CN104789846A - Vanadium carbonitride titanium-base hard alloy and production method thereof - Google Patents
Vanadium carbonitride titanium-base hard alloy and production method thereof Download PDFInfo
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Abstract
The invention relates to vanadium carbonitride titanium-base hard alloy and a production method thereof, and belongs to the field of metal ceramics. The technical problem to be solved by the invention is to provide the vanadium carbonitride titanium-base hard alloy (Ti, V, M) (C, N). The vanadium carbonitride titanium-base hard alloy comprises the following components in percentage by weight: 12.1-57.1wt% of Ti, 6.7-51.5wt% of V, 0-10wt% of M, 7.6-14.3wt% of C, 1.9-10wt % of N, less than or equal to 20wt% of Co and less than or equal to 20wt% of Ni, wherein M is at least one of Mo and Ta. The bending strength of the vanadium carbonitride titanium-base hard alloy is 1089-1437Mpa. The hardness of the vanadium carbonitride titanium-base hard alloy is HV2000-HV2400.
Description
Technical field
The present invention relates to vanadium carbide nitride titanium based hard alloy and production method thereof, belong to sintering metal field.
Background technology
Titanium based hard alloy is intended to saving and alternatives tungsten carbide base carbide alloy, early stage titanium based hard alloy with titanium carbide (TiC) for matrix.Develop again the unlimited solid solution boride based cemented carbide (Ti (C that TiC and TiN is formed on this basis, N)), the cutter made of this Wimet, although there is good wear resistance, but it is low to go back flexible, be easy to collapse the problems such as cutter.
In order to develop (Ti (C, N)) base cemented carbide, publication number is that the Chinese patent application of CN102534340A0 discloses one " the nitrogenous Wimet based on multi-element composite titanium carbonitride solid solution ", it is by wolfram varbide (WC) and sosoloid (Ti, M) (C, N) be main component (wherein M is at least two kinds in W, Mo, Ta, Nb, V, Cr, Hf, Y and lanthanon), Co or Ni is the Wimet that Binder Phase is formed.Wherein the mass percent of WC is 45 ~ 96.9%, and the mass percent of sosoloid (Ti, M) (C, N) is 0.1 ~ 30%, Co, the mass percent of Ni is 3 ~ 25%.Although (Ti, M) (C, N) is one of matrix phase in technical scheme disclosed in this application, WC remains another kind of matrix phase, and V is trace mineral supplement.
Publication number is that the Chinese patent application of CN104129994A discloses one " preparation method of vanadium carbide titanium ", and it is the continuous solid solution ((Ti, V) C) formed by TiC and VC.Because (Ti, V) C density is low, hardness is high, is expected to go out a class novel hard alloy at aspect developings such as wear part, cutter, grinding tools, substitutes traditional WC base cemented carbide, is conducive to the tungsten cobalt resource saving China's preciousness.Although (Ti, V) C has the application prospect replacing WC in scheme disclosed in this application, N and other advantageous metal element (M) is not also had to add.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of vanadium carbide nitride titanium based hard alloy (Ti, V, M) (C, N)).
Vanadium carbide nitride titanium based hard alloy of the present invention is made up of following component by mass percentage: Ti:12.1 ~ 57.1wt%, V:6.7 ~ 51.5wt%, M:0 ~ 10wt%, C:7.6 ~ 14.3wt%, N:1.9 ~ 10wt%, Co≤20wt%, Ni≤20wt%; Wherein, M is at least one in Mo, Ta.
Wherein, as preferred technical scheme, M content is 1 ~ 10wt%.
Further, vanadium carbide nitride titanium based hard alloy of the present invention, also preferably be made up of following component by mass percentage: Ti:30.7 ~ 50.2wt%, V:12 ~ 32.6wt%, Mo:1 ~ 2wt%, Ta:1.9 ~ 7.5wt%, C:7.7 ~ 11wt%, N:5 ~ 9wt%, Co:4 ~ 7wt%, Ni:1.3 ~ 16wt%.More preferably be made up of following component by mass percentage: Ti:46.4wt%, V:12.3wt%, Mo:2wt%, Ta:3.8wt%, C:10.4wt%, N:5.1wt%, Co:4wt%, Ni:16wt%.
The bending strength of vanadium carbide nitride titanium based hard alloy of the present invention is 1089 ~ 1437MPa, and hardness is HV2000 ~ HV2400.
