CN1410574A - Metal-ceramic cutting tool material and its preparation method - Google Patents
Metal-ceramic cutting tool material and its preparation method Download PDFInfo
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Abstract
The invention discloses the Ti(C,N) based metal ceramics and its preparation method. The weight ratio of each constituent of the metal ceramics is as following Ti30-65, W8-25, Ta1.0-15.0, Zr0.1-5.0, Nb0-10, Cr0-1.0 etc as well as C and N as the rest. The powder of ceramics of carbonitride with Multiple elements in duplex type of two or more different element combinations is mixed with the powders of carbide of Ti, W, Ta, Nb, V, Zr etc. and/or powders of carbide of their solid solution as well as the powders of Co, Ni, Mo. The metal ceramics are made from the admixture through the procedures of ball mill crushing, pressure moulding, vacuum dewaxing and vacuum sintering. With the good wear resistance being kept, the metal ceramics possesses high intensity and toughness.
Description
Technical field
The present invention relates to stupalith and preparation method thereof, particularly Ti (C, N) based ceramic metal and preparation method thereof.
Background technology
Ti (C, N) based ceramic metal is a kind of novel cermet material of being born in nineteen seventies, and it is low that it has density, and chemical stability and good in oxidation resistance are little to the coefficient of friction of steel, and hardness and red hardness are higher than advantages such as Wimet.Ti (C, N) based ceramic metal is as cutter material, the high speed cutting and the DRY CUTTING that are suitable for cast iron, ordinary steel, glass hard steel, especially be better than Wimet and cutting tool coated with hard alloy in use properties aspect precision work, the semi-finishing, thereby the enterprise of various countries and research institution are in recent years at Ti (C, N) many work have been done in the research aspect of based ceramic metal, and launch products is arranged.With the Japanese market is example, and (C, N) base ceramet tool bit has accounted for about 25～30% market to Ti in the numerical control blade, the performance of its main trade mark: hardness (HRA) 91.0～94.0, bending strength 1200～2000Mpa.Is (open day 1985 to Chinese patent 88107079.3? on May 10, in) provides a kind of cermet cutting tool, its composition is: 3.5≤Ni≤6.5,4.5≤Co≤7.5,20≤W≤25,5≤Mo≤11,0≤Ta+Nb≤6, Cr≤0.05, Al≤1.0, V≤3,8≤Co+Ni≤11 wherein, all the other compositions are Ti, C and N.The main raw material carbonitride powder of this cermet material is that (purpose is to keep improving the toughness of cutter on the better wear resistance of cutter and the basis in work-ing life to Ti for C, N) powder.Provide a kind of composite cermet and preparation method thereof in the Chinese patent 01133646.3 (open day is on May 1st, 2002), sintering metal composition weight percent is in this invention: 25≤Ti≤30,6≤C≤8.5,25≤Ni≤40,12≤Mo≤20,2≤N≤3,5≤W≤10,0.4≤Cr≤1.0.Its preparation technology is: with the powder mixes of simple substance element ti, C, Ni, Mo, under the Ar gas shiled, comprise nano level TiC by prepared by mechanical alloy
xWith the mixture of NiMo sosoloid, again with TiN, WC, Cr
3C
2, the C powder is mixed with the mixture that meets above-mentioned composition together, adds forming agent, compression moulding is higher than in vacuum tightness under the condition of 5Pa and dewaxes, and is higher than 1.0 * 1.0 in vacuum tightness
-1Sintering under the condition of Pa is 100～150MPa at pressure, carries out hip treatment under the condition that treatment temp is 1350～1400 ℃.The purpose of this invention provides a kind of higher-strength (σ that has
bComposite cermet of=2500～2630MPa) and preparation method thereof, but its wear resistance lower (HRA=91.7～90.0).Although in recent years Ti (C, N) based ceramic metal obtains bigger development at home and abroad, it is above-mentioned that to put the subject matter that product and patented technology exist on market be to remain obdurability deficiency, product performance instability.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of novel Ti (C is provided, N) base metal-ceramic material, under the prerequisite that keeps high rigidity, high-wearing feature, improve its intensity and toughness greatly, make it have excellent comprehensive performances, both can be applicable to cutting tool material well, can be used as moulding stock such as wortle, pressing die again.The present invention simultaneously also provides this new Ti (C, N) preparation method of base metal-ceramic material.
Ti of the present invention (C, N) each composition weight percent of based ceramic metal is: Ti30～65, W8～25, Ta1.0～15.0, Zr0.1～5.0, Nb0～10, Cr0～1.0, V0～5.0, Al0～1.0, Mo4.5～20, Ni3.5～15.0, Co4.5～15, all the other compositions are C and N.
