is used cooperatively, in combination with higher ratio of grinding media to material, it is ensured that Co6W6C powder obtains sufficiently high energy in mechanical milling process, makes
A large amount of crystal defects are generated inside its polycrystal, are finally resulted in lattice unstability avalanche, are obtained the powder of amorphous structural state.
(2) the object phase purity of WC-Co hard alloy block materials is very sensitive to carbon content, and what is used in this method is best
Carbon additive amount is obtained by great deal of calculation and analysis and experimental exploring, and one will guarantee chemistry needed for meeting generation pure substance phase
Ratio is measured, two will be in conjunction with ball-milling technology, each parameter combination of discharge plasma sintering process to copmbined-carbon changes of contents, carbon distribution etc.
Influence, it is accurate to adjust initial carbon additive amount.Comprehensively consider and is carried out in combination with carbon content in the powder detected in step (2)
With carbon, to guarantee in the sintering cemented carbide block finally prepared other than WC, Co without other miscellaneous phases, and nothing in reaction product
Extra free carbon.
(3) using dehydrated alcohol as ball-milling medium in step (3), carbon dust is added and carries out wet-milling, be conducive to powder dispersion, eliminate
Reunite, due to the lubricating action of carbon dust, is conducive to amorphous state Co6W6It is sufficiently mixed between C powder and carbon dust.This step is another
One feature is that weight is relatively low between abrading-ball and powder, and Ball-milling Time is shorter.This technique be by reach uniformly mixing for the purpose of,
The object for avoiding the ball milling of excess energy from making amorphous powder mutually changes, and guarantees that follow-up sintering process is gone on smoothly.
(4) using the unique advantage of discharge plasma sintering technique in step (4), Crystallizing treatment is carried out to amorphous powder
And with reaction synthesis, sintering densification, this process is different from vacuum reaction, vacuum-sintering or low pressure sintering densification and waited
Journey.In this step, amorphous state Co6W6C is synchronous to occur crystallization, the nanocrystalline WC and Co two-phase of reaction generation, then then sintering causes
Densification obtains nanocrystalline WC-Co hard alloy block materials.
(5) during discharge plasma sintering technological parameter determination, need to combine material composition, reaction holding temperature etc.
Determine the rate of heat addition and soaking time, with obtain reaction sufficiently, object is mutually pure and the WC-Co block obviously grown up does not occur for crystal grain
Body material.Excessive pressure is unfavorable for the progress of crystallization and reaction process, and excessive temperature and too long soaking time will lead to crystal grain
Size is larger.In this method during discharge plasma sintering combination of process parameters it is preferable to determine visited by many experiments
Rope attempts acquisition, it can be ensured that amorphous Co6W6C powder complete crystallization, reacted constituent obtain pure WC and Co, while not sending out
Raw obvious crystal grain grows up and WC average grain size in block is made to be maintained at nanoscale, and WC average grain size of the invention subtracts
It is small to 100nm or less.
Detailed description of the invention
(a) is Co in Fig. 16W6The X-ray diffractogram of C powder original state, (b) amorphous state to be prepared in embodiment 1
Co6W6The X-ray diffractogram of C powder, (c) the amorphous state Co to be prepared in embodiment 26W6The X-ray diffractogram of C powder.
(a) is the amorphous state Co prepared in embodiment 1 in Fig. 26W6The scanning electron microscope microstructure of C powder is (b) implementation
The amorphous state Co prepared in example 26W6The scanning electron microscope microstructure of C powder.
Fig. 3 is the X-ray diffractogram of the nanocrystalline WC-Co hard alloy block prepared in embodiment 2.
Fig. 4 (a) is that the Nanoindentation of the nanocrystalline WC-Co hard alloy block prepared in embodiment 2 measures hardness,
(b) elasticity modulus is measured for the Nanoindentation of the nanocrystalline WC-Co hard alloy block prepared in embodiment 2.
