CN102220534B - Method for reinforcing binder phase of hard alloy - Google Patents
Method for reinforcing binder phase of hard alloy Download PDFInfo
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- CN102220534B CN102220534B CN2011102033858A CN201110203385A CN102220534B CN 102220534 B CN102220534 B CN 102220534B CN 2011102033858 A CN2011102033858 A CN 2011102033858A CN 201110203385 A CN201110203385 A CN 201110203385A CN 102220534 B CN102220534 B CN 102220534B
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Abstract
The invention discloses a method for reinforcing the binder phase of a hard alloy, which is to allow the binder phase of the alloy to produce a nano disperse phase reinforcing effect by adding Cr3C2 in an amount which is 3 to 5 percent based on the mass of Co or Co and Ni in the alloy and Ln (rare earth) in an amount which is 0.3 to 0.5 percent based on the mass of the Co or Co and Ni in the alloy in the preparation process of the mixed material of a WC-Co or WC-Co-Ni hard alloy and performing integrated subsequence treatment including super solid-phase linear quenching heat treatment, liquid nitrogen deep treatment at -180 to -190 DEG C and medium-temperature tempering treat method at 400 to 450 DEG C, so that the modulus of elasticity and hardness of the binder phase of the alloy as well as the comprehensive performance of the hard alloy can be improved.
Description
Technical field
The present invention relates to a kind of wimet improvement in performance, especially ultra coarse-grain wimet improvement in performance method, particularly a kind of wimet bonding phase performance is improved one's methods.
Background technology
Wimet is produced with powder metallurgy process; Form by refractory metal compound (WC, TiC, TaC, NbC etc.) and matrix metal (Co, Ni, Fe etc.); Has hard phase+bonding phase constitution constitutional features; Engineered composite material with suitable strength, hardness and toughness matching, the sosoloid bonding is called for short the bonding phase mutually in the alloy, and the mean grain size of hard phase is called for short the alloy grain degree in the alloy.Alloy phase ratio with bonding grain fineness number＜5.0 μ m that massfraction is suitable mutually; The ultra coarse-grain wimet of alloy grain degree >=5.0 μ m has high thermal, higher fracture toughness property, higher heat shock resistance and thermal fatigue resistance; The working continuously of the continuous exploitation (like coal mining, subway and tunnel construction) that is mainly used in soft rock under the extreme operating condition condition and modern highway, bridge (like road breaking, pave the way), the punching die that toughness and thermal fatigue resistance, thermal shock resistance are had relatively high expectations, cold heading die, roll etc.The mfp of bonding phase in the ultra coarse-grain wimet (mean thickness of bonding phase thin layer) is bigger; Compare with the wimet of traditional grain fineness number; The hardness and wear resistance of bonding phase can have a strong impact on the wear resistance and the work-ing life of ultra coarse-grain alloy; Therefore must strengthen the bonding phase in the ultra coarse-grain wimet, to improve the over-all properties of ultra coarse-grain wimet.
About the thermal treatment of wimet and the existing patent report of sub-zero treatment (Guo Zhixing, the bear meter, Chen Jianzhong, etc. a kind of preparation method .CN101397615,2009-04-01 with nearly equiaxed WC grain hard alloy.Guo Zhixing, the bear meter, Chen Jianzhong, etc. a kind of preparation method .CN101397614 of Ni cementing WC base cemented carbide, 2009-04-01.Hu Ming. a kind of double metal saw belt and wimet very low temperature treatment process .CN1401796,2003-03-12).Report about the sintering cemented carbide subsequent disposal mainly is single thermal treatment or single sub-zero treatment at present.Present inventor's early-stage Study result shows that thermal treatment and cryogenic treatment process parameter directly influence the strengthening effect of wimet; Wimet behind the sintering is comprised ultra solidus curve quenching heat treatment, the integrated subsequent disposal that liquid nitrogen deep is handled and average tempering is handled, the improved combination properties best results of alloy successively; Pure WC-Co or pure WC-Co-Ni wimet are carried out above-mentioned integrated subsequent disposal, can not form the disperse phase strengthening effect in mutually at alloy bonding.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of ability efficient hardening wimet bonding phase.
