CN102383020A - Ultrathin hard alloy with high hardness and preparation method thereof - Google Patents

Ultrathin hard alloy with high hardness and preparation method thereof Download PDF

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CN102383020A
CN102383020A CN2011103617777A CN201110361777A CN102383020A CN 102383020 A CN102383020 A CN 102383020A CN 2011103617777 A CN2011103617777 A CN 2011103617777A CN 201110361777 A CN201110361777 A CN 201110361777A CN 102383020 A CN102383020 A CN 102383020A
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ultra
cemented carbide
sintering
high firmness
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蒋显全
姜爱民
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Chongqing Academy of Science and Technology
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Chongqing Academy of Science and Technology
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Abstract

The invention discloses an ultrathin hard alloy with high hardness and a preparation method thereof. In the alloy, ultrathin carbide WC is taken as a hard phase, Co is taken as a bonding phase, and VC, NbC and TaC are taken as inhibitors; the alloy comprises the following components in percentage by weight: 90-90.4 percent of WC, 8 percent of Co, 0.2-0.6 percent of VC, 0.6 percent of NbC and 0.8 percent of TaC; and the preparation method for the ultrathin hard alloy with high hardness comprises the following steps of: performing wet grinding; drying; doping rubber; pressing; sintering; and cooling. The ultrathin hard alloy with high hardness, which is prepared by the preparation method, has small and thin crystal grains, high temperature hardness and strength and excellent wear resistance, and can be used as an alloy material for refined tools.

Description

A kind of high firmness ultra-fine cemented carbide and method of manufacture thereof
Technical field
The invention belongs to the alloy material manufacturing process technology field, specifically, is a kind of high firmness ultra-fine cemented carbide and method of manufacture thereof.
Background technology
Wimet is a kind of alloy material of being processed through powder metallurgical technique by refractory metal box matrix metal.Have hardness height, wear-resisting, intensity and good toughness, a series of premium propertiess such as heat-resisting, corrosion-resistant, it is widely used as cutter material.At present domesticly be generally YT and YW serial carbide alloy cutter in metal cutting semi-finishing and the used cutter of precision work; The TiC that adds can improve the hardness and the red hardness of cutter; But TiC can make the toughness of alloy on the low side, is unfavorable for that work brittleness material and cutting have ballistic field, and the crystal grain of common YT series hard alloy is thicker simultaneously; The cutting edge roundness that makes is sharp inadequately, can not make high-precision component.
Summary of the invention
The purpose of this invention is to provide a kind of high firmness ultra-fine cemented carbide, a kind of new composite hard alloy prescription is provided with superior hardness and excellent toughness; Another object of the present invention provides a kind of process method of making the high firmness ultra-fine cemented carbide.
For achieving the above object, the scheme that the present invention adopted is following:
A kind of high firmness ultra-fine cemented carbide, its main points are: this alloy adopts superfine carbide WC as the hard phase, with Co as the bonding phase; With VC, NbC and TaC as suppressor factor; The moity and the weight content of this alloy are following: WC:90-90.4%, Co:8%, VC:0.2~0.6%; NbC:0.6%, TaC:0.8%.
In order to make the present invention have more superior hardness and excellent toughness, the grain fineness number of above-mentioned WC is chosen as 0.4 μ m, and the grain fineness number of said Co is chosen as 1.42 μ m.
A kind of method of manufacture of high firmness ultra-fine cemented carbide is characterized in that comprising the steps:
(1) wet-milling: WC, VC, NbC and TaC are added the ball milling bucket in proportion; The absolute ethyl alcohol of pressing 300~400ml/kg adding purity 99.99% simultaneously is as ball-milling medium; Elder generation's ball milling 20~48 hours; Adding bonding phase Co, again 60~80 hours ball milling time, whenever stirred ball grinding cylinder once in the mechanical milling process then at a distance from 12 hours;
(2) drying: the wet feed behind the ball milling is crossed 320 eye mesh screens filter, and dry in vacuum drying oven, 80~120 ℃ of drying temperatures;
(3) mix glue: dried powder is crossed 80 eye mesh screens, presses 110ml/kg and adds gasoline rubber solution after drying, and it is for use to cross 60 eye mesh screens then;
(4) compacting: the powder that step (3) is obtained is pressed into 7.02 * 8.04 * 24.74 mm on hydraulic single column press 3The Type B bar;
(5) sintering: the Type B bar of step (4) gained is positioned over sintering in the vacuum sintering all-in-one oven;
(6) cooling: cool to the Type B in the step (5) with the furnace room temperature, and this Type B bar is taken out, thereby make the high firmness ultra-fine cemented carbide.
