CN109652671A - A kind of graphene carbon source WC-Co hard alloy - Google Patents
A kind of graphene carbon source WC-Co hard alloy Download PDFInfo
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- CN109652671A CN109652671A CN201710948774.0A CN201710948774A CN109652671A CN 109652671 A CN109652671 A CN 109652671A CN 201710948774 A CN201710948774 A CN 201710948774A CN 109652671 A CN109652671 A CN 109652671A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000000956 alloy Substances 0.000 title claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 229910009043 WC-Co Inorganic materials 0.000 title claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000000280 densification Methods 0.000 claims abstract description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 230000010534 mechanism of action Effects 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- 238000013401 experimental design Methods 0.000 claims description 3
- 238000007373 indentation Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000003966 growth inhibitor Substances 0.000 claims description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- -1 graphite Alkene Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- HZLBQBQEGLFWLA-UHFFFAOYSA-N cobalt;oxotungsten Chemical compound [W].[Co]=O HZLBQBQEGLFWLA-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
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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)
-
- 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
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- 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
-
- 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
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
In order to improve hardness, the wearability of WC-Co hard alloy, it is prepared for a kind of graphene carbon source WC-Co hard alloy.Using ten layers of graphene, WO2.9And Co3O4For raw material, graphene can successfully improve the mechanical property of hard alloy as carbon source.Its mechanism of action is that graphene is film-form substance, and alloy grain during sintering can preferably be inhibited to grow up, and so that hard alloy obtained is had the crystallite dimension and internal structure more evenly more refined, to obtain the higher hard alloy of densification degree.Obtained graphene carbon source WC-Co hard alloy, hardness, densification degree, fracture toughness are all increased dramatically.The present invention can provide a kind of new production technology to prepare high performance WC-Co hard alloy.
Description
Technical field
The present invention relates to a kind of cemented carbide material more particularly to a kind of graphene carbon source WC-Co hard alloys.
Background technique
Hard alloy is by one or more high rigidity, the interstitial compound of high-modulus and magnesium-yttrium-transition metal or its alloy group
At composite material.Since it has the characteristics that high rigidity, wearability, red hardness and obdurability, it is widely used in various cuttings
Tool, mining tool and wear-and corrosion-resistant components.Hard alloy belongs to fragile material, hardness and strength, that is, wearability and toughness it
Between contradiction be always perplex its development principal element.
Graphene (Graphene) is a kind of honeycomb flat film formed by carbon atom with sp2 hybrid form, is one
The quasi- two-dimensional material of only one atomic layer level thickness of kind, does monoatomic layer graphite so being called.Univ Manchester UK's physics
Scholar An Deliegaimu and Constantine's Nuo Woxiao love isolate graphite with micromechanics stripping method success from graphite
Alkene, therefore Nobel Prize in physics in 2010 is obtained jointly.The method of the common power production of graphene is mechanical stripping method, oxygen
Change reduction method, SiC epitaxial growth method, film production method is chemical vapour deposition technique (CVD).Since it is very good strong
Degree, flexible, conductive, thermally conductive, optical characteristics, all in fields such as physics, materialogy, electronic information, computer, aerospaces
Significant progress is arrived.
Summary of the invention
The purpose of the invention is to improve the hardness of WC-Co hard alloy, wearability, a kind of graphene carbon source is devised
WC-Co hard alloy.
The technical solution adopted by the present invention to solve the technical problems is:
The raw material for preparing of graphene carbon source WC-Co hard alloy includes: that diameter is 5 ~ 10 μm and is dispersed in organic solvent N- methyl
Ten layers of graphene in pyrrolidones, the blue tungsten (WO that purity 99.5%, average grain diameter are 50 μm2.9) and purity be 98.5%,
Average grain diameter is 35 μm of cobalt oxide (Co3O4).
