CN101070577A - Super-fine TiC0.7N0.3 base metal ceramic and preparing method - Google Patents

Super-fine TiC0.7N0.3 base metal ceramic and preparing method Download PDF

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CN101070577A
CN101070577A CN 200710049108 CN200710049108A CN101070577A CN 101070577 A CN101070577 A CN 101070577A CN 200710049108 CN200710049108 CN 200710049108 CN 200710049108 A CN200710049108 A CN 200710049108A CN 101070577 A CN101070577 A CN 101070577A
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sintering
superfine
milling
wet
powder
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CN 200710049108
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Chinese (zh)
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熊计
郭智兴
杨梅
沈保罗
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四川大学
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Abstract

This invention has publicized one kind of superfine cermet and its preparation method. Each composition ingredient weight percent of this cermet is: Mo2C: 8-13wt %; WC: 10-15wt %; TaC: 5-8wt %; NiCo:10.5-14.5wt % (also Co: Ni = 60: 40); the reminder is TiC0.7N0.3. This cermet uses the superfine TiC0.7N0.3 solid solution as raw material powder, and deoxidation process the superfine powder, it solved the technical difficult problems of preparation superfine cermet such as wet milling easy to to be agglomeration, compaction easy to dehiscence and easy to form holes after being sintered because powder granularity thin and breath. The processed powder adopt optimization wet milling craft, and add stearic acid mountain ash grain fat dispersing agent; Suppressed under 300 -400MPa pressure to shape; do dewaxing under 10-15Pa higher than vacuum degree; sinter vacuum degree is higher than 1-5X10-2Pa, sinter temperature is 1400degree C-1,480degree C, then holding 1-1.5h; do the hot isostatic pressing processing at 1,350degree C, holding 90-120min, the argon pressure is 70-120MPa. The prepared cermet has crystal grain size 0.5mum and the typical core - link structure, its hardness is>=93HRA, anti-curved intensity>=2200MPa, it may used as half precision work and precision work cutting tool material.

Description

Superfine Ti C 0.7N 0.3Based ceramic metal and preparation method thereof
Technical field
The present invention is sintering metal and preparation method thereof, particularly superfine Ti C 0.7N 0.3Based ceramic metal and preparation method thereof.
Background technology
(C, N) (C N) is main hard phase to based ceramic metal to Ti, and Ni/Co is the bonding phase, and adds WC, Mo with Ti 2C, TaC, VC, ZrC, Cr 3C 2, carbide such as HfC improves performance.Compare with traditional sintered carbide tool material, sintering metal has good hardness, wear resistance, excellent chemical stability, oxidation-resistance and anti-stick cutter ability and low frictional coefficient.Therefore sintering metal can be used as the cutting tool of difficult-to-machine materials such as high mangaenese steel, structural alloy steel, Special Casting Iron (as containing niobium, boracic, high chromium and hard cast iron etc.), superalloy, roll and hot surfacing coated material, and can allow the higher cutting speed and the bigger depth of cut, enhance productivity.Simultaneously, sintering metal uses reserves abundant Ti, Ni, has avoided traditional Wimet strategic resource W rare to costliness, and the mass consumption of Co has great resources advantage and cost advantage.For these reasons, ceramic tool abroad developed country obtained the application of arriving very much.According to statistics, in the metal cutting field of Japan, ceramic tip has accounted for 30% of indexable insert tip, throw away tip sum, is still enlarging its range of application so far, and the main trade mark of Japanese market sees Table 1 at present; And the U.S. only accounts for 5%, but has begun to widely apply ceramic tool in Americanized industry.Along with the development of sintering metal manufacturing technology, the Application Areas of ceramic tool and usage quantity enlarge rapidly and increase.China also develops the Ti (C of multiple model during " eight or five ", N) base ceramet tool bit, and mass marketed, but unstable properties, obdurability is on the low side, under the high speed cutting condition, shakes very big, therefore these blades do not obtain practical application basically, and table 2 is several ceramic-metallic trade mark and a performance on probation on the Chinese market.