As preferably: when in the ball milling bucket, adding WC, VC, NbC and TaC in the step (1) in proportion, ball-to-powder weight ratio 3:1~6:1.
As preferably: it is characterized in that: sintering process is divided into three sintering stages in the step (5), comes unstuck the stage: temperature is appreciated 500 ℃ from room temperature, and the time is 1.5h; The solid state sintering stage: temperature rises to 1230 ℃ from 500 ℃, and the time is 1.5h; The highest sintering stage: temperature is 1400 ℃, insulation 1.5h.
As preferably: the high firmness ultra-fine cemented carbide that makes is carried out performance test, and the bending strength according to GB3851-83 test wimet thereby obtain bending strength is: 1500~1700MPa; Vickers' hardness according to GB7887-87 test wimet thereby obtain Vickers' hardness is: 2000~2100 HV 30According to the microstructure of GB3488-83 standard detection wimet, thereby the grain fineness number that obtains wimet is: 380~540nm.
Unusual effect of the present invention is: owing to selected thin WC powder for use and adopted an amount of VC, NbC and TaC to do grain growth inhibitor; Refinement the crystal grain of alloy; Reduce the voidage of alloy; And improved the content of F.C.C. Co in the alloy, can make that the mean grain size of WC reaches 390~540nm, the hardness HV of wimet in the wimet 30Reach: 2000~2100, the bending strength MPa:1500 of wimet~1700; The NbC that adds can improve the hot hardness and the hot strength of alloy, in working angles, improves the sticking temperature of alloy and steel simultaneously, slows down alloying constituent and in steel, spreads, and improves cutter life.Alloy grain of the present invention is tiny, has hot hardness and intensity, and has good wear resistance, can be used as the alloy material of finishing tool.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the microtexture organization chart of high firmness ultra-fine cemented carbide of the present invention;
Fig. 3 is the microtexture organization chart of ordinary rigid alloy.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done further explain.
Embodiment 1:
As shown in Figure 1, a kind of high firmness ultra-fine cemented carbide, this alloy adopt superfine carbide WC as the hard phase; As the bonding phase, as suppressor factor, the moity and the weight content of this alloy are following: WC:90% with VC, NbC and TaC with Co; Co:8%; VC:0.6%, NbC:0.6%, TaC:0.8%; The grain fineness number of wherein said WC is 0.4 μ m, and the grain fineness number of said Co is 1.42 μ m.
Above-mentioned high firmness ultra-fine cemented carbide adopts following steps to make:
(1) wet-milling: WC, VC, NbC and TaC are added the ball milling bucket in proportion; Press absolute ethyl alcohol that 300ml/kg adds purity 99.99% simultaneously as ball-milling medium, when in the ball milling bucket, adding WC, VC, NbC and TaC in proportion, ball-to-powder weight ratio 3:1; Elder generation's ball milling 20 hours; Adding bonding phase Co, again 60 hours ball milling time, whenever stirred ball grinding cylinder once in the mechanical milling process then at a distance from 12 hours;
(2) drying: the wet feed behind the ball milling is crossed 320 eye mesh screens filter, and dry in vacuum drying oven, 100 ℃ of drying temperatures;
(3) mix glue: dried powder is crossed 80 eye mesh screens, presses 110ml/kg and adds gasoline rubber solution after drying, and it is for use to cross 60 eye mesh screens then;
(4) compacting: the powder that step (3) is obtained is pressed into 7.02 * 8.04 * 24.74 mm on hydraulic single column press 3The Type B bar;
(5) sintering: the Type B bar of step (4) gained is positioned over sintering in the vacuum sintering all-in-one oven, and sintering process is divided into three sintering stages, comes unstuck the stage: temperature is appreciated 500 ℃ from room temperature, and the time is 1.5h; The solid state sintering stage: temperature rises to 1230 ℃ from 500 ℃, and the time is 1.5h; The highest sintering stage: temperature is 1400 ℃, insulation 1.5h.
