CN107739950A - A kind of WC Co cBN composite hard alloys and preparation method thereof - Google Patents
A kind of WC Co cBN composite hard alloys and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 37
- 239000000956 alloy Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 238000003754 machining Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000011812 mixed powder Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910003470 tongbaite Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001238 wet grinding Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 7
- 229910009043 WC-Co Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 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
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B22F3/02—Compacting only
-
- 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
-
- 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
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to ultra-hard cutting tool technical field, is related to a kind of WC Co cBN composite hard alloys and preparation method thereof.The chemical composition of the WC Co cBN composite hard alloys is by weight percentage：Ultra-fine/nanometer WC powder 70%~90%, Co powder 3%~15%, grain inhibitor 0.35%~0.75%, surface has been coated with the cBN micro mists 1%~10.75% of excellent metal Mo, Ni or Ti film of one layer of stability at elevated temperature, a kind of spherical mixed-powder 0.25%~5% selected from Al, Ni, Cr, Y or its combination, above component are prepared into composite hard alloy by discharge plasma sintering.Alloy grain degree prepared by the present invention is tiny, and hardness, intensity, toughness are high, and anti-wear performance is good, can overcome the low difficulty of dry cutting heat endurance, processing cost is reduced, especially suitable for high performance machine machining cutting tool.
Description
Technical field
The invention belongs to ultra-hard cutting tool technical field, and in particular to a kind of WC-Co-cBN composite hard alloys and its
Preparation method.
Background technology
CBN is the material that hardness and thermal conductivity are only second to diamond, and its hardness and thermal conductivity are far above WC, have high abrasion
Property, be finishing tool, dry cutting cutter, emery wheel product prepare etc. field popular research material.
At present, cBN adulterates WC-Co hard alloy it has been reported that wherein, in hard alloy system cBN addition compared with
High (volume ratio>20vol%), it is while more using compared with coarseness cBN powder (more than 3 μm), and Binder Phase Co content all compared with
Low (<10wt%).Thicker cBN is not susceptible to phase in version in hard alloy densification sintering process, and cBN granularity is thinner, table
Face is more active, is more prone to phase in version in sintering process, higher Co contents in liquid sintering process can with dissolving-
The appearance of precipitation process and promote hBN from cBN to graphite state change, these problems are unfavorable to the performance of enhancing hard alloy
's.
Further, cBN is poor with WC/Co wetabilitys as hardening agent.First, in liquid-phase sintering, cBN (thermal coefficient of expansions
For 2.0 × 10-6/ DEG C, fusing point 3500K) (thermal coefficient of expansion is 4.5 × 10 with WC-Co-6/ DEG C~7.1 × 10-6/ DEG C, Co phases melt
Point is about 1600K) liquid Co phase wetabilitys it is bad, directly addition easily produces many holes and metallurgical interface in sintered body and made
With difference, the performance of composite is deteriorated；Second, the boron in cBN has certain compatibility with cobalt, the two can react generation cobalt
Boride；Third, under the WC-Co liquid phase sintering conditions of routine during (about 1400 DEG C) sintering, superhard cubic boron nitride can be in Co
Dissolving-precipitation process in change to the hexagonal phase boron nitride particle of soft, the appearance of liquid phase cobalt can accelerate transition process.
At present, pertinent literature research shows：By cBN film-coating modifications, using corrective measures such as solid-phase sinterings, can improve
Metallurgical junction between cBN and WC/Co is made a concerted effort, and cBN heat endurance and crystal structure state is kept, so as to improve cBN composite ganoines
The combination property of alloy.But the problems such as WC-Co-cBN hard alloy consistency is low, cBN particles come off, cBN heat endurance differences
Still exist.
WC-Co-cBN hard alloy provided by the invention, comprehensive cBN modifications, solid-phase sintering, crystal grain thinning, addition wetting
The methods of agent and approach, the high intensity, high rigidity and high abrasion characteristic of WC-Co hard alloy can be not only kept, and dry cut
Cutting the defects of heat endurance is low is also improved, and reduces processing cost, is a weight of current exploitation Novel cutting tool material
Developing direction is wanted, there is great commercial value.
The content of the invention
The problem of existing for the WC-Co hard alloy of cBN doping at present described above, the present invention provides a kind of WC-Co-
CBN composite hard alloys and preparation method thereof.
A kind of WC-Co-cBN composite hard alloys, its chemical composition are by weight percentage：Ultra-fine/nanometer WC powder
70%~90%, Co powder 3%~15%, grain inhibitor 0.35%~0.75%, hardening agent 1%~10.75%, wetting agent
0.25%~5%；
Wherein, ultra-fine/nanometer WC powder is matrix, and Fisher particle size is less than 0.6 μm；
Co powder is binding agent, and Fisher particle size is less than 1.0 μm.
The grain inhibitor is TaC, VC, Cr3C2, one or more in TiC.