Ti of the present invention (C, N) based ceramic metal is pressed the weight percent meter in composition, Ta+Nb+V=1.0～20, Ni+Co=8～25 and Ni/ (Ni+Co)=0.2～0.8 are better.
Ti (C of the present invention, N) preparation method of based ceramic metal, in turn include the following steps: carbonitride ceramic powder, carbide ceramics powder that (1) will be finally can satisfy above-mentioned each composition weight percent of sintering metal of the present invention mix with metal-powder and carry out wet-milling, wet-milling makes compound after precipitation is dry; (2) press 8～15% of compound weight and add forming agent, carry out drying and granulating after the mixing, repressed moulding; (3) will be pressed into moulding mixture and dewax in vacuum oven and sintering, dewaxing vacuum tightness is higher than 5Pa, respectively is incubated 90～150min when being warming up between 250～350 ℃ and 400～650 ℃; Sintering vacuum tightness is higher than 0.1Pa, and sintering process is: be warming up to 1300 ℃ of insulation 30～50min; Be warming up to 1400～1500 ℃ of insulation 30～100min again; And under vacuum environment, cool off.
Adopt sintering metal preparation method of the present invention, the carbonitride ceramic powder comprises the polynary compound carbonitride solid solution ceramic powder of two or more different constituent elements at least in the used raw material, particularly contains a kind of Ti (C, N) powder and (Ti at least, W, Ta, Nb, Mo) (C, N), (Ti, W) (C, N), (Ti, W, Ta) (C, N), (Ti, W, Ta, Nb) (C, Ti such as N), W, Ta, Nb, a kind of in the polynary compound carbonitride solid-solution powder of Mo, and by weight timing, Ti (C, N) in the powder, N/ (N+C)=0.6～0.8, Ti, W, Ta, Nb, in the polynary compound carbonitride solid-solution powder such as Mo, N/ (N+C)=0.3～0.6.
In addition, metal element Ti in the used polynary compound carbonitride solid solution powder powder stock, W, Ta, Nb, the weight of Mo has certain ratio, in general, and in the time of by weight percentage, (Ti, W) (C, N) 0.3≤Ti in the powder≤0.9,0.1≤W≤0.7; (Ti, W, Ta) (C, N) 0.3≤Ti in the powder≤0.8,0.1≤W≤0.3,0.1≤Ta≤0.4; (Ti, W, Ta, Nb) (C, N) 0.3≤Ti in the powder≤0.7,0.1≤W≤0.3,0.1≤Ta≤0.3,0.05≤Nb≤0.3; (Ti, W, Ta, Nb, Mo) (C, N) in the powder, 0.3≤Ti≤0.7,0.1≤W≤0.3,0.1≤Ta≤0.3,0.05≤Nb≤0.3,0.05≤Mo≤0.3.
Adopt sintering metal preparation method of the present invention, the carbide ceramics powder adopts Ti, W, Ta, Nb, V, Zr, the carbide of Cr, Mo etc. and/or their carbide of solid solution powder in the used raw material, and metal-powder then adopts Ni, Co and/or Mo powder.
Adopt sintering metal preparation method of the present invention, carbonitride, carbide ceramics powder and metal-powder granularity are generally Fsss≤3.5 in the used raw material, preferably Fsss≤1.5.
The forming agent that sintering metal preparation method of the present invention adopts is styrene-butadiene-styrene edge section polymkeric substance or polyoxyethylene glycol.
The present invention adopts the polynary compound carbonitride solid solution ceramic powdered preparation sintering metal of two or more different constituent elements, and contain small amount of metallic elements Zr, with the Ti (C on aforementioned patent technology and the market, N) based ceramic metal is compared, Ti (C of the present invention, N) base metal-ceramic material has higher hardness (HRA92.0～93.5), higher bending strength (σ
b=2050～1400Mpa), therefore remove and have wear resistance, red hardness, excellent chemical stability preferably, outside extremely low and the advantages such as intermetallic coefficient of friction, its obdurability is also very good, the cutter material that both can be used for cutting metal and alloy, can be used for moulding stock such as wortle, pressing die again.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1: with granularity is 1.0 (Fsss, down with) and meet the Ti (C of the final moiety weight percent of setting, N) and (Ti, W, Ta) (C, N) carbonitride ceramic powder, (Ti, W, Ta) wet ball-milling 48～96 hours after C, WC, TiC, ZrC, NbC and Mo2C carbide ceramics powder and metal Ni, the Co powder mixes is at Ti (C, N) N/ (N+C)=0.7 (weight ratio, down together) in the powder; (Ti, W, Ta) (C, N) N/ (N+C)=0.37 in the powder, Ti0.7, W0.2, Ta0.1 (weight percent, down together).The compound of preparation is precipitated 36～96 hours, vacuum-drying, add forming agent styrene-butadiene-styrene edge section polymkeric substance again, adding weight is 10% of compound weight, mix after drying and granulating, compression moulding, in vacuum oven, carry out dewaxing treatment then, vacuum tightness is higher than 5Pa during processing, and at 300 ℃ of insulation 120min, 520 ℃ of insulation 120min, carry out vacuum sintering subsequently, its vacuum tightness is higher than 0.1Pa, be warming up to 1300 ℃ the insulation 30min after, be warming up to 1500 ℃ again, insulation 60min cools off under vacuum environment at last.