(6) cooling: cool to the Type B in the step (5) with the furnace room temperature, and this Type B bar is taken out, thereby make the high firmness ultra-fine cemented carbide.
High firmness ultra-fine cemented carbide to making carries out Performance Detection, and according to the bending strength of GB3851-83 test wimet, its value is: 1500MPa; According to the webster hardness of GB7887-87 test wimet, its value is: 2000 HV 30According to the microstructure of GB3488-83 standard wimet, its grain fineness number is: 540nm.
Embodiment 2:
As shown in Figure 1, a kind of high firmness ultra-fine cemented carbide, this alloy adopt superfine carbide WC as the hard phase; As the bonding phase, as suppressor factor, the moity and the weight content of this alloy are following: WC:90.2% with VC, NbC and TaC with Co; Co:8%; VC:0.4%, NbC:0.6%, TaC:0.8%; The grain fineness number of wherein said WC is 0.4 μ m, and the grain fineness number of said Co is 1.42 μ m.
Above-mentioned high firmness ultra-fine cemented carbide adopts following steps to make:
(1) wet-milling: WC, VC, NbC and TaC are added the ball milling bucket in proportion; Press absolute ethyl alcohol that 350ml/kg adds purity 99.99% simultaneously as ball-milling medium, when in the ball milling bucket, adding WC, VC, NbC and TaC in proportion, ball-to-powder weight ratio 4.7:1; Elder generation's ball milling 34 hours; Adding bonding phase Co, again 72 hours ball milling time, whenever stirred ball grinding cylinder once in the mechanical milling process then at a distance from 12 hours;
(2) drying: the wet feed behind the ball milling is crossed 320 eye mesh screens filter, and dry in vacuum drying oven, 80 ℃ of drying temperatures;
(3) mix glue: dried powder is crossed 80 eye mesh screens, presses 110ml/kg and adds gasoline rubber solution after drying, and it is for use to cross 60 eye mesh screens then;
(4) compacting: the powder that step (3) is obtained is pressed into 7.02 * 8.04 * 24.74 mm on hydraulic single column press 3The Type B bar;
(5) sintering: the Type B bar of step (4) gained is positioned over sintering in the vacuum sintering all-in-one oven, and sintering process is divided into three sintering stages, comes unstuck the stage: temperature is appreciated 500 ℃ from room temperature, and the time is 1.5h; The solid state sintering stage: temperature rises to 1230 ℃ from 500 ℃, and the time is 1.5h; The highest sintering stage: temperature is 1400 ℃, insulation 1.5h.
(6) cooling: cool to the Type B in the step (5) with the furnace room temperature, and this Type B bar is taken out, thereby make the high firmness ultra-fine cemented carbide.
High firmness ultra-fine cemented carbide to making carries out Performance Detection, and according to the bending strength of GB3851-83 test wimet, its value is: 1600MPa; According to the webster hardness of GB7887-87 test wimet, its value is: 2068 HV30; According to the microstructure of GB3488-83 standard wimet, its grain fineness number is: 380nm.
Fig. 2 and Fig. 3 are seen in high firmness ultra-fine cemented carbide in the present embodiment 2 and the contrast of ordinary rigid alloy microstructure tissue respectively: in the present invention through after adding 0.4%VC+0.6%NbC+0.8%TaC; VC, NbC and TaC can effectively reduce the average grain size of alloy, thereby improve hardness of alloy, wear resistance.
Embodiment 3:
As shown in Figure 1, a kind of high firmness ultra-fine cemented carbide, this alloy adopt superfine carbide WC as the hard phase; As the bonding phase, as suppressor factor, the moity and the weight content of this alloy are following: WC:90.4% with VC, NbC and TaC with Co; Co:8%; VC:0.2%, NbC:0.6%, TaC:0.8%; The grain fineness number of wherein said WC is 0.4 μ m, and the grain fineness number of said Co is 1.42 μ m.