The ceramic-metallic trade mark and the performance used always on table 1 Japanese market
Performance ????N302 ??N308 ????N310 ??N350 ??NX252 ?5
The main energy of giving birth to High-wearing feature High tenacity High tenacity more High tenacity more High-wearing feature and toughness
Form ??TiCN-WC-TaC ??TiCN-WC-TaC ??TiCN-WC-TaC ??(Ti.W.Ta)CN Ultra-fine grain
Hardness (HRA) ??93.0~94.0 ??91.0~92.0 ??91.0~92.0 ??91.5~92.5 ??92.5
Bending strength (N/mm 2) ??1300~1500 ??1600~1800 ??1700~1900 ??1700~1900 ??1800
Density (g/cm 3) ??6.4 ??7.0 ??7.0 ??7.0 ??7.0
Using several ceramic-metallic trade mark and performance on table 2 Chinese market
Performance ??TN05 ?TN10 ??TN20 ??TN30 ??NT6
Salient features High-wearing feature Toughness is than the Tnu5 height The toughness wear resisting property is better Toughness wear resistancies etc. are better High anti-abrasion and high toughness
Hardness (HRA) ??≥93 ?≥92.5 ??≥91.5 ??≥90.5 ??≥92.5
Bending strength (N/mm 2) ??1000 ?1200 ??≥1400 ??≥1550 ??≥1300
Density (g/cm 3) ??≥6.2 ?≥6.5 ??≥16.8 ??≥6.8 ??≥6.8
Patent CN1093121, CN1410574 disclose a kind of Ti (C, N) based ceramic metal and preparation method thereof respectively.But the sintering metal grain fineness number in the patent belongs to middle coarse particles, is not the superfine metal pottery, and has used difficult at present the acquisition, and expensive polynary complicated sosoloid (Ti, W, Ta, Nb).And present studies show that, by crystal grain thinning, particularly grain fineness number drops to 0.5 μ m (ultra-fine) when following, can obtain hardness, intensity, the cermet material that toughness three is high.But adopt very difficulty of ultra-fine following feedstock production sintering metal, along with the refinement of granularity, surface energy increases, and reunites easily during wet-milling, is difficult for disperseing; And the refinement of powder causes, and powder activity is increased sharply, oxygen uptake easily, and the oxygen level of particulate powders increases that retarded elasticity increases in the time of can causing powder forming, and the easy delamination splitting of pressed compact is difficult to moulding; Make goods produce hole in a large number during sintering, cause the hurried decline of alloy property.Control for Oxygen Content is a difficult problem in the ultra-fine following sintering metal preparation process.
Patent CN1346816 adopts the method for mechanical alloying to prepare nano level TiC, prepares Ti (C, N) based ceramic metal; Patent CN1477222 adopt part add nano TiC and (or) method of TiN comes modification Ti (C, N) based ceramic metal; The sintering metal performance is improved, but two patents all are to take the method for TiC+TiN to introduce N,, can suppress the decomposition of nitride when sintering, reduce defective and form and improve material density if introduce N with the form of sosoloid.
Therefore, 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.Therefore must when guaranteeing premium propertiess such as its hardness, wear-resisting life, red hardness, improve its strength and toughness.Only in this way, just might make find application on the cutter market at home purpose of this patent of the coming material of this kind adopt ultra-fine feed stock exactly, and introduce N, come superfine Ti (C, N) based ceramic metal of processability excellence with the form of sosoloid
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of novel superfine Ti (C, N) based ceramic metal, and the preparation method of superfine metal pottery is provided are provided.
Sintering metal of the present invention, its each composition weight percent is: Mo 2C:8~13wt%; WC:10~15wt%; TaC:5~8wt%; Ni/Co:10.5~14.5wt% (and Co: Ni=60: 40); All the other are TiC 0.7N 0.3
The aforesaid sintering metal of the present invention is characterized in that the granularity of each moiety is: TiC 0.7N 0.3:<0.1 μ m; WC:<0.4 μ mMo 2C:<0.7 μ m; TaC:<1 μ m; Ni/Co:<1 μ m.
The aforesaid ceramic-metallic preparation method of the present invention in turn includes the following steps:
(1) with the superfine Ti C described in the claim 1 0.7N 0.3Make deoxidation treatment in powder;
(2) various carbide, carbonitride and the metal-powder that will finally can satisfy each moiety weight percentage of the described sintering metal of claim 1 mixes wet-milling;
(3) material after the wet-milling is dry through precipitation, makes compound, compression moulding;
(4) the compacting green compact are made sintering metal through vacuum sintering and hip treatment.
The aforesaid ceramic-metallic preparation method of the present invention, it is further characterized in that:
(1) superfine Ti C 0.7N 0.3Deng the deoxidation treatment of powder at H 2The continuous pusher Mo silk calcining furnace of protection, or carry out in the vacuum sintering furnace;
(2) wet-milling is carried out in the roller milling machine, and wet grinding media is a hexane, and mill ball is the WC-8wt%Co sintered carbide ball;
(3) add stearic acid sorb grain fat during wet-milling and make dispersion agent, add the wax moulding agent before wet-milling finishes;
(4) hip treatment is carried out under argon shield.