Each the moiety weight percent of sintering metal that makes with above-mentioned feed composition and preparation process condition is: Ti40.1, W15.8, Ta5.3, Nb1.0, Zr0.3, V0, Al0, Mo10, Ni10, Co5.1, C+N12.4, Ta+Nb+V=6.3 wherein, Ni＞Co and Ni/ (Ni+Co)=0.66; The cermet material performance index are hardness HRA92.2, bending strength 2050MPa.
Embodiment 2: be 1.5 with granularity and meet the Ti (C of the final moiety weight percent of setting, N) and (Ti, W, Ta, Nb) (C, N) carbonitride ceramic powder, (Ti, W, Ta, Nb) C, WC, TiC, ZrC, TaC and VC carbide ceramics powder and metal Ni, Co, Mo powder mixes wet-milling 20 hours in high energy ball mill, Ti (C, N) N/ (N+C)=0.65 in the powder wherein; (Ti, W, Ta, Nb) (C, N) N/ (N+C)=0.3 in the powder, Ti0.7, W0.1, Ta0.1, Nb0.1.With the preparation compound without the precipitation direct vacuum-drying, add the forming agent polyvinyl alcohol again, adding weight is 8% of compound weight, mix after drying and granulating, compression moulding, in vacuum oven, carry out dewaxing treatment then, vacuum tightness is higher than 5Pa during processing, and at 350 ℃ of insulation 150min, 600 ℃ of insulation 150min; Carry out vacuum sintering subsequently, its vacuum tightness is higher than 0.1Pa, be warming up to 1300 ℃ the insulation 30min after, be warming up to 1480 ℃ again, the insulation 90min, under vacuum environment, cool off at last.
Each the moiety weight percent of sintering metal that makes with above-mentioned feed composition and preparation process condition is: Ti37.2, W14.2, Ta6.6, Nb0.9, Zr0.1, V1.0, Al0, Mo9.5, Ni12, Co6, C+N12.5, Ta+Nb+V=8.5 wherein, Ni＞Co and Ni/Ni+Co=0.66; The cermet material performance index are hardness HRA92.5, bending strength 1860MPa.
Embodiment 3: with granularity be 2.5 and meet the final moiety weight percent of setting Ti (C, N) and (Ti, W, Ta, Nb, Mo) (C, N) carbonitride ceramic powder, (Ti, Ta) C, WC, TiC, ZrC, Cr
3C
2And Mo
2C carbide ceramics powder and metal Ni, Co powder mixes wet ball-milling 72 hours, wherein Ti (C, N) N/ (N+C)=0.6 5 in the powder; (Ti, W, Ta, Nb, Mo) (C, N) N/ (N+C)=0.5 in the powder, Ti0.7, W0.1, Ta0.1, Nb0.05, Mo0.05.The compound of preparation is precipitated 96 hours, vacuum-drying, add forming agent styrene-butadiene-styrene edge section polymkeric substance again, adding weight is 15% of compound weight, mix after drying and granulating, compression moulding carry out dewaxing treatment then in vacuum oven, vacuum tightness is higher than 5Pa during processing, and at 250 ℃ of insulation 150min, 550 ℃ of insulation 150min; Carry out vacuum sintering subsequently, its vacuum tightness is higher than 0.1Pa, be warming up to 1300 ℃ the insulation 30min after, be warming up to 1490 ℃ again, the insulation 75min, under vacuum environment, cool off at last.
Each the moiety weight percent of sintering metal that makes with above-mentioned feed composition and preparation process condition is: Ti38.0, W17.0, Ta8.4, Nb1.6, Cr1.0, Zr0.5, V0, Al0.5, Mo4.5, Ni6.5, Co10, C+N12.7, Ta+Nb+V=10 wherein, Ni＜Co and Ni/Ni+Co=0.39; The cermet material performance index are hardness HRA92.7, bending strength 1825MPa.
