CN1888104A - Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy - Google Patents
Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy Download PDFInfo
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- CN1888104A CN1888104A CN 200610089744 CN200610089744A CN1888104A CN 1888104 A CN1888104 A CN 1888104A CN 200610089744 CN200610089744 CN 200610089744 CN 200610089744 A CN200610089744 A CN 200610089744A CN 1888104 A CN1888104 A CN 1888104A
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- 238000000034 method Methods 0.000 title abstract description 8
- 229910000531 Co alloy Inorganic materials 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 44
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 238000000498 ball milling Methods 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 238000000280 densification Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract 2
- 238000011049 filling Methods 0.000 abstract 1
- 238000004663 powder metallurgy Methods 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 30
- 238000000227 grinding Methods 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910009043 WC-Co Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
The preparation process of high performance superfine crystalline hard WC-10wt%Co alloy belongs to the field of powder metallurgy technology. The preparation process includes the following steps: ball milling pure Co powder of 30-60 micron size under Ar protection for over 16 hr to obtain micron level Co powder with nanometer crystal structure; mixing 0.2 micron size WC powder and the Co powder in the weight ratio of 9, ball milling the mixture in anhydrous ethanol for 20-24, vacuum drying to obtain mixture powder, filling into mold and cold pressing to form; and sintering in a discharging plasma sintering apparatus. The technological process is simple, and prepared WC-10wt%Co alloy has high performance.
Description
Technical field
A kind of high-performance superfine WC-Co cemented carbide preparation methods belongs to powder metallurgical technology.
Background technology
Traditional coarse-grain WC-Co Hardmetal materials, its hardness and toughness are the contradiction of a pair of mutual restriction always.Recent study finds, when the WC grain yardstick drops to 0.5 μ m when following, the hardness of Hardmetal materials and fracture toughness property can keep high value simultaneously.Among the preparation method of existing Hardmetal materials, as at traditional hot pressing agglomerating shortcoming and methods such as improved HIP sintering, ultra-high pressure sintering and Rapid Thermal isostatic sinterings, though reduced sintering temperature to a certain extent and shortened sintering time, but still need be incubated several usually to tens hours, cause WC grain to be grown up inevitably, generally can only obtain the fine grained cemented carbide material of grain-size 1.0～0.5 μ m.
Summary of the invention
The invention provides the preparation method of a kind of ultra-fine brilliant WC-10wt.%Co (YG10) Hardmetal materials.By coupling of the particle diameter between design and optimizing materials powder and bonding state, use discharge plasma sintering (SPS) technology in recent years develop rapidly, utilize simple procedures to synthesize grain-size fast less than 250 nanometers, superfine WC-Co cemented carbide material with high hardness and fracture toughness property.This preparation method there is no report at present both at home and abroad.
The preparation method of the ultra-fine brilliant WC-10wt.%Co Wimet of high-performance provided by the invention is characterized in that, may further comprise the steps:
1) with particle diameter be the pure Co powder of 30-60 micron at ball milling under the argon shield more than 16 hours, obtain the micron order particle diameter but Co powder with nanocrystalline microstructure;
2) WC powder and the Co powder behind the ball milling with 0.2 micron of average particle size carries out mixing and ball milling by mass ratio at 9: 1, ball-milling medium is a dehydrated alcohol, ball milling 20-24 hour, and the mixed powder that the obtains mould of in vacuum drying oven, packing into after the drying, coldmoulding is sent in the SPS equipment;
3) adopt following processing parameter to carry out sintering densification: 1120 ℃-1150 ℃ of final state sintering temperatures, temperature rise rate 80-120 ℃/min, sintering pressure 30-60MPa, soaking time 0-10min under the final state sintering temperature.