Above-mentioned high firmness ultra-fine cemented carbide adopts following steps to make:
(1) wet-milling: WC, VC, NbC and TaC are added the ball milling bucket in proportion; Press absolute ethyl alcohol that 400ml/kg adds purity 99.99% simultaneously as ball-milling medium, when in the ball milling bucket, adding WC, VC, NbC and TaC in proportion, ball-to-powder weight ratio 6:1; Elder generation's ball milling 48 hours; Adding bonding phase Co, again 80 hours ball milling time, whenever stirred ball grinding cylinder once in the mechanical milling process then at a distance from 12 hours;
(2) drying: the wet feed behind the ball milling is crossed 320 eye mesh screens filter, and dry in vacuum drying oven, 120 ℃ of drying temperatures;
(3) mix glue: dried powder is crossed 80 eye mesh screens, presses 110ml/kg and adds gasoline rubber solution after drying, and it is for use to cross 60 eye mesh screens then;
(4) compacting: the powder that step (3) is obtained is pressed into 7.02 * 8.04 * 24.74 mm on hydraulic single column press 3The Type B bar;
(5) sintering: the Type B bar of step (4) gained is positioned over sintering in the vacuum sintering all-in-one oven, and sintering process is divided into three sintering stages, comes unstuck the stage: temperature is appreciated 500 ℃ from room temperature, and the time is 1.5h; The solid state sintering stage: temperature rises to 1230 ℃ from 500 ℃, and the time is 1.5h; The highest sintering stage: temperature is 1400 ℃, insulation 1.5h.
(6) cooling: cool to the Type B in the step (5) with the furnace room temperature, and this Type B bar is taken out, thereby make the high firmness ultra-fine cemented carbide.
High firmness ultra-fine cemented carbide to making carries out Performance Detection, and according to the bending strength of GB3851-83 test wimet, its value is: 1700MPa; According to the webster hardness of GB7887-87 test wimet, its value is: 2100 HV30; According to the microstructure of GB3488-83 standard wimet, its grain fineness number is: 460nm.
The suppressor factor VC that adds among the present invention, NbC and TaC different ratios are that measured hardness and bending strength is as shown in the table:
Experiment numbers VC NbC TaC Hardness Bending strength
0 0 0 0 1700 1500
1 0.2 0.6 0.8 2002 1580
2 0.3 0.6 0.8 2050 1624
3 0.4 0.6 0.8 2068 1680
4 0.5 0.6 0.8 2040 1700
5 0.6 0.6 0.8 1990 1750
The above is merely preferred embodiment of the present invention, is not restriction with the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. high firmness ultra-fine cemented carbide is characterized in that: this alloy adopts superfine carbide WC as the hard phase, and as the bonding phase, as suppressor factor, the moity and the weight content of this alloy are following with VC, NbC and TaC with Co:
WC:90-90.4%,Co:8%,VC:0.2~0.6%,NbC:0.6%,TaC:0.8%。
2. a kind of high firmness ultra-fine cemented carbide according to claim 1 is characterized in that: the grain fineness number of said WC is 0.4 μ m, and the grain fineness number of said Co is 1.42 μ m.
3. the method for manufacture of a kind of high firmness ultra-fine cemented carbide according to claim 1 is characterized in that comprising the steps:
(1) wet-milling: WC, VC, NbC and TaC are added the ball milling bucket in proportion; The absolute ethyl alcohol of pressing 300~400ml/kg adding purity 99.99% simultaneously is as ball-milling medium; Elder generation's ball milling 20~48 hours; Adding bonding phase Co, again 60~80 hours ball milling time, whenever stirred ball grinding cylinder once in the mechanical milling process then at a distance from 12 hours;
(2) drying: the wet feed behind the ball milling is crossed 320 eye mesh screens filter, and dry in vacuum drying oven, 80~120 ℃ of drying temperatures;
(3) mix glue: dried powder is crossed 80 eye mesh screens, presses 110ml/kg and adds gasoline rubber solution after drying, and it is for use to cross 60 eye mesh screens then;
(4) compacting: the powder that step (3) is obtained is pressed into 7.02 * 8.04 * 24.74 mm on hydraulic single column press 3The Type B bar;
(5) sintering: the Type B bar of step (4) gained is positioned over sintering in the vacuum sintering all-in-one oven;
(6) cooling: cool to the Type B in the step (5) with the furnace room temperature, and this Type B bar is taken out, thereby make the high firmness ultra-fine cemented carbide.