The preparation step of graphene carbon source WC-Co hard alloy are as follows: by experimental design weigh graphene, blue tungsten and
Cobalt oxide carries out ingredient, then adds to and carries out ball milling in hard alloy ball grinder, ball-milling medium is ethyl alcohol, and rotational speed of ball-mill is
180r/min, Ball-milling Time are respectively 30,40,50h.Then powder is dried in vacuo, and 850 DEG C at a temperature of carry out
Reduction and carbonization reaction, reaction time 1h.A certain amount of grain growth inhibitor VC is added in the good powder of reduction and carbonization simultaneously
Continue ball milling, Ball-milling Time 10h.Then discharge plasma sintering densification, sintering temperature 1130 are carried out to composite powder
DEG C, keep the temperature 5min, sintering pressure 60MPa.
The detecting step of graphene carbon source WC-Co hard alloy are as follows: material phase analysis uses D/max-3 type X-ray diffractometer,
Fracture toughness uses indentation method, and microstructure uses NovaNanoSEM type field emission scanning electron microscope and Flied emission high score
Resolution transmission electron microscope.
The graphene carbon source WC-Co hard alloy, graphene can successfully improve the power of hard alloy as carbon source
Learn performance.Its mechanism of action is that graphene is film-form substance, and alloy grain during sintering can preferably be inhibited to grow up,
Make hard alloy obtained that there is the crystallite dimension and internal structure more evenly more refined, to obtain densification degree more
High hard alloy.
The graphene carbon source WC-Co hard alloy, graphene can be such that hard alloy obtained has as carbon source
Object phase composition more evenly, compatible degree is preferable between each object phase.Prepared Nanograin Cemented Carbide, object is mutually pure, crystal grain
Fine microstructures, microstructure are evenly distributed.
The graphene carbon source WC-Co hard alloy, because graphene can refine crystal grain, promotion hard conjunction as carbon source
Golden consistency so can make reaction that can carry out at lower temperatures, and improves the efficiency of reaction.Prepared is hard
Matter alloy has good hardness and fracture toughness, Vickers hardness 29.76GPa, fracture toughness 15.37MPam1/2。
Its mechanical property promotes about 20% or more compared with hard alloy prepared by common process.
The beneficial effects of the present invention are:
Using ten layers of graphene, WO2.9And Co3O4For raw material, by ingredient, ball milling, drying, granulation, discharge plasma sintering
Technique is successfully prepared the graphene carbon source WC-Co hard alloy with excellent mechanical performance.Wherein, using graphene as carbon
Source can successfully prepare nanocrystalline WC-Co hard alloy under lower reaction temperature.Obtained graphene carbon source WC-Co
Hard alloy, hardness, densification degree, fracture toughness are all increased dramatically.The present invention can be to prepare high performance WC-
Co hard alloy provides a kind of new production technology.
Specific embodiment
Case study on implementation 1:
The raw material for preparing of graphene carbon source WC-Co hard alloy includes: that diameter is 5 ~ 10 μm and is dispersed in organic solvent N- methyl
Ten layers of graphene in pyrrolidones, the blue tungsten (WO that purity 99.5%, average grain diameter are 50 μm2.9) and purity be 98.5%,
Average grain diameter is 35 μm of cobalt oxide (Co3O4).The preparation step of graphene carbon source WC-Co hard alloy are as follows: press experimental design
It weighs graphene, blue tungsten and cobalt oxide and carries out ingredient, then add to and carry out ball milling in hard alloy ball grinder, ball-milling medium is
Ethyl alcohol, rotational speed of ball-mill 180r/min, Ball-milling Time are respectively 30,40,50h.Then powder is dried in vacuo, and
Reduction and carbonization reaction, reaction time 1h are carried out at a temperature of 850 DEG C.A certain amount of crystalline substance is added in the good powder of reduction and carbonization
The big inhibitor VC of grain length simultaneously continues ball milling, Ball-milling Time 10h.Then it is fine and close discharge plasma sintering to be carried out to composite powder
Change, sintering temperature is 1130 DEG C, keeps the temperature 5min, sintering pressure 60MPa.The detection of graphene carbon source WC-Co hard alloy walks
Suddenly are as follows: material phase analysis uses D/max-3 type X-ray diffractometer, and fracture toughness uses indentation method, and microstructure uses
NovaNanoSEM type field emission scanning electron microscope and Flied emission high resolution TEM.