Present invention also offers the method for producing above-mentioned vanadium carbide nitride titanium based hard alloy, it comprises the steps:
A, batching: based on TiVCN, add metal additive Co, M and Ni, obtain compound; Wherein, the consumption of each raw material configures by the mass percent of technique scheme;
B, compression moulding: by compound compression moulding, obtain briquetting;
C, vacuum sintering: sintered under vacuum atmosphere by briquetting, cooling, obtains vanadium carbide nitride titanium based hard alloy.
Further, in order to obtain performance better vanadium carbide nitride titanium based hard alloy, above-mentioned a step batch mixing carries out in ball mill, wherein batch mixing medium is dehydrated alcohol, ball used is that tungsten base hard closes ball, ratio of grinding media to material is 5:1 ~ 10:1, liquid-solid ratio 0.5 ~ 0.8g/ml, and Ball-milling Time is 8 ~ 108h.
Wherein, the method for above-mentioned production vanadium carbide nitride titanium based hard alloy, in its b step, pressing pressure is preferably 120 ~ 550MPa, and the density of briquetting is preferably 3.4 ~ 4.0gcm
-3.In described b step, pressing pressure is more preferably 320 ~ 550MPa.
Further, in order to make the vanadium carbide nitride titanium based hard alloy property of production better, being preferably as follows technical scheme: above-mentioned step c vacuum sintering vacuum tightness < 5MPa, adopting four sections of sintering that heat up simultaneously, one section is warming up to 300 ~ 350 DEG C, insulation 1 ~ 1.5h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1 ~ 1.5h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1 ~ 1.5h; Four sections are warming up to 1430 DEG C ~ 1510 DEG C, insulation 1 ~ 1.5h.More preferably, one section is warming up to 320 DEG C, insulation 1h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1h; Four sections are warming up to 1450 ~ 1480 DEG C, insulation 1h.
Wherein, the vanadium carbide nitride titanium based hard alloy powder granularity that aforesaid method is produced is 2 ~ 3um.
The present invention compares with existing method, has following beneficial effect:
1, in the present invention, (Ti, V, M) (C, N) base cemented carbide bending strength is 1089 ~ 1437MPa, and hardness is HV2000 ~ HV2400.
2, (Ti, V, M) (C, N) base cemented carbide is prepared with (Ti, V, M) (C, N) solid solution powder body in the present invention.For the research and development of nitrogenous Novel Titanium base cemented carbide provide new approach.
Accompanying drawing explanation
Fig. 1 (Ti, V) (C, N) base cemented carbide micro-organization chart;
Fig. 2 (Ti, V, Mo) (C, N) base cemented carbide micro-organization chart;
Fig. 3 (Ti, V, Mo, Ta) (C, N) base cemented carbide micro-organization chart;
Embodiment
Vanadium carbide nitride titanium based hard alloy of the present invention is made up of following component by mass percentage: Ti:12.1 ~ 57.1wt%, V:6.7 ~ 51.5wt%, M:0 ~ 10wt%, C:7.6 ~ 14.3wt%, N:1.9 ~ 10wt%, Co≤20wt%, Ni≤20wt%; Wherein, M is at least one in Mo, Ta.
Wherein, as preferred technical scheme, M content is 1 ~ 10wt%.
Further, vanadium carbide nitride titanium based hard alloy of the present invention, also preferably be made up of following component by mass percentage: Ti:30.7 ~ 50.2wt%, V:12 ~ 32.6wt%, Mo:1 ~ 2wt%, Ta:1.9 ~ 7.5wt%, C:7.7 ~ 11wt%, N:5 ~ 9wt%, Co:4 ~ 7wt%, Ni:1.3 ~ 16wt%.More preferably be made up of following component by mass percentage: Ti:46.4wt%, V:12.3wt%, Mo:2wt%, Ta:3.8wt%, C:10.4wt%, N:5.1wt%, Co:4wt%, Ni:16wt%.
The bending strength of vanadium carbide nitride titanium based hard alloy of the present invention is 1089 ~ 1437MPa, and hardness is HV2000 ~ HV2400.
Present invention also offers the method for producing above-mentioned vanadium carbide nitride titanium based hard alloy, it comprises the steps:
A, batching: based on TiVCN, add metal additive Co, M and Ni, obtain compound; Wherein, the consumption of each raw material configures by the mass percent of technique scheme;
B, compression moulding: by compound compression moulding, obtain briquetting;
C, vacuum sintering: sintered under vacuum atmosphere by briquetting, cooling, obtains vanadium carbide nitride titanium based hard alloy.