In order to solve the problems of the technologies described above, the method for enhancing hard alloy bonding phase provided by the invention accounts for the Cr that Co in the alloy or Co+Ni massfraction are respectively 3wt%～5wt% through preparing at WC-Co or WC-Co-Ni carbide alloy mixture to unite in the process to add
3C
2Ln (rare earth) with 0.3wt%～0.5wt%; Simultaneously the sintered state alloy is comprised ultra solidus curve quenching heat treatment, the integrated subsequent disposal that liquid nitrogen deep is handled and average tempering is handled, with the purpose that realizes the Ni-based sosoloid bonding of cobalt-based or cobalt in WC-Co or the WC-Co-Ni wimet is strengthened mutually.Ln adds with Ln-Co pre-alloyed powder form or with oxide form in the alloy, and addition is with oxide compound when adding in oxide form.Ultra solidus curve quenching heat treatment is meant the sintered state alloy at vacuum or H
2In the atmosphere, be heated to 1360 ℃～1400 ℃, promptly be heated to the temperature between alloy liquid phase sintering temperature and alloy liquid phase appearance temperature (eutectic temperature), quench behind insulation 40min～50min.The liquid nitrogen deep processing is meant quenching attitude alloy is incubated 8h～14h in-180 ℃～-190 ℃ liquid nitrogen.Average tempering is meant sub-zero treatment attitude alloy at vacuum or H
2Or N
2In the atmosphere, be heated to 400 ℃～450 ℃, insulation 5h～10h.Alloy bonding is strengthened mutually and is meant through Cr
3C
2The above-mentioned integrated subsequent disposal that adds with the sintered state alloy of uniting with Ln; Form the disperse phase of the about 3nm of median size in mutually at alloy bonding; Improve the Young's modulus and the hardness of alloy bonding property through the dispersion-strengthened effect; Improve wimet thereby reach, especially the purpose of the alloy grain degree>=ultra coarse-grain wimet of 5 μ m over-all properties.
The present invention bonding mutually in the ultimate principle that forms mutually of nano-diffusion be, utilize the solid solution cooperative behavior of Cr-W-Ln-C in Co or Co+Ni, change the character of sosoloid bonding phase, thereby cause (W, Cr)
xCo
yC or (W, Cr)
x(Co, Ni)
yThe remarkable reduction of C compound formation free energy; Make in the alloy sosoloid bonding be in hypersaturated state mutually through thermal treatment and follow-up sub-zero treatment; Handle through average tempering, be present in Cr, W, Ln, C, Co or Cr, W, Ln, C, Co, Ni atom short range diffusion reorganization rapidly in Co or the Co+Ni matrix, form a large amount of (W, Cr)
xCo
yC or (W, Cr)
x(Co, Ni)
yThe C nucleus; Because WC hard and Co or the Co+Ni based solid solution significant difference of (alloy bonding phase) thermal expansivity mutually that bonds in the alloy; Cause alloy bonding to receive big action of pulling stress mutually; Under tensile stress constraint short range diffusional environment, alloy bonding mutually in formation nano-diffusion phase.
In sum, the present invention is the method for the ultra coarse-grain wimet bonding of a kind of efficient hardening wimet bonding phase, especially efficient hardening phase.
Description of drawings
Fig. 1 is that the alloy grain degree is the WC-8.5Co-0.255Cr of 11 μ m
3C
2The microtexture photo of-0.0425La alloy;
Fig. 2 is that the alloy grain degree is the WC-8.5Co-0.255Cr of 11 μ m
3C
2The high-resolution-ration transmission electric-lens photo of-0.0425La alloy bonding phase, magnification are 300,000 times;
Fig. 3 is that the alloy grain degree is the WC-4.25Co-4.25Ni-0.35Cr of 3 μ m
3C
2-0.035CeO
2The high-resolution-ration transmission electric-lens photo of alloy bonding phase, magnification are 600,000 times.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment 1:
Adopting Fisher particle size is that 34.1 μ m, total carbon are the WC powder of 6.14wt%, and Fisher particle size is that 1.02 μ m, total carbon are the Cr of 13.26wt%
3C
2Powder ,-200 order La-65wt%Co prealloy powder are raw material, adopt chemical coating method and auxiliary wet-grinding technology and relative device to prepare WC-8.5wt%Co-0.255wt%Cr
3C
2-0.0425wt%La (rare earth) compound.The sintering of alloy carries out in pressure sintering furnace, and sintering temperature is 1450 ℃, and soaking time is 90min, and furnace pressure is 5.6MPa during sintered heat insulating.The metallurgical structure observations shows that alloy is two phase alloys, does not have decarburization phase or carburizing phase in the alloy, and the grain fineness number of alloy is 11 μ m.The sintered state alloy is heated to 1360 ℃ in the double-chamber vacuum heat treatment furnace, insulation 50min, product is transferred to quenching chamber by Vakuumkammer, and product is carried out N
2Quench.Quenching attitude alloy is incubated 8h in-190 ℃ liquid nitrogen.With sub-zero treatment attitude alloy at H
2In 430 ℃ of temperature, be incubated 7h in the atmosphere.