Case study on implementation 2:
Using WC as main phase, cobalt oxide and tungsten oxide are reduced completely and are carbonized as WC and scarce carbon phase composite powder.Lack carbon phase
And the presence of free graphene can be such that reaction temperature reduces, and effectively inhibit the size of WC grain during the reaction because anti-
It answers temperature high and grows up.It is further reacted in subsequent sintering process, scarce carbon phase and free graphite alkene can be eliminated.It is lower anti-
The crystal grain for answering temperature not only to inhibit WC in composite powder is grown up, and energy consumption is effectively reduced, and shortens the system of powder and hard alloy
In the standby period, improve production efficiency.
Case study on implementation 3:
In ball milling 42h, there is part graphene film not to be crushed well, maintains original laminar structured.Due to
During reaction, the tungsten-cobalt oxide around graphene film can not completely be consumed this graphene film, there is the stone of part
Black alkene lamella residual.When increasing Ball-milling Time and arriving 60h, the graphene presence of sheet substantially in composite powder.When ball milling
Between when increasing to 90h, it is already possible to obtain the composite powder of particle fine uniform.With further increasing for Ball-milling Time,
Grain refinement is unobvious.The average particle size particle size of composite powder particle when reacting more abundant is about 173nm, particle diameter distribution
Very narrow, particle size distribution is uniform in powder.
Case study on implementation 4:
Sintered block only has WC, Co two-phase, and object is mutually pure.The a small amount of graphene occurred and scarce carbon phase are during sintering
Secondary complete reduction and carbonization reaction has been carried out, free graphite alkene and scarce carbon phase had not only been eliminated under the pressure of 110MPa, but also very
Growing up for crystallite dimension is controlled well, and available object is mutually pure, the tiny WC-12Co hard alloy block of crystal grain.Sintering
Block compactness is preferable, and grain size distribution is uniform, and crystal grain is tiny, and do not note abnormalities long big crystal grain.WC average crystal grain ruler
Very little about 218nm, particle diameter distribution is relatively narrow, and crystallite dimension is mainly distributed on 260nm hereinafter, it is with good hardness, toughness group
It closes.
Case study on implementation 5:
For material during stress deformation, good interface orientation relationship can effectively hinder dislocation motion, have and common crystal boundary
Similar invigoration effect can be effectively reduced intercrystalline interface energy, enhance to the maximum extent hard in WC-Co hard alloy
Bond strength between matter phase and Binder Phase makes the framework of entire material have optimal mechanical property.
Case study on implementation 6:
Complete coherent grain boundary orientation is presented between WC grain, crystal boundary has the characteristics that minimum energy, existence are most stable of,
The fracture that just deforms after outside energy can be absorbed when by stress to the maximum extent, the crystal boundary of such bonding state also has
Preferable mechanical property can increase the hardness, toughness and intensity of material.
Case study on implementation 7:
The graphene contacted with WC grain have extraordinary flexibility, in interface the distortion of atom form in WC grain
The higher matching of atom, WC grain atom does not strain substantially, and atomic arrangement is significantly bent in graphene
And deformation, but still maintain the ordered arrangement of atom.It can be seen that graphene can play the role of absorbing stress in alloy.Graphene
By self-deformation and not broken, extraneous work done can be offset, the extension of dislocation crack can also be prevented well, protected
The integrality of WC grain, collaboration Binder Phase jointly improve the intensity of alloy.
Claims (4)
1. a kind of graphene carbon source WC-Co hard alloy, preparing raw material includes: that diameter is 5 ~ 10 μm and is dispersed in organic solvent N-
Ten layers of graphene in methyl pyrrolidone, the blue tungsten (WO that purity 99.5%, average grain diameter are 50 μm2.9) and purity be
98.5%, average grain diameter is 35 μm of cobalt oxide (Co3O4).