Further, in order to obtain performance better vanadium carbide nitride titanium based hard alloy, above-mentioned a step batch mixing carries out in ball mill, wherein batch mixing medium is dehydrated alcohol, ball used is tungsten base cemented carbide ball, ratio of grinding media to material is 5:1 ~ 10:1, liquid-solid ratio 0.5 ~ 0.8g/ml, and Ball-milling Time is 8 ~ 108h.
Wherein, the method for above-mentioned production vanadium carbide nitride titanium based hard alloy, in its b step, pressing pressure is preferably 120 ~ 550MPa, and the density of briquetting is preferably 3.4 ~ 4.0gcm
-3.In described b step, pressing pressure is more preferably 320 ~ 550MPa.
Further, in order to make the vanadium carbide nitride titanium based hard alloy property of production better, being preferably as follows technical scheme: above-mentioned step c vacuum sintering vacuum tightness < 5MPa, adopting four sections of sintering that heat up simultaneously, one section is warming up to 300 ~ 350 DEG C, insulation 1 ~ 1.5h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1 ~ 1.5h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1 ~ 1.5h; Four sections are warming up to 1430 DEG C ~ 1510 DEG C, insulation 1 ~ 1.5h.More preferably, one section is warming up to 320 DEG C, insulation 1h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1h; Four sections are warming up to 1450 ~ 1480 DEG C, insulation 1h.
Wherein, the vanadium carbide nitride titanium based hard alloy powder granularity that aforesaid method is produced is 2 ~ 3um.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1 adopts the inventive method to prepare (Ti, V) (C, N) base cemented carbide
Take (Ti, V) (C, N) solid solution powder 80g (TiC32.8g, VC23g, TiN24.2g), Co powder 10g, Ni powder 10g, then load in ball grinder, ratio of grinding media to material is 5:1, adds 60mL alcohol, and ball milling crosses aperture after 32 hours be that the screen cloth of 0.04mm obtains mixing wet feed, in vacuum drying oven at 80 DEG C dry 3.5 hours, after drying aperture be the screen cloth of 0.2mm.Take 6.05g compound, load in the former of forming mould, base of colding pressing is made at the pressure of 320MPa, put it in vacuum oven and sinter, its vacuum sintering technology is as follows: be evacuated to lower than 5Pa, is slowly warmed up to 320 DEG C of insulations 1 hour, is warmed up to 800 DEG C of insulations 1 hour, continue to be warming up to 1150 DEG C of insulations 1 hour, be finally warming up to sintering temperature 1480 DEG C insulation and terminate after 1 hour.This Wimet bending strength is 1100MPa, and dimension formula hardness is HV2100.
Embodiment 2 adopts the inventive method to prepare (Ti, V, Mo) (C, N) base cemented carbide
The raw material that the present embodiment is used and processing step as follows:
Take (Ti, V) (C, N) solid solution powder 80g (TiC38.2g, VC16.1g, TiN23.7g), Mo powder 2g, Co powder 4g, Ni powder 16g, then load in ball grinder, ratio of grinding media to material is 8:1, adds 75mL alcohol, and ball milling crosses aperture after 32 hours be that the screen cloth of 0.04mm obtains mixing wet feed, in vacuum drying oven at 80 DEG C dry 5 hours, after drying aperture be the screen cloth of 0.2mm.Take 6.05g compound, load in the former of forming mould, base of colding pressing is made at the pressure of 470MPa, put it in vacuum oven and sinter, its vacuum sintering technology is as follows: be evacuated to lower than 5Pa, is slowly warmed up to 320 DEG C of insulations 1 hour, is warmed up to 1000 DEG C of insulations 1 hour, continue to be warming up to 1150 DEG C of insulations 1 hour, be finally warming up to sintering temperature 1510 DEG C insulation and terminate after 1 hour.This Wimet bending strength is 1324MPa, and dimension formula hardness is HV2200.