The aforesaid ceramic-metallic preparation method of the present invention, its processing parameter:
(1) at H 2In the continuous pusher Mo silk calcining furnace of protection when carrying out deoxidation treatment: push away boat speed and be 20 boats/minute, high temperature zone temperature is 400 ℃, H 2Flow velocity is 2m 3/ h; When carrying out deoxidation treatment in vacuum sintering furnace: be incubated 1 hour down at 1500 ℃, vacuum tightness is 0.5Pa;
(2) grinding rate is 48h for the 68r/min milling time, and the mill ball diameter is 6mm, and ratio of grinding media to material is 15: 1, and the add-on of dispersion agent stearic acid sorb grain fat is 0.3wt%;
(3) add-on of wax moulding agent is 5wt~8wt%, and the joining day is that wet-milling finishes preceding 2~3 hours; Pressing pressure is 300~400MPa;
(4) dewaxing is higher than under 10~15Pa in vacuum tightness and carries out, and is incubated 2~4h between 400 ℃~500 ℃;
(5) sintering vacuum tightness is higher than 1~5 * 10 -2Carry out under the Pa, sintering temperature is 1400 ℃~1480 ℃, and soaking time is 1~1.5h;
(6) hip treatment is carried out under 1350 ℃, insulation 90~120min, and argon pressure is 70~120MPa;
The invention has the advantages that:
The present invention adopts TiC 0.7N 0.3The sosoloid raw material has been avoided the shortcoming with the form introducing N of TiC+TiN, can suppress the decomposition of nitride when sintering, reduces defective and forms also raising material density.To TiC 0.7N 0.3Solid-solution powder is a ultrafine powder, and has carried out deoxidation treatment, has solved this difficult problem of Control for Oxygen Content in the superfine metal Production of Ceramics process; Add dispersion agent stearic acid sorb grain fat during wet-milling and make the ultrafine powder homodisperse; Adopt hip treatment behind the sintering, eliminate the space.Prepared superfine metal pottery has typical core/ring structure, its grain fineness number≤0.5 μ m, its hardness 〉=93HRA, bending strength 〉=2200Mpa, can be used for semi-finishing and precision work cutter material, compare, have suitable cutting ability with external suitable superfine metal ceramic tip.
Description of drawings
Example 1 superfine Ti C among Fig. 1 the present invention 0.7N 0.3Pattern after the powder deoxidation treatment
Pattern among Fig. 2 the present invention after the example 1 mixed powder wet-milling
Example 1 superfine Ti C among Fig. 3 the present invention 0.7N 0.3Pattern behind the sintering metal sintering
Example 2 superfine Ti C among Fig. 4 the present invention 0.7N 0.3Pattern after the powder deoxidation treatment
Pattern among Fig. 5 the present invention after the example 2 mixed powder wet-millings
Example 2 superfine Ti C among Fig. 6 the present invention 0.7N 0.3Pattern behind the sintering metal sintering
Embodiment
Example 1: the granularity of each moiety is: TiC 0.7N 0.3: 0.05~0.13 μ m; WC:0.2~0.4 μ m; Mo 2C:0.4 0.7 μ m; TaC:0.8~1 μ m; Ni/Co:<1 μ m.Mo wherein 2C:10wt%; WC:15wt%; TaC:7wt%; NiCo:14.5wt% (and Co: Ni=60: 40); All the other are TiC 0.7N 0.3Sosoloid.Superfine Ti C 0.7N 0.3The deoxidation treatment of powder is at H 2Carry out in the continuous pusher Mo silk calcining furnace of protection.Superfine Ti C 0.7N 0.3Powder places on the clean graphite boat, sends into logical H 2Carry out deoxidation treatment in the continuous pusher Mo silk calcining furnace of protection, push away boat speed and be 20 boats/minute, 400 ℃ of high temperature zone temperatures, H 2Flow velocity 2m 3/ hour.Pattern after the processing is seen Fig. 1, and composition analysis sees Table 3.To meet various carbide, carbonitride and the metal-powder of forming weight percentage then and mix, and grind in the drum-type wet wheeling machine, wet grinding media is a hexane, and mill ball is the WC-8wt%Co sintered carbide ball; Grinding rate is 68r/min, and milling time is 48h, and the mill ball diameter is 6mm, and ratio of grinding media to material is 15: 1, adds stearic acid sorb grain fat during wet-milling and makes dispersion agent, adds the wax moulding agent before wet-milling finishes; The add-on of dispersion agent stearic acid sorb grain fat is 0.3wt%, and the add-on of wax moulding agent is 5wt~8wt%, and the joining day is that wet-milling finishes preceding 2~3 hours; SEM pattern after the grinding is seen Fig. 2.Slip, is pressed after the drying through precipitation, is pressed into SNUN120408 machine folder throw away chip, and pressing pressure is 300~400MPa.Sintering in vacuum sintering furnace, dewaxing is higher than under 10~15Pa in vacuum tightness to be carried out, and is incubated 2-4h between 400 ℃~500 ℃; Sintering vacuum tightness is higher than 1~5 * 10 -2Carry out under the Pa, sintering temperature is 1450 ℃, and soaking time is 1h.Carry out hip treatment then, hip treatment is carried out under 1350 ℃, and to be 70MPa. have typical core/ring structure, its grain fineness number≤0.5 μ m according to the sintering metal of mentioned component and processing condition preparation to insulation 90min argon pressure, bending strength 2250MPa, hardness 93.5HRA.Its microscopic appearance is seen Fig. 3.