2. graphene carbon source WC-Co hard alloy according to claim 1, it is characterized in that graphene carbon source WC-Co hard
The preparation step of alloy are as follows: weigh graphene, blue tungsten and cobalt oxide by experimental design and carry out ingredient, then add to hard
Carry out ball milling in alloy ball grinder, ball-milling medium is ethyl alcohol, rotational speed of ball-mill 180r/min, Ball-milling Time is respectively 30,40,
Then powder is dried in vacuo by 50h, and 850 DEG C at a temperature of carry out reduction and carbonization reaction, reaction time 1h,
A certain amount of grain growth inhibitor VC is added in the good powder of reduction and carbonization and continues ball milling, Ball-milling Time 10h is then right
Composite powder carries out discharge plasma sintering densification, and sintering temperature is 1130 DEG C, keeps the temperature 5min, sintering pressure 60Mpa.
3. graphene carbon source WC-Co hard alloy according to claim 1, it is characterized in that graphene carbon source WC-Co hard
The detecting step of alloy are as follows: material phase analysis uses D/max-3 type X-ray diffractometer, and fracture toughness uses indentation method, microstructure
Using NovaNanoSEM type field emission scanning electron microscope and Flied emission high resolution TEM.
4. graphene carbon source WC-Co hard alloy according to claim 1, it is characterized in that the graphene carbon source WC-
Co hard alloy, graphene can successfully improve the mechanical property of hard alloy as carbon source, and the mechanism of action is that graphene is
Film-form substance can preferably inhibit alloy grain during sintering to grow up, and have hard alloy obtained more thin
The crystallite dimension of change and internal structure more evenly, to obtain the higher hard alloy of densification degree, the graphene
Carbon source WC-Co hard alloy, graphene can make hard alloy obtained with object phase composition more evenly, each object as carbon source
Compatible degree is preferable between phase, and prepared Nanograin Cemented Carbide, object is mutually pure, and grain structure is tiny, microstructure distribution
Uniformly, the graphene carbon source WC-Co hard alloy, because graphene can refine crystal grain, promotion hard alloy as carbon source
Consistency so can make reaction that can carry out at lower temperatures, and improves the efficiency of reaction, prepared hard
Alloy has good hardness and fracture toughness, Vickers hardness 29.76GPa, fracture toughness 15.37MPam1/2,
Mechanical property promotes about 20% or more compared with hard alloy prepared by common process.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710948774.0A CN109652671A (en) | 2017-10-12 | 2017-10-12 | A kind of graphene carbon source WC-Co hard alloy |
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| CN201710948774.0A CN109652671A (en) | 2017-10-12 | 2017-10-12 | A kind of graphene carbon source WC-Co hard alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453107A (en) * | 2019-08-01 | 2019-11-15 | 天津大学 | Preparation method of graphene-tungsten carbide synergistically reinforced copper matrix composites |
| CN110527891A (en) * | 2019-09-16 | 2019-12-03 | 东华大学 | Hard alloy in low cobalt surface diamond coating and preparation method thereof |
| CN114277298A (en) * | 2020-09-27 | 2022-04-05 | 四川大学 | A kind of WC-Co cemented carbide added with graphene/nano Al2O3 particles and preparation method thereof |
-
2017
- 2017-10-12 CN CN201710948774.0A patent/CN109652671A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110453107A (en) * | 2019-08-01 | 2019-11-15 | 天津大学 | Preparation method of graphene-tungsten carbide synergistically reinforced copper matrix composites |
| CN110453107B (en) * | 2019-08-01 | 2021-01-05 | 天津大学 | Preparation method of graphene-tungsten carbide synergistically reinforced copper matrix composites |
| CN110527891A (en) * | 2019-09-16 | 2019-12-03 | 东华大学 | Hard alloy in low cobalt surface diamond coating and preparation method thereof |
| CN110527891B (en) * | 2019-09-16 | 2021-11-02 | 东华大学 | Diamond coating on the surface of low cobalt cemented carbide and preparation method thereof |
| CN114277298A (en) * | 2020-09-27 | 2022-04-05 | 四川大学 | A kind of WC-Co cemented carbide added with graphene/nano Al2O3 particles and preparation method thereof |
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Application publication date: 20190419 |