Adopt high-resolution-ration transmission electric-lens to observe the heterogeneous microstructure of alloy bonding phase.Adopt the ultra nano-hardness tester of CSM to measure the vickers hardness hv of alloy bonding under 2mN load
2mNWith Young's modulus (EIT), measure dot number is 10.The alloy microtexture photo that ultra nano-hardness tester is taken is seen Fig. 1, and light tone is the bonding phase mutually among the figure, and between the bonding phase is WC hard phase.Magnification is that the high-resolution-ration transmission electric-lens photo of 300,000 times of following alloy bonding phases is seen Fig. 2.The dark color of the about 3nm of equally distributed median size is disperse phase mutually among the figure.Original sintered state that the nano impress method records and alloy bonding average HV mutually under integrated subsequent disposal (the being called for short integrated subsequent disposal attitude) two states that comprises ultra solidus curve quenching heat treatment, liquid nitrogen deep processing and average tempering processing
2mNSee table 1 with average EIT.Can know the HV of alloy bonding phase after integrated subsequent disposal by table 1
2mNImproved 11.63% and 13.28% respectively with EIT.
Original sintered state of table 1 and integrated subsequent disposal attitude WC-8.5Co-0.255Cr
3C
2The HV of-0.0425La alloy bonding phase
2mNWith EIT
Embodiment 2:
Adopting Fisher particle size is that 34.1 μ m, total carbon are the WC powder of 6.14wt%, and Fisher particle size is that 1.02 μ m, total carbon are the Cr of 13.26wt%
3C
2Powder, specific surface area average diameter are the Y of 67.2nm
2O
3(rare earth) is raw material, adopts chemical coating method and auxiliary wet-grinding technology and relative device to prepare WC-4.25wt%Co-4.25wt%Ni-0.425wt%Cr
3C
2-0.0255wt%Y
2O
3Compound.The sintering of alloy carries out in pressure sintering furnace, and sintering temperature is 1450 ℃, and soaking time is 90min, and furnace pressure is 5.6MPa during sintered heat insulating.The metallurgical structure observations shows that alloy is two phase alloys, does not have decarburization phase or carburizing phase in the alloy, and the grain fineness number of alloy is 9.5 μ m.The sintered state alloy placed carbon containing Al is housed
2O
3In the graphite boat of filler, in molybdenum wire furnace in H
2Be heated to 1400 ℃ under the atmosphere, be pushed into colling end rapidly behind the insulation 40min and quench.Quenching attitude alloy is incubated 14h in-180 ℃ liquid nitrogen.Sub-zero treatment attitude alloy in a vacuum in 450 temperature, is incubated 5h.
Adopt the ultra nano-hardness tester of CSM to measure the HV of alloy bonding phase
2mNWith EIT, measure dot number is 10.Alloy bonding average HV mutually under the original sintered state that the nano impress method records and the integrated subsequent disposal attitude two states
2mNSee table 2 with average EIT.Can know the HV of alloy bonding phase after subsequent disposal by table 2
2mNImproved 13.19% and 13.18% respectively with EIT.
Original sintered state of table 2 and integrated subsequent disposal attitude
WC-4.25Co-4.25Ni-0.425Cr
3C
2-0.0255Y
2O
3The HV of alloy bonding phase
2mNWith EIT
Embodiment 3:
Adopting Fisher particle size is that 10.0 μ m, total carbon are the WC powder of 6.14wt%, and Fisher particle size is Co powder and the Ni powder of 1.5 μ m, and Fisher particle size is that 1.02 μ m, total carbon are the Cr of 13.26wt%
3C
2Powder, specific surface area average diameter are the CeO of 60.2nm
2(rare earth) is raw material, adopts the conventional wet grinding process to prepare WC-4.25wt%Co-4.25wt%Ni-0.35wt%Cr
3C
2-0.035wt%CeO
2Compound.The sintering of alloy carries out in pressure sintering furnace, and sintering temperature is 1450 ℃, and soaking time is 90min, and furnace pressure is 5.6MPa during sintered heat insulating.The metallurgical structure observations shows that alloy is two phase alloys, does not have decarburization phase or carburizing phase in the alloy, and the grain fineness number of alloy is 2.4 μ m.The sintered state alloy placed carbon containing Al is housed
2O
3In the graphite boat of filler, in molybdenum wire furnace in H
2Be heated to 1380 ℃ under the atmosphere, be pushed into colling end rapidly behind the insulation 45min and quench.Quenching attitude alloy is incubated 11h in-185 ℃ liquid nitrogen.With sub-zero treatment attitude alloy at N
2In in 400 ℃ of temperature, the insulation 10h.