Table 3 superfine Ti C 0.7N 0.3Powder chemical ingredients of powder after the deoxidation treatment in Mo silk calcining furnace
Project Oxygen Nitrogen Total carbon Uncombined carbon Chloride residue Other
Content wt% ????0.22 ????6.98 ????14.96 ????1 ????0.25 ????-
Sintering metal according to mentioned component and processing condition preparation, on grinding machine, use the diamond wheel sharpening with plain metal pottery and Japanese NX2525 superfine metal sintex, adopt NJ-CK6140 digital controlled lathe (digital control system FANUC OTD) to carry out the cutting ability experiment, the work material of testing is modified 9CrSi, and hardness is HRC50.The tool setting angle is: anterior angle γ o=-8 ° of relief angle α o=-6, tool cutting edge angle χ r=45 °, auxiliary angle χ r`=45 °, cutting edge inclination λ s=-3 °, blade radius R=0.3mm; The Tool in Cutting parameter is: amount of feed F=0.1mm/r; Cutting speed V=200m/min; Depth of cut a p=1mm;
Cutting experiment is the result show: under above-mentioned cutting experiment condition, the durability of superfine metal pottery is 4 times of plain metal pottery, than Japanese NX2525 slightly good when knife face VB=0.23mm (behind the blade, the cutting time of several blades is for seeing Table 4); The workpiece surface roughness of superfine metal pottery NT6B cutter processing is 0.7 μ m, is better than the 0.9 μ m of Japanese NX2525 and 1.2 μ m of plain metal pottery.
The cutting time t (min) of several blades during knife face VB=0.23mm behind table 4 blade
The blade trade mark ????NX2525 The superfine metal pottery The plain metal pottery
Cutting time t ????5.83min ????5.98min ????1.53min
Example 2: the granularity of each moiety is: TiC 0.7N 0.3: 0.05~0.13 μ m; WC:0.2~0.4 μ m; Mo 2C:0.4-0.7 μ m; TaC:0.8~1 μ m; Ni/Co:<1 μ m.Mo wherein 2C:13wt%; WC:15wt%; TaC:8wt%; NiCo:13wt% (and Co: Ni=60: 40); All the other are TiC 0.7N 0.3Sosoloid.Superfine Ti C 0.7N 0.3Deoxidation treatment in powder is carried out in vacuum sintering furnace.Superfine Ti C 0.7N 0.3Place on the clean graphite boat in powder, send into and carry out deoxidation treatment in the vacuum sintering furnace, be incubated 1 hour down at 1500 ℃, vacuum tightness is 0.5Pa.Pattern after the processing is seen Fig. 4, and composition analysis sees Table 5.To meet various carbide, carbonitride and the metal-powder of forming weight percentage then and mix, and grind in the drum-type wet wheeling machine, wet grinding media is a hexane, and mill ball is the WC-8wt%Co sintered carbide ball; Grinding rate is 68r/min, and milling time is 48h, and the mill ball diameter is 6mm, and ratio of grinding media to material is 15: 1, adds stearic acid sorb grain fat during wet-milling and makes dispersion agent, adds the wax moulding agent before wet-milling finishes; The add-on of dispersion agent stearic acid sorb grain fat is 0.3wt%, and the add-on of wax moulding agent is 5wt~8wt%, and the joining day is that wet-milling finishes preceding 2~3 hours; SEM pattern after the grinding is seen Fig. 5.Slip, is pressed after the drying through precipitation, is pressed into SNUN120408 machine folder throw away chip, and pressing pressure is 300~400MPa.Sintering in vacuum sintering furnace, dewaxing is higher than under 10~15Pa in vacuum tightness to be carried out, and is incubated 2-4h between 400 ℃~500 ℃; Sintering vacuum tightness is higher than 1~5 * 10 -2Carry out under the Pa, sintering temperature is 1480 ℃, and soaking time is 1.5h.Carry out hip treatment then, hip treatment is carried out under 1350 ℃, insulation 120min, argon pressure is 90MPa, has typical core/ring structure, its grain fineness number≤0.5 μ m according to the sintering metal of mentioned component and processing condition preparation, bending strength 2450MPa, hardness 93HRA.Its microscopic appearance is seen Fig. 6.