4. the method for manufacture of a kind of high firmness ultra-fine cemented carbide according to claim 3 is characterized in that: when in the ball milling bucket, adding WC, VC, NbC and TaC in the step (1) in proportion, and ball-to-powder weight ratio 3:1~6:1.
5. the method for manufacture of a kind of high firmness ultra-fine cemented carbide according to claim 3 is characterized in that: sintering process is divided into three sintering stages in the step (5), comes unstuck the stage: temperature is appreciated 500 ℃ from room temperature, and the time is 1.5h; The solid state sintering stage: temperature rises to 1230 ℃ from 500 ℃, and the time is 1.5h; The highest sintering stage: temperature is 1400 ℃, insulation 1.5h.
6. the method for manufacture of a kind of high firmness ultra-fine cemented carbide according to claim 3 is characterized in that: the hardness of the high firmness ultra-fine cemented carbide that makes is: 2000~2100 HV 30Bending strength is: 1500~1700MPa, grain fineness number is: 380~540nm.
CN2011103617777A 2011-11-16 2011-11-16 Ultrathin hard alloy with high hardness and preparation method thereof Pending CN102383020A (en)

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CN103212729A (en) * 2013-04-17 2013-07-24 重庆市硅酸盐研究所 Numerical control cutting tool with CrAlTiN superlattice coating and manufacturing method thereof
CN103276270A (en) * 2013-05-17 2013-09-04 中南大学 Ultrafine/nanocrystalline carbide alloy binding phase and preparation and application thereof
CN103386417A (en) * 2013-07-30 2013-11-13 株洲硬质合金集团有限公司 Method for producing hard alloy product by metallurgical bonding
CN103614604A (en) * 2013-12-16 2014-03-05 重庆市科学技术研究院 Hard alloy for rotary drilling cutting drill bit for mining and preparation method of hard alloy
CN103667843A (en) * 2013-12-23 2014-03-26 四川大学 Method for preparing superfine cemented carbide cutter material for deep hole machining
CN104308232A (en) * 2014-09-18 2015-01-28 宁波市荣科迈特数控刀具有限公司 Multifunctional drilling rod
CN104308230A (en) * 2014-09-18 2015-01-28 宁波市荣科迈特数控刀具有限公司 Side fixed type shovel drill
CN105127419A (en) * 2015-09-29 2015-12-09 浙江恒成硬质合金有限公司 Method for firing low-cobalt fine-grain hard alloy by using ordinary sintering furnace
CN105671398A (en) * 2016-01-29 2016-06-15 柳州市安龙机械设备有限公司 Machining method for hard alloy rock excavating drilling tooth
CN105714170A (en) * 2014-12-03 2016-06-29 自贡硬质合金有限责任公司 Hard alloy and preparation method thereof
CN107475549A (en) * 2017-07-21 2017-12-15 浙江唯精合金科技有限公司 A kind of preparation method of hard alloy
CN109468516A (en) * 2018-12-13 2019-03-15 株洲金韦硬质合金有限公司 A kind of hard alloy wear resistant parts and its preparation method and application
CN109485425A (en) * 2019-01-04 2019-03-19 燕山大学 A kind of tungsten carbide composite and preparation method thereof
CN111020337A (en) * 2020-01-02 2020-04-17 荆门德威格林美钨资源循环利用有限公司 Inhibitor applied to preparation of superfine tungsten carbide and preparation method thereof
CN113201677A (en) * 2021-05-07 2021-08-03 四川坤天硬质合金有限责任公司 Production process for producing ultrafine grain hard alloy by using sub-fine tungsten carbide
CN113462946A (en) * 2021-06-03 2021-10-01 中南大学 Cobalt-nickel-iron-chromium-based hard alloy material and preparation method thereof

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CN101845579A (en) * 2010-06-28 2010-09-29 株洲钻石切削刀具股份有限公司 Inhomogeneous hard alloy and preparation method thereof
