CN1180110C - Metal ceramic and its preparation method - Google Patents
Metal ceramic and its preparation method Download PDFInfo
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- CN1180110C CN1180110C CNB021397929A CN02139792A CN1180110C CN 1180110 C CN1180110 C CN 1180110C CN B021397929 A CNB021397929 A CN B021397929A CN 02139792 A CN02139792 A CN 02139792A CN 1180110 C CN1180110 C CN 1180110C
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Abstract
The present invention discloses Ti(C, N)-base cermet and a preparing method thereof. The cermet comprises the following components: 30 to 65 wt% of Ti, 8 to 25 wt% of W, 1.0 to 15.0 wt% of Ta, 0.1 to 5.0 wt% of Zr, 0 to 10 wt% of Nb, 0 to 1.0 wt% of Cr, 0 to 5.0 wt% of V, 0 to 1.0 wt% of Al, 4.5 to 20 wt% of Mo, 3.5 to 15 wt% of Ni, 4.5 to 15 wt% of Co, and C and N as the rest. The cermet is prepared by mixing two or more than two kinds of multiple-element combined type carbon nitride ceramic powder with different elements, carbide powder and/or solid solution carbide powder of Ti, W, Ta, Nb, V, Zr, Cr, Al, Mo, etc., and powder of metal Co, Ni and Mo, etc. by the steps of ball mill pulverization, pressing and shaping, dewaxing in vacuum and sintering in vacuum. The cermet has the advantages of excellent abrasion resistance and high strength and ductility, and can be used as mold materials of cutting tools, wire-drawing molds, compression molds, etc.
Description
Technical field
This 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 every industry or trade 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) the Base Metal cutter has accounted for about 25～30% market to numerical control blade aspect Ti, the salient features of its main trade mark: hardness (HRC) 91.0～94.0, bending strength 1200～2000Mpa.Chinese patent CN88107079.3 (open day is on May 10th, 1989) provides a kind of cermet cutting tool.Composition is: 3.5≤Ni≤6.5,4.5≤Co≤7.5,20≤W≤25,5≤Mo≤11,0≤Ta+Nb≤6, and 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 TiC for C, N) powder.Provide a kind of composite cermet and preparation method thereof among the Chinese patent CN01133646.3 (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 have higher-strength (composite cermet of σ b=2500～2630Mpa) and preparation method thereof, but its wear resistance lower (HRA=91.7～90.0).Although (C, N) based ceramic metal obtains bigger development at home and abroad to TiC, above-mentionedly puts the subject matter that product and patented technology exist on market and remains the obdurability deficiency, the product performance instability in recent years.
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 hard high-wearing feature, improve the intensity and the toughness of cermet material greatly, make it have excellent comprehensive performances, both can well be used for cutting tool material, can be used for 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, Co4.5～15, all the other compositions are C and N; 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.
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 each moiety weight percent of above-mentioned sintering metal mix with metal-powder and carry out wet-milling, wet-milling makes compound after precipitation is dry; Described carbonitride ceramic powder comprises the polynary compound carbonitride solid solution ceramic powder of two or more different constituent elements at least, and described carbide ceramics powder is by the carbide of Ti, W, Ta, Nb, V, Zr, Cr, Mo and/or their carbide of solid solution powder constituent; Described metal-powder adopts Ni, Co and/or Mo powder; (2) press 81～5% of compound weight and add forming agent, carry out drying and granulating after the mixing, repressed moulding; Described forming agent is styrene-butadiene-styrene edge section polymkeric substance or polyoxyethylene glycol; (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.
Described material carbon nitride ceramics powder contains a kind of Ti (C, N) powder and a kind of (Ti, W, Ta at least, Nb, and Mo) (C, N), (Ti, W) (C, N), (Ti, W, Ta) (C, N), (Ti, W, Ta, Nb) (C, N) polynary compound carbonitride solid-solution powder, and by weight timing, Ti (C, N) N/ (N+C)=0.6～0.8 in the powder, in the polynary compound carbonitride solid-solution powder of Ti, W, Ta, Nb, Mo, N/ (N+C)=0.3～0.6.
In addition, metal element Ti in 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≤0.7,0.1≤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.
Adopt Ti of the present invention (C, the N) preparation method of based ceramic metal, carbonitride, carbide ceramics powder and the general Fsss of metal-powder granularity≤3.5, preferably Fsss≤1.5 in the used raw material.
The present invention adopts the polynary compound carbonitride solid solution ceramic powdered preparation cermet material of two or more different constituent elements, and contain a spot of metallic element 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 (HRA=91.7～90.0), higher bending strength (σ b=2050～1400Mpa), therefore remove and have wear resistance preferably, red hardness, excellent chemical stability, outside the low advantages such as coefficient of friction of metal compole, 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
The invention will be further described below in conjunction with embodiment.