Table 5 superfine Ti C 0.7N 0.3Powder chemical ingredients of powder after the deoxidation treatment in vacuum sintering furnace
Project Oxygen Nitrogen Total carbon Uncombined carbon Chloride residue
Content wt% ????0.06 ????7.55 ????13.51 ????0.5
Sintering metal according to mentioned component and processing condition preparation, on grinding machine, use the diamond wheel sharpening with plain metal pottery and Japanese NX2525 superfine metal sintex, adopt NJ-CK6140 digital controlled lathe (digital control system FANUC OTD) to carry out the cutting ability experiment, the work material of testing is modified 9CrSi, and hardness is HRC50.The tool setting angle is: anterior angle γ o=8 ° of relief angle α o=6, tool cutting edge angle χ r=45 °, auxiliary angle χ r`=45 °, cutting edge inclination λ s=-3 °, blade radius R=0.3mm; The Tool in Cutting parameter is: amount of feed F=0.1mm/r; Cutting speed V=200m/min; Depth of cut a p=1mm;
Cutting experiment is the result show: under above-mentioned cutting experiment condition, the durability of superfine metal pottery is 4 times of plain metal pottery, than Japanese NX2525 slightly good when knife face VB=0.23mm (behind the blade, the cutting time of several blades is for seeing Table 6); The workpiece surface roughness of superfine metal pottery NT6B cutter processing is 0.72 μ m, is better than the 0.9 μ m of Japanese NX2525 and 1.2 μ m of plain metal pottery.
The cutting time t (min) of several blades during knife face VB=0.23mm behind table 6 blade
The blade trade mark ????NX2525 The superfine metal pottery The plain metal pottery
Cutting time t ????5.83min ????6.01min ????1.53min

Claims (5)

1. sintering metal, its each composition weight percent is: Mo 2C:8~13wt%; WC:10~15wt%; TaC:58wt%; Ni/Co:10.5~14.5wt% (and Co: Ni=60: 40); All the other are TiC 0.7N 0.3
2. sintering metal according to claim 1 is characterized in that the granularity of each moiety is: TiC 0.7N 0.3:<0.1 μ m; WC:<0.4 μ m; Mo 2C:<0.7 μ m; TaC:<1 μ m; Ni/Co:<1 μ m.
3. ceramic-metallic preparation method according to claim 1 in turn includes the following steps:
(1) with the superfine Ti C described in the claim 1 0.7N 0.3Make deoxidation treatment in powder;
(2) various carbide, carbonitride and the metal-powder that will finally can satisfy each moiety weight percentage of the described sintering metal of claim 1 mixes wet-milling;
(3) material after the wet-milling is dry through precipitation, makes compound, compression moulding;
(4) the compacting green compact are made sintering metal through vacuum sintering and hip treatment.
4. sintering metal preparation method according to claim 3 is characterized in that:
(1) superfine Ti C 0.7N 0.3Deng the deoxidation treatment of powder at H 2The continuous pusher Mo silk calcining furnace of protection, or carry out in the vacuum sintering furnace;
(2) wet-milling is carried out in the roller milling machine, and wet grinding media is a hexane, and mill ball is the WC-8wt%Co sintered carbide ball;
(3) add stearic acid sorb grain fat during wet-milling and make dispersion agent, add the wax moulding agent before wet-milling finishes;
(4) hip treatment is carried out under argon shield.