To be the mechanism of the SPS technology discovered according to us and raw material particle size coupling and bonding state propose the Hardmetal materials tissue and the Effect on Performance of preparation in the present invention.Utilize the micron order Co powder that has nanocrystalline microstructure behind submicron WC powder and the ball milling as raw material powder, after mixing and ball milling, obtain the two-phase powder bonding state that Co coats WC particle.When carrying out the SPS sintering subsequently, thereby the pulsed current major part makes powder particle by the quick and even heating of self joule effect realization by composite powder, has significantly improved WC particle, shortcomings such as temperature rise inhomogeneous, material property instability low because of the sintering efficient that bad electroconductibility causes.The WC-10wt.%Co Hardmetal materials of preparing has high density, less than the ultra fine grain size of 250 nanometers, excellent hardness and fracture toughness property over-all properties.This method technology is simple, and the technical parameter controllability is strong, and the material property of preparation reaches the international most advanced level of present same material.
Description of drawings
The pattern of Co powder particle (electron scanning micrograph) behind the ball milling among Fig. 1 embodiment 1.
Co granule interior nanocrystal tissue and selected area electron diffraction thereof spectrum (transmission electron microscope photo) behind the ball milling among Fig. 2 embodiment 1.
WC that obtains after the mixing and ball milling among Fig. 3 embodiment 1 and Co composite powder (high resolution scanning electron microscope photo).
The fracture apperance figure (high resolution scanning electron microscope photo) of Fig. 4 embodiment 1 final ultra-fine brilliant WC-10wt.%Co Hardmetal materials that obtains.
The fracture apperance figure (high resolution scanning electron microscope photo) of Fig. 5 embodiment 2 final ultra-fine brilliant WC-10wt.%Co Hardmetal materials that obtain.
The fracture apperance figure (high resolution scanning electron microscope photo) of Fig. 6 embodiment 3 final ultra-fine brilliant WC-10wt.%Co Hardmetal materials that obtain.
Embodiment
The median size of initial WC powder is 0.2 micron (being produced by Xiamen Jin Lu company) among all embodiment, and the median size of Co powder is about 30-60 micron (being produced by non-ferrous metal research institute).Use the homogeneous raw material powder, the WC-10wt.%Co Hardmetal materials that adopts existing hot pressed sintering and HIP sintering to prepare, its grain-size is generally greater than 0.5 micron, and hardness value is HRA 90-92, and fracture toughness property is 7-10MPa m
1/2And the average grain size of the WC-10wt.%Co Hardmetal materials of the present invention preparation is less than 250 nanometers, and hardness and fracture toughness property all obviously improve.
Example 1, elder generation carry out ball milling with the Co powder, and ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 500r/min, and the ball milling time is 20 hours, adopt argon shield.Obtain median size and be 16 microns and Co powder (as Fig. 1 and Fig. 2) with nanocrystalline microstructure.Then 0.2 micron WC powder and the Co powder behind the ball milling carried out mixing and ball milling by mass ratio at 9: 1, ratio of grinding media to material is 3: 1, and rotational speed of ball-mill is 300r/min, and the ball milling time is 24 hours, and ball-milling medium is a dehydrated alcohol.Mixed powder behind the ball milling is to obtain being used for agglomerating initial powder (as Fig. 3) after dry 24 hours in 100 ℃ the vacuum drying oven at design temperature.With this powder graphite jig of packing into, extrusion forming.Send into the vacuum sintering chamber of SPS system.Sintering process parameter is: 1120 ℃ of sintering temperatures; 120 ℃/min of sintering temperature rise rate; The sintering initial stage does not pressurize, and applies 60MPa pressure and keep this pressure when peak value appears in the change in displacement rate curve of sintered compact; When reaching sintering temperature, be not incubated.Obtain ultra-fine brilliant YG10 Wimet block material (microstructure is seen Fig. 4, and material property parameter sees Table 1) by above-mentioned prepared.