CN101967593A (en) * 2010-11-16 2011-02-09 西华大学 Ultrafine grain solid carbide material containing rare earth and preparation method thereof

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CN101760685A (en) * 2008-12-25 2010-06-30 北京有色金属研究总院 Superfine WC-Co cemented carbide containing rare-earth elements and preparation method thereof
CN101845579A (en) * 2010-06-28 2010-09-29 株洲钻石切削刀具股份有限公司 Inhomogeneous hard alloy and preparation method thereof
CN101967593A (en) * 2010-11-16 2011-02-09 西华大学 Ultrafine grain solid carbide material containing rare earth and preparation method thereof

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CN103212729A (en) * 2013-04-17 2013-07-24 重庆市硅酸盐研究所 Numerical control cutting tool with CrAlTiN superlattice coating and manufacturing method thereof
CN103212729B (en) * 2013-04-17 2016-04-13 重庆市硅酸盐研究所 A kind of have NC cutting tool of CrAlTiN superlattice coating and preparation method thereof
CN103276270A (en) * 2013-05-17 2013-09-04 中南大学 Ultrafine/nanocrystalline carbide alloy binding phase and preparation and application thereof
CN103276270B (en) * 2013-05-17 2015-11-04 中南大学 A kind of ultra-fine/Nanograin Cemented Carbide Binder Phase and Synthesis and applications
CN103386417A (en) * 2013-07-30 2013-11-13 株洲硬质合金集团有限公司 Method for producing hard alloy product by metallurgical bonding
CN103614604B (en) * 2013-12-16 2016-02-03 重庆市科学技术研究院 For mining Wimet of rotary drilling cut drill and preparation method thereof
CN103614604A (en) * 2013-12-16 2014-03-05 重庆市科学技术研究院 Hard alloy for rotary drilling cutting drill bit for mining and preparation method of hard alloy
CN103667843A (en) * 2013-12-23 2014-03-26 四川大学 Method for preparing superfine cemented carbide cutter material for deep hole machining
CN104308232A (en) * 2014-09-18 2015-01-28 宁波市荣科迈特数控刀具有限公司 Multifunctional drilling rod
CN104308232B (en) * 2014-09-18 2016-10-05 宁波市荣科迈特数控刀具有限公司 A kind of Multifunctional drill rod
CN104308230A (en) * 2014-09-18 2015-01-28 宁波市荣科迈特数控刀具有限公司 Side fixed type shovel drill
CN105714170B (en) * 2014-12-03 2017-12-05 自贡硬质合金有限责任公司 Hard alloy and preparation method thereof
CN105714170A (en) * 2014-12-03 2016-06-29 自贡硬质合金有限责任公司 Hard alloy and preparation method thereof
CN105127419A (en) * 2015-09-29 2015-12-09 浙江恒成硬质合金有限公司 Method for firing low-cobalt fine-grain hard alloy by using ordinary sintering furnace
CN105671398A (en) * 2016-01-29 2016-06-15 柳州市安龙机械设备有限公司 Machining method for hard alloy rock excavating drilling tooth
CN105671398B (en) * 2016-01-29 2017-07-11 柳州市安龙机械设备有限公司 The processing method of hard alloy rock drilling tooth
CN107475549A (en) * 2017-07-21 2017-12-15 浙江唯精合金科技有限公司 A kind of preparation method of hard alloy
CN109468516A (en) * 2018-12-13 2019-03-15 株洲金韦硬质合金有限公司 A kind of hard alloy wear resistant parts and its preparation method and application
CN109485425A (en) * 2019-01-04 2019-03-19 燕山大学 A kind of tungsten carbide composite and preparation method thereof
CN111020337A (en) * 2020-01-02 2020-04-17 荆门德威格林美钨资源循环利用有限公司 Inhibitor applied to preparation of superfine tungsten carbide and preparation method thereof
CN113201677A (en) * 2021-05-07 2021-08-03 四川坤天硬质合金有限责任公司 Production process for producing ultrafine grain hard alloy by using sub-fine tungsten carbide
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Application publication date: 20120321