Fig. 5 (a) is that the Nanoindentation of the nanocrystalline WC-Co hard alloy block prepared in embodiment 3 measures hardness,
(b) to implement, the Nanoindentation measurement elasticity modulus of the nanocrystalline WC-Co hard alloy block prepared in 3.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
Have granted patent technology (granted patent number: CN201510491451.4) with applicant and prepares average grain in batches
The ternary compound Co of diameter about 300nm6W6Hard alloy ball grinder is added using it as raw material in C powder together with sintered carbide ball
In, in every tank be packed into diameter be respectively 4mm, 5mm, 8mm and 10mm four kinds of hard alloy abrading-balls, mass ratio 2:2:4:2,
Using argon gas as protective atmosphere, hard alloy abrading-ball and ternary compound Co6W6The weight ratio of C is 18:1, Ball-milling Time 70
Hour, rotational speed of ball-mill 600r/min obtains amorphous Co after ball milling6W6C powder；To the amorphous state Co of preparation6W6C powder
Carbon content detection is carried out, measurement carbon content is 1.10wt.%, according to reaction equation Co6W6Corresponding charcoal is added in C+5C=6WC+6Co
Black 4.90wt.%, so that the carbon content in mixed-powder is 6.00%；The hard that gained mixed-powder and diameter are 8mm is closed
Golden abrading-ball is added together in hard alloy ball grinder, and ball-milling medium is dehydrated alcohol, the weight of hard alloy abrading-ball and mixed-powder
For amount than being 3:1, Ball-milling Time is 15 hours, rotational speed of ball-mill 300r/min, and evenly dispersed mixed of carbon dust is this time obtained after ball milling
Close powder；After above-mentioned mixed-powder is dried, a certain amount of be fitted into hot pressing die is taken to carry out precompressed, pressure 1MPa, with
The mold equipped with mixed-powder is put into discharge plasma sintering system afterwards and carries out crystallization and sintering densification, wherein pressing
Power is 40MPa, and heating rate is 100 DEG C/min, and temperature is 870 DEG C, and it is mutually pure, flat to finally obtain object by soaking time 5min
Equal crystallite dimension is less than the fine and close WC-Co hard alloy block materials of 100nm.
Amorphous state Co manufactured in the present embodiment6W6The X-ray diffraction of C powder is illustrated in Fig. 1 (a), the micro- shape of scanning electron microscope
Looks are shown in Fig. 2 (a).
Embodiment 2
Have granted patent technology (granted patent number: CN201510491451.4) with applicant and prepares average grain in batches
The ternary compound Co of diameter about 500nm6W6Hard alloy ball grinder is added using it as raw material in C powder together with sintered carbide ball
In, in every tank be packed into diameter be respectively 4mm, 5mm, 8mm and 10mm four kinds of hard alloy abrading-balls, mass ratio 2:2:4:2,
Using argon gas as protective atmosphere, hard alloy abrading-ball and ternary compound Co6W6The weight ratio of C is 22:1, Ball-milling Time 65
Hour, rotational speed of ball-mill 550r/min obtains amorphous Co after ball milling6W6C powder；To the amorphous state Co of preparation6W6C powder
Carbon content detection is carried out, measurement carbon content is 1.20wt.%, according to reaction equation Co6W6Corresponding charcoal is added in C+5C=6WC+6Co
Black 5.30wt.%, so that the carbon content in mixed-powder is 6.50%；The hard that gained mixed-powder and diameter are 8mm is closed
Golden abrading-ball is added together in hard alloy ball grinder, and ball-milling medium is dehydrated alcohol, the weight of hard alloy abrading-ball and mixed-powder
For amount than being 4:1, Ball-milling Time is 12 hours, rotational speed of ball-mill 280r/min, and evenly dispersed mixed of carbon dust is this time obtained after ball milling
Close powder；After above-mentioned mixed-powder is dried, a certain amount of be fitted into hot pressing die is taken to carry out precompressed, pressure 1.5MPa,
Then the mold equipped with mixed-powder is put into discharge plasma sintering system and carries out crystallization and sintering densification, wherein
Pressure is 40MPa, and heating rate is 140 DEG C/min, and temperature is 930 DEG C, soaking time 3min, finally obtain object it is mutually pure,
Average grain size is less than the fine and close WC-Co hard alloy block materials of 100nm.
Amorphous state Co manufactured in the present embodiment6W6The X-ray diffraction of C powder is illustrated in Fig. 1 (b), the micro- shape of scanning electron microscope
Looks are shown in Fig. 2 (b), and the X-ray diffraction of the nanocrystalline WC-Co hard alloy block of preparation is illustrated in Fig. 3, Nanoindentation measurement
Hardness and elastic modulus be shown in Fig. 4.