The hardening agent is that powder surface has been coated with excellent metal Mo, Ni or Ti film of one layer of stability at elevated temperature
CBN micro mists, Fisher particle size are 1~2 μm.
The wetting agent is a kind of spherical mixed-powder selected from Al, Ni, Cr, Y or its combination, and Fisher particle size is 1~2 μ
m。
A kind of WC-Co-cBN composite hard alloys described above, its preparation method, are mainly included the following steps that：
(1) batch mixing, ball milling：By WC powder, Co powder and grain inhibitor 24~48h of mixing and ball milling, cBN powder is then added,
Continue ball milling 2h~8h under identical ball milling parameter, be eventually adding wetting agent ball milling 0.5h~2h again；
Wherein, the ball grinding technique used is rolls wet-milling, and ball-milling medium is absolute alcohol, and abrading-ball is YG8 balls (Φ 6),
Ratio of grinding media to material is 4:1, rotational speed of ball-mill 60r/min.
(2) it is dried in vacuo：Temperature is 60~90 DEG C, and vacuum is 0~-0.1Pa, and the time is 5~10h.
(3) sieve, suppress：Every time weigh 15g sieving after compound be placed in graphite jig, be pressed into advance Φ 20mm ×
5mm disk.
(4) sinter：Using discharge plasma sintering process, heating rate is 80~200 DEG C/min, sintering pressure is 30~
40MPa, sintering temperature are 1000 DEG C~1350 DEG C, 2~12min of soaking time, furnace cooling.
The invention has the advantages that：
1. the alloy prepared by the present invention, its cBN has good heat endurance, does not undergo phase transition, film-coating modification and profit
Humectant action effect is good so that the metallurgy action power between cBN and WC/Co is strong, particle strengthening positive effect, is advantageous to improve alloy
Consistency, improve its comprehensive mechanical property.
2. preparation method provided by the invention, using grain inhibitor, solid-phase sintering and ball-milling technology, be advantageous to suppress WC
Crystal grain is grown up, and is kept cBN granule integrities, is formed equally distributed duplex grain structure, can effectively prevent to enter one the defects of crackle
Step extension so that the grain size of alloy is tiny, hardness is high, intensity is high, good toughness, anti-wear performance are good.
3. WC-Co-cBN hard alloy prepared by the present invention, it can not only keep high intensity, the height of WC-Co hard alloy
Hardness, high-wearing feature and high tenacity, and the low difficulty of dry cutting heat endurance can be overcome, processing cost is reduced, improves and adds
Work precision and processing efficiency, suitable for the difficult processing material such as hardened steel, titanium alloy, high temperature alloy, high-strength spheroidal graphite cast-iron, composite
The cemented carbide cutting tool of material.
Brief description of the drawings
Fig. 1：Surface plating is formed with the ESEM microstructure of the cBN powder of Mo films.
Fig. 2：The ESEM microstructure of wetting agent 6AlY24Cr70Ni powder.
Fig. 3：WC-12Co-cBN composite hard alloy Fracture scan Electronic Speculum microstructures,
Wherein, a：WC, cBN grains distribution shape appearance figure；b：CBN granule-morphologies and interface topography figure；c：Fracture crack pattern
Figure.
Embodiment
The present invention provides a kind of WC-Co-cBN composite hard alloys and preparation method thereof, the WC-Co-cBN composite ganoines
Alloy, mainly it is made up of WC powder matrix, Co powder binding agent, grain inhibitor, hardening agent, wetting agent, is burnt by plasma discharging
Knot is prepared into composite hard alloy.The present invention will be further described with reference to the accompanying drawings and detailed description.
Embodiment 1：
1) weigh：By the WC powder (Fisher particle size be 0.4 μm) of mass fraction 82.9%, (Fisher particle size is for 12% Co powder
0.8 μm), 0.35% VC powder, 0.25% Cr3C2Powder, 4% surface plating Mo cBN powder (original 2 μm of Fisher particle size, such as
Shown in Fig. 1), 0.5% 6AlY24Cr70Ni globular powders (as shown in Figure 2).
2) batch mixing, ball milling：Raw material WC powder, Co powder, VC powder, Cr are weighed in proportion3C2Powder is added in roller ball grinding jar, ball milling
Medium is absolute alcohol, and abrading-ball is that YG8 balls (Φ 6) ratio of grinding media to material is 4:1, rotational speed of ball-mill 60r/min, ball milling 36h；Then press
Ratio adds surface plating Mo cBN powder, continues ball milling 3h under identical ball milling parameter；It is eventually adding 6AlY24Cr70Ni powder
End, ball milling 1h.
3) it is dried in vacuo：Drying temperature is 85 DEG C, and vacuum is -0.1Pa, drying time 7h.
4) sieve：Compound after vacuum drying is sieved using (- 80) mesh sieve.