Embodiment 3 adopts the inventive method to prepare (Ti, V, Mo, Ta) (C, N) base cemented carbide
The raw material that the present embodiment is used and processing step as follows:
Take (Ti, V) (C, N) solid solution powder 80g (TiC37.3g, VC15.6g, TiN23.1g), Mo powder 2g, TaC powder 2g, Co powder 4g, Ni powder 16g, then load in ball grinder, ratio of grinding media to material is 8:1, adds 50mL alcohol, and ball milling crosses aperture after 32 hours be that the screen cloth of 0.04mm obtains mixing wet feed, in vacuum drying oven at 80 DEG C dry 3.5 hours, after drying aperture be the screen cloth of 0.2mm.Take 6.05g compound, load in the former of forming mould, base of colding pressing is made at the pressure of 470MPa, put it in vacuum oven and sinter, its vacuum sintering technology is as follows: be evacuated to lower than 5Pa, is slowly warmed up to 320 DEG C of insulations 1 hour, is warmed up to 1000 DEG C of insulations 1 hour, continue to be warming up to 1150 DEG C of insulations 1 hour, be finally warming up to sintering temperature 1450 DEG C insulation and terminate after 1 hour.This Wimet bending strength is 1437MPa, and dimension formula hardness is HV2280.
Embodiment 4 adopts the inventive method to prepare (Ti, V, Mo, Ta) (C, N) base cemented carbide
The raw material that the present embodiment is used and processing step as follows:
Take (Ti, V) (C, N) solid solution powder 80g (VC37.3g, TiN36.7g), Mo powder 2g, TaC powder 4g, Co powder 6.7g, Ni powder 13.3g, then load in ball grinder, ratio of grinding media to material is 8:1, add 70mL alcohol, ball milling crosses aperture after 72 hours be that the screen cloth of 0.04mm obtains mixing wet feed, in vacuum drying oven at 80 DEG C dry 5 hours, after drying aperture be the screen cloth of 0.2mm.Take 6.05g compound, load in the former of forming mould, base of colding pressing is made at the pressure of 470MPa, put it in vacuum oven and sinter, its vacuum sintering technology is as follows: be evacuated to lower than 5Pa, is slowly warmed up to 320 DEG C of insulations 1 hour, is warmed up to 1000 DEG C of insulations 1 hour, continue to be warming up to 1150 DEG C of insulations 1 hour, be finally warming up to sintering temperature 1480 DEG C insulation and terminate after 1 hour.This Wimet bending strength is 1322MPa, and dimension formula hardness is HV2100.
Embodiment 5 adopts the inventive method to prepare (Ti, V, Mo, Ta) (C, N) base cemented carbide
The raw material that the present embodiment is used and processing step as follows:
Take (Ti, V) (C, N) solid solution powder 80g (TiC27.3g, VC28.6g, TiN14.1g), Mo powder 2g, TaC powder 8g, Co powder 12g, Ni powder 8g, then load in ball grinder, ratio of grinding media to material is 8:1, adds 80mL alcohol, and ball milling crosses aperture after 108 hours be that the screen cloth of 0.04mm obtains mixing wet feed, in vacuum drying oven at 80 DEG C dry 7 hours, after drying aperture be the screen cloth of 0.2mm.Take 6.05g compound, load in the former of forming mould, base of colding pressing is made at the pressure of 470MPa, put it in vacuum oven and sinter, its vacuum sintering technology is as follows: be evacuated to lower than 5Pa, is slowly warmed up to 320 DEG C of insulations 1 hour, is warmed up to 1000 DEG C of insulations 1 hour, continue to be warming up to 1150 DEG C of insulations 1 hour, be finally warming up to sintering temperature 1510 DEG C insulation and terminate after 1 hour.This Wimet bending strength is 1200MPa, and dimension formula hardness is HV2150.
Claims (10)
1. vanadium carbide nitride titanium based hard alloy, is characterized in that being made up of following component by mass percentage: Ti:12.1 ~ 57.1wt%, V:6.7 ~ 51.5wt%, M:0 ~ 10wt%, C:7.6 ~ 14.3wt%, N:1.9 ~ 10wt%, Co≤20wt%, Ni≤20wt%; Wherein, M is at least one in Mo, Ta.
2. vanadium carbide nitride titanium based hard alloy according to claim 1, is characterized in that: M content is 1 ~ 10wt%.
3. vanadium carbide nitride titanium based hard alloy according to claim 2, it is characterized in that being made up of following component by mass percentage: Ti:30.7 ~ 50.2wt%, V:12 ~ 32.6wt%, Mo:1 ~ 2wt%, Ta:1.9 ~ 7.5wt%, C:7.7 ~ 11wt%, N:5 ~ 9wt%, Co:4 ~ 7wt%, Ni:1.3 ~ 16wt%.
4. vanadium carbide nitride titanium based hard alloy according to claim 3, is characterized in that being made up of following component by mass percentage: Ti:46.4wt%, V:12.3wt%, Mo:2wt%, Ta:3.8wt%, C:10.4wt%, N:5.1wt%, Co:4wt%, Ni:16wt%.