Embodiment 1: with granularity is 1.0 (Fsss, down with) and meet the Ti (C of the final moiety weight percent of setting, N), (Ti, W, Ta) (C, N) carbonitride ceramic powder, (Ti, W, Ta) C, WC, TiC, ZrC, NbC, Mo2C carbide ceramics powder and metal Ni, Mo powder mixes were carried out wet ball-milling 48～96 hours, at Ti (C, N) N/ (N+C)=0.7 (weight ratio, down together) in the powder; (Ti, W, Ta) N/ (N+C)=0.37 in the C powder, Ti0.7, W0.2, Ta0.1 (weight percent, down together).The compound of preparation is precipitated 36-96 hour, 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, after being warming up to 1300 ℃ of insulation 30min,, under vacuum environment, cool off at last being warming up to 1500 ℃ of insulation 60min.
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+N) 12.4, 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 σ b2050Mpa.
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, VC carbide ceramics powder and metal Ni, Co, Mo powder mixes ball milling 20 hours in the high-performance ball mill, wherein N/ (N+C)=0.65; (Ti, W, Ta, Nb) (C, N) N/ (N+C)=0.3 in the powder, Ti0.7, W0.1, Ta0.1, Nb0.1.The compound of preparation without the direct vacuum-drying of precipitation, is added the forming agent polyvinyl alcohol again, and adding weight is 8% 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 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, being warming up to 1480 ℃ of 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+N) 12.5, 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 σ b1860Mpa.
Embodiment 3: be 2.5 with granularity and meet the Ti (C of the final moiety weight percent of setting, N) and (Ti, W, Ta, Nb) (C, N) the carbonitride ceramic powder, (Ti, Ta) C, WC, TiC, ZrC, Cr3C2 and Mo2C carbide ceramics powder and metal Ni, Co powder mixes wet ball-milling are 72 hours, Ti (C, N) N/ (N+C)=0.65 in the powder wherein; (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, in vacuum oven, carry out dewaxing treatment then, 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, after being warming up to 1300 ℃ of insulation 30min,, under vacuum environment, cool off at last being warming up to 1490 ℃ of insulation 75min.
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, Zr1.0, Zr0.5, V0, Al0.5, Mo4.5, Ni6.5, Co10, (C+N) 12.7, Ta+Nb+V=10 wherein, Ni＜Co and Ni/ (Ni+Co)=0.39; The cermet material performance index are hardness HRA92.7, bending strength σ b1825Mpa.
Embodiment 4: with granularity be 3.5 and meet the final moiety weight percent of setting Ti (C, 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, in vacuum oven, carry out dewaxing treatment then, 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, after being warming up to 1300 ℃ of insulation 30min,, under vacuum environment, cool off at last being warming up to 1460 ℃ of insulation 90min.
Each the moiety weight percent of sintering metal that makes with above-mentioned feed composition and preparation process condition is: Ti45.6, and W10.2, Ta1.0, Nb0, Zr 5.0, V0, Al0, Mo10.1, Ni9.0, Co7.5, (C+N) 11.6, Ta+Nb+V=1.0 wherein, Ni＞Co and Ni/ (Ni+Co)=0.5 5; The cermet material performance index are hardness HRA93.5, bending strength σ b1437Mpa.
Claims (7)
1, a kind of 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; By the weight percent meter in composition, Ta+Nb+V=1.0～20, Ni+Co=8～25, and Ni/ (Ni+Co)=0.2～0.8.
2, 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; Described carbonitride ceramic powder comprises the polynary compound carbonitride solid solution ceramic powder of two or more different constituent elements at least, described carbide ceramics powder is by the carbide of Ti, W, Ta, Nb, V, Zr, Cr, Mo and/or their carbide of solid solution powder constituent, and described metal-powder adopts Ni, Co and/or Mo powder;
(2) press 81～5% of compound weight and add forming agent, carry out drying and granulating after the mixing, repressed moulding; Described forming agent is styrene-butadiene-styrene edge section polymkeric substance or polyoxyethylene glycol;
(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.
3, ceramic-metallic preparation method according to claim 2 is characterized in that described carbonitride ceramic powder contains a kind of Ti (C, N) the polynary compound carbonitride solid-solution powder of powder and a kind of Ti, W, Ta, Nb, Mo at least.
4, ceramic-metallic preparation method according to claim 3, it is characterized in that described Ti (C, N) in the powder, by weight timing, N/ (N+C)=0.6～0.8.
5, ceramic-metallic preparation method according to claim 3 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.
6, ceramic-metallic preparation method according to claim 5, 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.
7,, it is characterized in that described carbonitride, carbide ceramics powder and metal-powder granularity are: Fsss≤3.5 according to each described ceramic-metallic preparation method in the claim 2 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634685A (en) * | 2011-02-10 | 2012-08-15 | 厦门金鹭特种合金有限公司 | Ultra-coarse grain cemented carbide secondary liquid-phase sintering process |
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