5) suppress：Compound is placed in graphite jig after weighing 15g sievings every time, is pressed into Φ 20mm × 5mm's in advance
Disk.
6) sinter：When discharge plasma sinters, heating rate is set as 100 DEG C/min, sintering pressure 40MPa,
Sintering temperature is 1250 DEG C, soaking time 5min, furnace cooling, wherein 800 DEG C are unloaded and are depressed into 20MPa.
7) sample preparation：Required test specimen is prepared by appropriate machining and polishing.
WC-12Co-cBN composite hard alloys manufactured in the present embodiment, WC-12Co-cBN composite ganoines as shown in Figure 3 close
Golden Fracture scan Electronic Speculum microstructure, cBN granule integrities are good, and metallurgical interface active force is strong, form equally distributed mixed crystal knot
Structure, it can effectively prevent to further expand the defects of crackle, its WC grain degree is 0.18 μm, hardness HV10For 2080, consistency is big
In 99.9%.
Claims (5)
- A kind of 1. WC-Co-cBN composite hard alloys, it is characterised in that the WC-Co-cBN composite hard alloys chemistry into Divide and be by weight percentage：Ultra-fine/nanometer WC powder 70%~90%, Co powder 3%~15%, grain inhibitor 0.35%~ 0.75%, hardening agent 1%~10.75%, wetting agent 0.25%~5%；Wherein, ultra-fine/nanometer WC powder is matrix, and Fisher particle size is less than 0.6 μm；Co powder is binding agent, and Fisher particle size is less than 1.0 μm.
- A kind of 2. WC-Co-cBN composite hard alloys according to claim 1, it is characterised in that the grain inhibitor For TaC, VC, Cr3C2, one or more in TiC.
- 3. a kind of WC-Co-cBN composite hard alloys according to claim 1, it is characterised in that the hardening agent is powder Last surface has been coated with the cBN micro mists of excellent metal Mo, Ni or Ti film of one layer of stability at elevated temperature, and Fisher particle size is 1~2 μm。
- 4. a kind of WC-Co-cBN composite hard alloys according to claim 1, it is characterised in that the wetting agent is one The spherical mixed-powder of kind selected from Al, Ni, Cr, Y or its combination, Fisher particle size are 1~2 μm.
- 5. a kind of preparation method of WC-Co-cBN composite hard alloys described in claim 1-4, it is characterised in that mainly include Following steps：(1) weigh：Raw material is weighed by the formula composition of above-mentioned WC-Co-cBN composite hard alloys；(2) batch mixing, ball milling：By WC powder, Co powder and grain inhibitor 24~48h of mixing and ball milling, cBN powder is then added, in phase Continue ball milling 2h~8h under same ball milling parameter, be eventually adding wetting agent ball milling 0.5h~2h again；Wherein, for the ball grinding technique used to roll wet-milling, ball-milling medium is absolute alcohol, and abrading-ball is YG8 balls (Φ 6), ball material Than for 4:1, rotational speed of ball-mill 60r/min；(3) it is dried in vacuo：Temperature is 60~90 DEG C, and vacuum is 0~-0.1Pa, and the time is 5~10h；(4) sieve：Compound after vacuum drying is sieved；(5) suppress：Compound is placed in graphite jig after weighing 15g sievings every time, is pressed into Φ 20mm × 5mm circle in advance Piece；(6) sinter：Using discharge plasma sintering process, heating rate is 80~200 DEG C/min, sintering pressure is 30~ 40MPa, sintering temperature are 1000 DEG C~1350 DEG C, 2~12min of soaking time, furnace cooling；(7) sample preparation：Required test specimen is prepared by appropriate machining and polishing.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467983A (en) * | 2018-03-07 | 2018-08-31 | 河源华盈科技有限公司 | Using submicron order TaC and Cr3C2Ti (C, the N) base metal-ceramic materials and preparation method of enhancing |
| CN108624772A (en) * | 2018-06-26 | 2018-10-09 | 南京理工大学 | Ultra-fine Grained tungsten carbide base carbide alloy material and preparation method thereof |
| CN109022997A (en) * | 2018-09-14 | 2018-12-18 | 河源富马硬质合金股份有限公司 | A kind of high tough high-wearing feature polycrystalline cemented carbide material |
| CN109202070A (en) * | 2018-10-25 | 2019-01-15 | 湖南工业大学 | A kind of hard alloy forming method based on cooled |
| CN109266940A (en) * | 2018-10-26 | 2019-01-25 | 南方科技大学 | A kind of carbon tungsten-cobalt composite material and preparation method and application |
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Cited By (17)
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Effective date of registration: 20191206 Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone Branch Hing Street No. 11 Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088 Beijing city Xicheng District Xinjiekou Avenue No. 2 Patentee before: General Research Institute for Nonferrous Metals |