Adopt high-resolution-ration transmission electric-lens to observe the heterogeneous microstructure of alloy bonding phase.Magnification is that the high-resolution-ration transmission electric-lens photo of 600,000 times alloy bonding phases is seen Fig. 3.The dark color of the about 3nm of equally distributed median size is disperse phase mutually among the figure.Receive the restriction of pressure head size, ultra nano-hardness tester brale be difficult to alloy bonding mutually in accurate location, the nano impress method is difficult to accurately to measure the bond correlated performance of phase of alloy grain degree＜5 μ m, the less wimet of bonding phase average free path.Therefore this combination gold does not have the HV of alloy bonding phase
2mNWith the EIT data.
Claims (2)
1. the method for enhancing hard alloy bonding phase is characterized in that: prepare to unite in the process to add at WC-Co or WC-Co-Ni carbide alloy mixture and account for the Cr that Co in the alloy or Co+Ni massfraction are respectively 3wt%～5wt%
3C
2Ln with 0.3wt%～0.5wt%; Described Ln is a rare earth; Simultaneously the sintered state alloy is comprised ultra solidus curve quenching heat treatment, the integrated subsequent disposal that liquid nitrogen deep is handled and average tempering is handled, described ultra solidus curve quenching heat treatment is meant the sintered state alloy at vacuum or H
2In the atmosphere, be heated to 1360 ℃～1400 ℃, quench behind insulation 40min～50min; Described liquid nitrogen deep processing is meant quenching attitude alloy is incubated 8h～14h in-180 ℃～-190 ℃ liquid nitrogen; Described average tempering is meant sub-zero treatment attitude alloy at vacuum or H
2Or N
2In the atmosphere, be heated to 400 ℃～450 ℃, insulation 5h～10h.
2. the method for enhancing hard alloy bonding phase according to claim 1 is characterized in that: described Ln adds with Ln-Co pre-alloyed powder form or with oxide form, and addition is with oxide compound when adding in oxide form.
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| TWI447230B (en) * | 2011-12-27 | 2014-08-01 | Metal Ind Res & Dev Ct | A manufacturing method for austempered ductile iron |
| CN102732768A (en) * | 2012-07-12 | 2012-10-17 | 中南大学 | High-ductility, corrosion-resistant and ultra/extra-thick crystalline cemented carbide and preparation method thereof |
| CN104120322B (en) * | 2014-08-01 | 2016-08-17 | 中南大学 | A kind of hard alloy and the method improving its PVD coating film-substrate cohesion |
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| CN106191610A (en) * | 2016-09-30 | 2016-12-07 | 柳州增程材料科技有限公司 | The processing method of Hardmetal materials |
| CN106399794B (en) * | 2016-10-28 | 2017-10-10 | 技锋精密刀具（马鞍山）有限公司 | A kind of hard alloy cutting tool material and preparation method thereof |
| CN106914624B (en) * | 2017-01-22 | 2019-08-20 | 苏州新锐合金工具股份有限公司 | A method of reducing hard alloy coefficient of friction |
| CN111705289B (en) * | 2020-06-30 | 2021-08-27 | 中南大学 | Self-lubricating high-temperature-abrasion-resistant hard surface material and preparation method thereof |
| CN115138849B (en) * | 2022-06-02 | 2024-01-12 | 湖南科技大学 | Preparation method of binding phase-free hard alloy cutter material |
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| CN1410575A (en) * | 2002-12-02 | 2003-04-16 | 株洲硬质合金集团有限公司 | Metal ceramic and its preparation method |
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| JP2001081526A (en) * | 1999-09-13 | 2001-03-27 | Kohan Kogyo Kk | Iron-base cemented carbide and its manufacture |
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|---|---|---|---|---|
| US5470372A (en) * | 1992-06-22 | 1995-11-28 | Sandvik Ab | Sintered extremely fine-grained titanium-based carbonitride alloy with improved toughness and/or wear resistance |
| US5984996A (en) * | 1995-02-15 | 1999-11-16 | The University Of Connecticut | Nanostructured metals, metal carbides, and metal alloys |
| CN1410575A (en) * | 2002-12-02 | 2003-04-16 | 株洲硬质合金集团有限公司 | Metal ceramic and its preparation method |
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Effective date of registration: 20221028 Address after: 314011 Factory Building 8 #, No. 1136 Bazi Road, Gaozhao Street, Xiuzhou District, Jiaxing City, Zhejiang Province Patentee after: Wald (Jiaxing) cemented carbide numerical control tools Co.,Ltd. Address before: Yuelu District City, Hunan province 410083 Changsha Lushan Road No. 932 Patentee before: CENTRAL SOUTH University |
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