Example 2, elder generation carry out ball milling with the Co powder, and ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 600r/min, and the ball milling time is 16 hours, adopt argon shield.Obtain median size and be 22 microns and Co powder with nanocrystalline microstructure.Then 0.2 micron WC powder and the Co powder behind the ball milling carried out mixing and ball milling by mass ratio at 9: 1, ratio of grinding media to material is 3: 1, and rotational speed of ball-mill is 400r/min, and the ball milling time is 20 hours, and ball-milling medium is a dehydrated alcohol.Mixed powder behind the ball milling is to obtain being used for the agglomerating initial powder after dry 24 hours in 100 ℃ the vacuum drying oven at design temperature.With this powder graphite jig of packing into, extrusion forming.Send into the vacuum sintering chamber of SPS system.Sintering process parameter is: 1150 ℃ of sintering temperatures; 100 ℃/min of sintering temperature rise rate; The sintering initial stage does not pressurize, and applies 30MPa pressure when peak value appears in sintered compact change in displacement rate curve, applies 60MPa pressure when the change in displacement rate returns to zero; After reaching sintering temperature, be incubated 5min.Obtain ultra-fine cemented carbide block materials (microstructure is seen Fig. 5, and material property parameter sees Table 1) by above-mentioned prepared.
Example 3, elder generation carry out ball milling with the Co powder, and ratio of grinding media to material is 10: 1, and rotational speed of ball-mill is 500r/min, and the ball milling time is 24 hours, adopt argon shield.Obtain median size and be 14 microns and Co powder with nanocrystalline microstructure.Then 0.2 micron WC powder and the Co powder behind the ball milling carried out mixing and ball milling by mass ratio at 9: 1, ratio of grinding media to material is 3: 1, and rotational speed of ball-mill is 300r/min, and the ball milling time is 24 hours, and ball-milling medium is a dehydrated alcohol.Mixed powder behind the ball milling is to obtain being used for the agglomerating initial powder after dry 24 hours in 100 ℃ the vacuum drying oven at design temperature.With this powder graphite jig of packing into, extrusion forming.Send into the vacuum sintering chamber of SPS system.Sintering process parameter is: 1150 ℃ of sintering temperatures; The about 80 ℃/min of sintering temperature rise rate; The sintering initial stage does not pressurize, and applies 30MPa pressure when peak value appears in sintered compact change in displacement rate, applies 60MPa pressure when the change in displacement rate returns to zero; After reaching sintering temperature, be incubated 10min.Obtain ultra-fine cemented carbide block materials (microstructure is seen Fig. 6, and material property parameter sees Table 1) by above-mentioned prepared.
The performance perameter of ultra-fine brilliant YG10 (WC-10Co) Hardmetal materials of the different embodiment preparations of table 1
Claims (1)
1, the preparation method of the ultra-fine brilliant WC-10wt.%Co Wimet of a kind of high-performance is characterized in that, may further comprise the steps:
1) with particle diameter be the pure Co powder of 30-60 micron at ball milling under the argon shield more than 16 hours, obtain the micron order particle diameter but Co powder with nanocrystalline microstructure;
2) be that 0.2 micron WC powder and the Co powder behind the above-mentioned ball milling carries out mixing and ball milling by mass ratio at 9: 1 with average particle size, ball-milling medium is a dehydrated alcohol, the ball milling time is 20-24 hour, the mixed powder that the obtains mould of in vacuum drying oven, packing into after the drying, coldmoulding is sent into and is prepared sintering in the discharging plasma sintering equipment;
3) adopt following processing parameter to carry out sintering densification: 1120-1150 ℃ of final state sintering temperature, temperature rise rate 80-120 ℃/min, sintering pressure 30-60MPa, soaking time 0-10min under the final state sintering temperature.