5. the vanadium carbide nitride titanium based hard alloy according to any one of Claims 1 to 4, is characterized in that: described vanadium carbide nitride titanium based hard alloy bending strength is 1089 ~ 1437MPa, and hardness is HV2000 ~ HV2400.
6. the method for the vanadium carbide nitride titanium based hard alloy described in any one of production claim 1-5, is characterized in that comprising the steps:
A, batching: based on TiVCN, add metal additive Co, M and Ni, obtain compound;
B, compression moulding: by compound compression moulding, obtain briquetting;
C, vacuum sintering: sintered under vacuum atmosphere by briquetting, cooling, obtains vanadium carbide nitride titanium based hard alloy.
7. the method for production vanadium carbide nitride titanium based hard alloy according to claim 6, it is characterized in that: described a step batch mixing carries out in ball mill, wherein batch mixing medium is dehydrated alcohol, ball used is that tungsten base hard closes ball, ratio of grinding media to material is 5:1 ~ 10:1, liquid-solid ratio 0.5 ~ 0.8g/ml, Ball-milling Time is 8 ~ 108h.
8. the method for production vanadium carbide nitride titanium based hard alloy according to claim 6, is characterized in that: in described b step, pressing pressure is 120 ~ 550MPa, and the density of briquetting is 3.4 ~ 4.0gcm
-3.
9. the method for production vanadium carbide nitride titanium based hard alloy according to claim 8, is characterized in that: in described b step, pressing pressure is 320 ~ 550MPa.
10. the method for the production vanadium carbide nitride titanium based hard alloy according to any one of claim 6-9, it is characterized in that: described step c vacuum sintering vacuum tightness < 5MPa, adopt four sections of sintering that heat up, one section is warming up to 300 ~ 350 DEG C simultaneously, insulation 1 ~ 1.5h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1 ~ 1.5h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1 ~ 1.5h; Four sections are warming up to 1430 DEG C ~ 1510 DEG C, insulation 1 ~ 1.5h.More preferably, one section is warming up to 320 DEG C, insulation 1h; Two sections are warming up to 800 ~ 1000 DEG C, insulation 1h; Three sections are warming up to 1100 ~ 1200 DEG C, insulation 1h; Four sections are warming up to 1450 ~ 1480 DEG C, insulation 1h.
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| CN105734383A (en) * | 2016-03-11 | 2016-07-06 | 河源泳兴硬质合金有限公司 | Vanadium carbide titanium-based hard alloy and production method thereof |
| CN109136709A (en) * | 2018-10-17 | 2019-01-04 | 攀枝花学院 | The production method of vanadium carbide nitride magnesium-titanium solid solution and its hard alloy |
| CN111172444A (en) * | 2020-01-16 | 2020-05-19 | 攀枝花学院 | Vanadium-titanium carbide-based metal ceramic and preparation method thereof |
| CN111943266A (en) * | 2020-08-28 | 2020-11-17 | 郑州轻工业大学 | Preparation method and application of vacancy vanadium-titanium nitride |
| CN113737076A (en) * | 2021-09-08 | 2021-12-03 | 王淅茹 | Low-nitrogen high-toughness Ti (C, N) cermet matrix and preparation process thereof |
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| CN105734383A (en) * | 2016-03-11 | 2016-07-06 | 河源泳兴硬质合金有限公司 | Vanadium carbide titanium-based hard alloy and production method thereof |
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| CN111172444A (en) * | 2020-01-16 | 2020-05-19 | 攀枝花学院 | Vanadium-titanium carbide-based metal ceramic and preparation method thereof |
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| CN111943266B (en) * | 2020-08-28 | 2022-06-21 | 郑州轻工业大学 | Preparation method and application of vacancy vanadium-titanium nitride |
| CN113737076A (en) * | 2021-09-08 | 2021-12-03 | 王淅茹 | Low-nitrogen high-toughness Ti (C, N) cermet matrix and preparation process thereof |
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Effective date of registration: 20220616 Address after: 476000 west of Zhengping road and south of Yueji Road, Shangqiu Economic Development Zone, Shangqiu City, Henan Province Patentee after: SHANGQIU SHANGDING REFRACTORY MATERIAL Co.,Ltd. Address before: 236400 Room 201, building 5, Bailian innovation and Technology Industrial Park, 16 Xiaguang Avenue, Xingtang sub district office, Linquan County, Fuyang City, Anhui Province Patentee before: Fuyang Shenbang New Material Technology Co.,Ltd. |