5. sintering metal preparation method according to claim 4 is characterized in that:
(1) at H 2In the continuous pusher Mo silk calcining furnace of protection when carrying out deoxidation treatment: push away boat speed and be 20 boats/minute, high temperature zone temperature is 400 ℃, H 2Flow velocity is 2m 3/ h; When carrying out deoxidation treatment in vacuum sintering furnace: be incubated 1 hour down at 1500 ℃, vacuum tightness is 0.5Pa;
(2) grinding rate is 68r/min, and milling time is 48h, and the mill ball diameter is 6mm, and ratio of grinding media to material is 15: 1, and the add-on of dispersion agent stearic acid sorb grain fat is 0.3wt%;
(3) add-on of wax moulding agent is 5wt~8wt%, and the joining day is that the preceding 2~3h. pressing pressure of wet-milling end is 300400MPa;
(4) dewaxing is higher than under 10~15Pa in vacuum tightness and carries out, and is incubated 2-4h between 400 ℃~500 ℃;
(5) sintering vacuum tightness is higher than 1~5 * 10 2Carry out under the Pa, sintering temperature is 1400 ℃~1480 ℃, and soaking time is 1-1.5h;
(6) hip treatment is carried out under 1350 ℃, insulation 90~120min, and argon pressure is 70~120MPa.
CN 200710049108 2007-05-16 2007-05-16 Super-fine TiC0.7N0.3 base metal ceramic and preparing method CN101070577A (en)

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CN101792880A (en) * 2010-03-12 2010-08-04 四川大学 Weak core ring structured novel cermet material based on (Ti, M) (C, N) solid solution powder
CN101845581A (en) * 2010-05-26 2010-09-29 四川大学 Production method of metal ceramic surface wear-resistant material
CN102337442A (en) * 2011-09-26 2012-02-01 四川大学 Metal ceramic seal ring material and preparation method thereof
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CN101792880A (en) * 2010-03-12 2010-08-04 四川大学 Weak core ring structured novel cermet material based on (Ti, M) (C, N) solid solution powder
CN101792880B (en) * 2010-03-12 2015-07-01 四川大学 Weak core ring structured novel cermet material based on (Ti, M) (C, N) solid solution powder
CN101845581A (en) * 2010-05-26 2010-09-29 四川大学 Production method of metal ceramic surface wear-resistant material
CN101845581B (en) * 2010-05-26 2012-01-25 四川大学 Production method of metal ceramic surface wear-resistant material
CN102337442B (en) * 2011-09-26 2012-11-28 四川大学 Metal ceramic seal ring material and preparation method thereof
CN102337442A (en) * 2011-09-26 2012-02-01 四川大学 Metal ceramic seal ring material and preparation method thereof
CN102534336A (en) * 2011-12-02 2012-07-04 厦门钨业股份有限公司 Metal ceramic and preparation method thereof
CN103060760A (en) * 2012-11-28 2013-04-24 厦门虹鹭钨钼工业有限公司 Preparation method for molybdenum-titanium alloy target
CN103552099A (en) * 2013-09-29 2014-02-05 河南华茂新材料科技开发有限公司 High-strength ceramic ultrathin cutting blade and production method thereof
CN104674098B (en) * 2015-02-13 2017-04-12 四川大学 Cermet material based on TiCN-(Ti,M)CN core mixed structure and preparation method thereof
CN104674098A (en) * 2015-02-13 2015-06-03 四川大学 Cermet material based on TiCN-(Ti,M)CN core mixed structure and preparation method thereof
CN104889466A (en) * 2015-06-11 2015-09-09 山东大学 Integral full-ceramic super dense-tooth three-edge milling cutter and manufacturing method thereof
CN106270493A (en) * 2016-08-03 2017-01-04 成都锦钛精工科技有限公司 A kind of ceramic metal composite alloy spherical powder and preparation method thereof
CN107245625A (en) * 2017-06-12 2017-10-13 长沙伟徽高科技新材料股份有限公司 A kind of Tungsten carbide titanium tantalum molybdenum solid-solution powder and preparation method thereof
CN108149108A (en) * 2017-12-04 2018-06-12 株洲夏普高新材料有限公司 Toughened cermet and preparation method thereof
CN109609829A (en) * 2018-12-25 2019-04-12 苏州新锐合金工具股份有限公司 Ti(C, N) based ceramic metal nitrogen balance control method
CN110512131A (en) * 2019-09-05 2019-11-29 四川轻化工大学 A kind of bulk metal ceramal bar and the preparation method and application thereof

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