Embodiment 3
Have granted patent technology (granted patent number: CN201510491451.4) with applicant and prepares average grain in batches
The ternary compound Co of diameter about 400nm6W6Hard alloy ball grinder is added using it as raw material in C powder together with sintered carbide ball
In, in every tank be packed into diameter be respectively 4mm, 5mm, 8mm and 10mm four kinds of hard alloy abrading-balls, mass ratio 2:2:4:2,
Using argon gas as protective atmosphere, hard alloy abrading-ball and ternary compound Co6W6The weight ratio of C is 25:1, Ball-milling Time 55
Hour, rotational speed of ball-mill 500r/min obtains amorphous Co after ball milling6W6C powder；To the amorphous state Co of preparation6W6C powder
Carbon content detection is carried out, measurement carbon content is 1.50wt.%, according to reaction equation Co6W6Corresponding charcoal is added in C+5C=6WC+6Co
Black 5.40wt.%, so that the carbon content in mixed-powder is 6.90%；The hard that gained mixed-powder and diameter are 8mm is closed
Golden abrading-ball is added together in hard alloy ball grinder, and ball-milling medium is dehydrated alcohol, the weight of hard alloy abrading-ball and mixed-powder
For amount than being 5:1, Ball-milling Time is 10 hours, rotational speed of ball-mill 250r/min, and evenly dispersed mixed of carbon dust is this time obtained after ball milling
Close powder；After above-mentioned mixed-powder is dried, a certain amount of be fitted into hot pressing die is taken to carry out precompressed, pressure 2MPa, with
The mold equipped with mixed-powder is put into discharge plasma sintering system afterwards and carries out crystallization and sintering densification, wherein pressing
Power is 35MPa, and heating rate is 120 DEG C/min, and temperature is 1000 DEG C, and it is mutually pure, flat to finally obtain object by soaking time 2min
Equal crystallite dimension is less than the fine and close WC-Co hard alloy block materials of 100nm.
Nanocrystalline WC-Co hard alloy block manufactured in the present embodiment uses the consistency and elasticity mould of Nanoindentation measurement
Amount is shown in Fig. 5.
Claims (1)
1. the method that Amorphous Crystallization prepares nanocrystalline WC-Co hard alloy, which is characterized in that prepare ternary compound first
Co6W6C powder, by the Co of preparation6W6C powder carries out high-energy ball milling and obtains amorphous Co6W6C powder, then in plasma discharging
Under conditions of sintering, make amorphous state Co6W6Crystallization occurs for C powder, and a step generates nano-polycrystalline WC-Co two-phase composite powder
End, and then it is sintered densification, finally obtain the fine and close WC-Co hard alloy block materials of nanometer crystal microstructure；Specifically include
Following steps:
(1) the ternary compound Co that average grain diameter is not more than 500nm is prepared in batches6W6C powder is closed using it as raw material with hard
Gold goal is added together in hard alloy ball grinder, and four kinds of hard that diameter is respectively 4mm, 5mm, 8mm and 10mm are packed into every tank
Alloy Balls In Milling, mass ratio 2:2:4:2, using argon gas as protective atmosphere, hard alloy abrading-ball and ternary compound Co6W6C
Weight ratio be (18~25): 1, Ball-milling Time is 55~70 hours, and rotational speed of ball-mill is 500~600r/min, is obtained after ball milling
Amorphous Co6W6C powder；
(2) to the amorphous state Co of preparation6W6C powder carries out carbon content detection, the carbon content and reaction equation Co of binding assay6W6C+5C
Corresponding carbon black is added in=6WC+6Co, so that the carbon element content in mixed-powder is 6.00%~6.90wt%；
(3) hard alloy ball grinder is added together with the hard alloy abrading-ball that diameter is 8mm in mixed-powder obtained by step (2)
In, ball-milling medium is dehydrated alcohol, and the weight ratio of hard alloy abrading-ball and mixed-powder is (3~5): 1, Ball-milling Time is 10~
15 hours, rotational speed of ball-mill was 250~300r/min, this time obtained the evenly dispersed mixed-powder of carbon dust after ball milling；
(4) after mixed-powder obtained by step (3) being dried, a certain amount of be fitted into hot pressing die is taken to carry out precompressed, pressure 1
Mold equipped with mixed-powder is then put into discharge plasma sintering system and carries out crystallization and densified sintering product by~2MPa
Change, wherein pressure is 30~40MPa, and heating rate is 100~140 DEG C/min, and temperature is 870~1000 DEG C/min, when heat preservation
Between be 2~5min, finally obtain that object is mutually pure, fine and close WC-Co hard alloy block material of the average grain size less than 100nm
Material.
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