Embodiment 4: be 3.5 with granularity and meet the Ti (C of the final moiety weight percent of setting, N) and (Ti, W) (C, N) carbonitride ceramic powder, (Ti, W, Ta) C, WC, ZrC and TiC carbide ceramics powder and metal Ni, Co and Mo powder mixes wet ball-milling are 36 hours, wherein Ti (C, N) N/ (N+C)=0.67 in the powder; (Ti, W) (C, N) N/ (N+C)=0.3 in the powder, Ti0.8, W0.2.The compound of preparation is precipitated 48 hours, vacuum-drying, add forming agent styrene-butadiene-styrene edge section polymkeric substance again, adding weight is 12% of compound weight, mix after drying and granulating, compression moulding carry out dewaxing treatment then in vacuum oven, vacuum tightness is higher than 5Pa during processing, and at 320 ℃ of insulation 90min, 600 ℃ of insulation 150min; Carry out vacuum sintering subsequently, its vacuum tightness is higher than 0.1Pa, be warming up to 1300 ℃ the insulation 30mir after, be warming up to 1460 ℃ again, the insulation 90min, under vacuum environment, cool off at last.
Each the moiety weight percent of sintering metal that makes with above-mentioned feed composition and preparation process condition is: Ti45.6, W10.2, Ta1.0, Nb0, Zr5.0, V0, Al0, Mo10.1, Ni9.0, Co7.5, C+N11.6, Ta+Nb+V=1.0 wherein, Ni＞Co and Ni/Ni+Co=0.55; The cermet material performance index are hardness HRA93.5, bending strength 1437MPa.
Claims (10)
1. sintering metal, its each composition weight percent is: Ti30～65, W8～25, Ta1.0～15.0, Zr0.1～5.0, Nb0～10, Cr0～1.0, V0～5.0, Al0～1.0, Mo4.5～20, Ni3.5～15, Co4.5～15, all the other compositions are C and N.
2. sintering metal according to claim 1 is characterized in that by the weight percent meter in composition, Ta+Nb+V=1.02～0, Ni+Co=8～25, and Ni/ (Ni+Co)=0.2～0.8.
3. the described ceramic-metallic preparation method of claim 1 in turn includes the following steps:
Carbonitride ceramic powder, the carbide ceramics powder that (1) will be finally can satisfy each moiety weight percent of the described sintering metal of claim 1 mix with metal-powder and carry out wet-milling, and wet-milling makes compound after precipitate drying;
(2) press 81～5% of compound weight and add forming agent, carry out drying and granulating after the mixing, repressed moulding;
(3) will be pressed into moulding mixture and dewax in vacuum oven and sintering, dewaxing vacuum tightness is higher than 5Pa, respectively is incubated 90～150min between 250～350 ℃ and 400～650 ℃ being warming up to; Sintering vacuum tightness is higher than 0.1Pa, and sintering process is: be warming up to 1300 ℃ of insulation 30～50min; Be warming up to 1400～1500 ℃ of insulation 30～100min again; And under vacuum environment, cool off.
4. ceramic-metallic preparation method according to claim 3, it is characterized in that described carbonitride ceramic powder comprises the polynary compound carbonitride solid solution ceramic powder of two or more different constituent elements at least, particularly contain a kind of Ti (C, N) the polynary compound carbonitride solid-solution powder of powder and a kind of Ti, W, Ta, Nb, Mo etc. at least.
5. ceramic-metallic preparation method according to claim 4, it is characterized in that described Ti (C, N) in the powder, by weight timing, N/ (N+C)=0.6～0.8.
6. ceramic-metallic preparation method according to claim 4 is characterized in that described polynary compound carbonitride solid-solution powder can be (Ti, W, Ta, Nb, Mo) (C, N) powder can also be (Ti, W) (C, N), or (Ti, W, Ta) (C, N), or (Ti, W, Ta, Nb) (C, N) powder, and by weight timing, N/ in these powder (N+C)=0.3～0.6.