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| CNB2006100897440A CN100390312C (en) | 2006-07-14 | 2006-07-14 | Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy |
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| CNB2006100897440A CN100390312C (en) | 2006-07-14 | 2006-07-14 | Prepn process of high-performance superfine crystal hard WC-10 wt.% Co alloy |
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| CN100390312C CN100390312C (en) | 2008-05-28 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572579C (en) * | 2008-04-21 | 2009-12-23 | 宜兴市甲有硬质合金制品厂 | The manufacture method of major diameter hard alloy metal trombone die |
| CN101265531B (en) * | 2007-03-13 | 2010-12-01 | 四川理工学院 | Method for producing granule structure hard alloy with multiple groups of different components |
| CN101624673B (en) * | 2009-08-14 | 2011-01-05 | 北京工业大学 | Industrialized preparation method of WC-Co hard alloy with low cost and high performance |
| CN102628138A (en) * | 2012-03-23 | 2012-08-08 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN105331842A (en) * | 2015-11-05 | 2016-02-17 | 江苏和田科技材料有限公司 | Manufacturing method for hard tungsten carbide-cobalt alloy material |
| CN106810236A (en) * | 2017-01-22 | 2017-06-09 | 苏州新锐合金工具股份有限公司 | A kind of preparation method of Ultra-fine Grained (Ti, Mo, W) (C, N) composite solid solution powder |
| CN106834778A (en) * | 2017-01-03 | 2017-06-13 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN108411137A (en) * | 2018-04-10 | 2018-08-17 | 南京理工大学 | The preparation method of Ultra-fine Grained tungsten carbide base carbide alloy |
| CN115679142A (en) * | 2022-10-26 | 2023-02-03 | 兰溪泛翌精细陶瓷有限公司 | Sintering method of submicron tungsten carbide ceramic |
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| CN1234894C (en) * | 2003-09-04 | 2006-01-04 | 株洲硬质合金集团有限公司 | Prepn of hard W-Co alloy |
| CN1749422A (en) * | 2005-09-30 | 2006-03-22 | 北京工业大学 | In-situ synthetic method for WC-Co hard alloy |
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2006
- 2006-07-14 CN CNB2006100897440A patent/CN100390312C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265531B (en) * | 2007-03-13 | 2010-12-01 | 四川理工学院 | Method for producing granule structure hard alloy with multiple groups of different components |
| CN100572579C (en) * | 2008-04-21 | 2009-12-23 | 宜兴市甲有硬质合金制品厂 | The manufacture method of major diameter hard alloy metal trombone die |
| CN101624673B (en) * | 2009-08-14 | 2011-01-05 | 北京工业大学 | Industrialized preparation method of WC-Co hard alloy with low cost and high performance |
| CN102628138A (en) * | 2012-03-23 | 2012-08-08 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN102628138B (en) * | 2012-03-23 | 2013-10-30 | 华南理工大学 | Trace cobalt-containing tungsten carbide without bonding phase and preparation method thereof |
| CN105331842A (en) * | 2015-11-05 | 2016-02-17 | 江苏和田科技材料有限公司 | Manufacturing method for hard tungsten carbide-cobalt alloy material |
| CN106834778A (en) * | 2017-01-03 | 2017-06-13 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN106834778B (en) * | 2017-01-03 | 2018-09-28 | 崇义恒毅陶瓷复合材料有限公司 | Hard alloy and preparation method |
| CN106810236A (en) * | 2017-01-22 | 2017-06-09 | 苏州新锐合金工具股份有限公司 | A kind of preparation method of Ultra-fine Grained (Ti, Mo, W) (C, N) composite solid solution powder |
| CN106810236B (en) * | 2017-01-22 | 2020-03-27 | 苏州新锐合金工具股份有限公司 | Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder |
| CN108411137A (en) * | 2018-04-10 | 2018-08-17 | 南京理工大学 | The preparation method of Ultra-fine Grained tungsten carbide base carbide alloy |
| CN115679142A (en) * | 2022-10-26 | 2023-02-03 | 兰溪泛翌精细陶瓷有限公司 | Sintering method of submicron tungsten carbide ceramic |
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| CN100390312C (en) | 2008-05-28 |
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