7. ceramic-metallic preparation method according to claim 6, when it is characterized in that metallic element is by weight percentage in the described polynary compound carbonitride solid solution powder, (Ti, W) (C, N) 0.3≤Ti in the powder≤0.9,0.1≤W≤0.7; (Ti, W, Ta) (C, N) 0.3≤Ti in the powder≤0.7,0.1≤W≤0.3,0.1≤Ta≤0.4; (Ti, W, Ta, Nb) (C, N) 0.3≤Ti in the powder≤0.7,0.1≤W≤0.3,0.1≤Ta≤0.3,0.05≤Nb≤0.3; (Ti, W, Ta, Nb, Mo) (C, N) in the powder, 0.3≤Ti≤0.7,0.1≤W≤0.3,0.1≤Ta≤0.3,0.05≤Nb≤0.3,0.05≤Mo≤0.3.
8. ceramic-metallic preparation method according to claim 3 is characterized in that described carbide ceramics powder is by carbide and/or their carbide of solid solution powder constituents such as Ti, W, Ta, Nb, V, Zr, Cr, Mo; Described metal-powder adopt Ni, Co and (or) the Mo powder.
9. according to each described ceramic-metallic preparation method in the claim 3 to 8, it is characterized in that described carbonitride, carbide ceramics powder and metal-powder granularity are: Fsss≤3.5.
10. ceramic-metallic preparation method according to claim 3 is characterized in that described forming agent is styrene-butadiene-styrene edge section polymkeric substance or polyoxyethylene glycol.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1304617C (en) * | 2005-04-19 | 2007-03-14 | 吉林省明洋刀具有限责任公司 | Blade material of artificial board chipping machine and its production method |
| CN1312078C (en) * | 2004-10-29 | 2007-04-25 | 华中科技大学 | Submicron grain Ti(C,N)-base cermet and its prepn process |
| CN101255512B (en) * | 2008-04-07 | 2010-06-02 | 株洲钻石切削刀具股份有限公司 | Boron-containing titanium carbide nitride based metal ceramic cutter material and preparation technique thereof |
| CN102191420A (en) * | 2011-05-26 | 2011-09-21 | 株洲钻石切削刀具股份有限公司 | Tungsten-free and cobalt-free Ti (C, N)-based metal ceramic and preparation method thereof |
| CN102383019A (en) * | 2011-10-18 | 2012-03-21 | 李海坤 | Superfine crystalline Ti(C,N)-based cermet and preparation method thereof |
| CN103820692A (en) * | 2014-03-07 | 2014-05-28 | 华中科技大学 | Ti (C, N) base cermet using Ni3Al and Ni as binder and its prepn |
| CN105149591A (en) * | 2015-09-21 | 2015-12-16 | 安庆创跃电器有限公司 | Composite alloy blade production process |
| 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 |
| CN110616357A (en) * | 2019-09-05 | 2019-12-27 | 长沙众鑫达工具有限公司 | Carbonitride-based cermet and preparation process thereof |
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- 2002-12-02 CN CNB021397902A patent/CN1180109C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1312078C (en) * | 2004-10-29 | 2007-04-25 | 华中科技大学 | Submicron grain Ti(C,N)-base cermet and its prepn process |
| CN1304617C (en) * | 2005-04-19 | 2007-03-14 | 吉林省明洋刀具有限责任公司 | Blade material of artificial board chipping machine and its production method |
| CN101255512B (en) * | 2008-04-07 | 2010-06-02 | 株洲钻石切削刀具股份有限公司 | Boron-containing titanium carbide nitride based metal ceramic cutter material and preparation technique thereof |
| CN102191420A (en) * | 2011-05-26 | 2011-09-21 | 株洲钻石切削刀具股份有限公司 | Tungsten-free and cobalt-free Ti (C, N)-based metal ceramic and preparation method thereof |
| CN102191420B (en) * | 2011-05-26 | 2012-11-21 | 株洲钻石切削刀具股份有限公司 | Tungsten-free and cobalt-free Ti (C, N)-based metal ceramic and preparation method thereof |
| CN102383019A (en) * | 2011-10-18 | 2012-03-21 | 李海坤 | Superfine crystalline Ti(C,N)-based cermet and preparation method thereof |
| CN103820692A (en) * | 2014-03-07 | 2014-05-28 | 华中科技大学 | Ti (C, N) base cermet using Ni3Al and Ni as binder and its prepn |
| CN103820692B (en) * | 2014-03-07 | 2015-03-04 | 华中科技大学 | Ti (C, N) base cermet using Ni3Al and Ni as binder and its prepn |
| CN105149591A (en) * | 2015-09-21 | 2015-12-16 | 安庆创跃电器有限公司 | Composite alloy blade production process |
| 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 |
| CN110616357A (en) * | 2019-09-05 | 2019-12-27 | 长沙众鑫达工具有限公司 | Carbonitride-based cermet and preparation process thereof |
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Granted publication date: 20041215 Termination date: 20201202 |