CN1609052A - Submicron grain Ti(C,N)-base cermet and its prepn process - Google Patents
Submicron grain Ti(C,N)-base cermet and its prepn process Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims description 51
- 239000011195 cermet Substances 0.000 title abstract description 9
- 238000000034 method Methods 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 150000004767 nitrides Chemical class 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 31
- 238000000498 ball milling Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000000748 compression moulding Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 22
- 239000000956 alloy Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000000713 high-energy ball milling Methods 0.000 abstract description 3
- 238000003825 pressing Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 58
- 239000002245 particle Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- 229910009043 WC-Co Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006263 metalation reaction Methods 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000003701 mechanical milling Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The present invention relates to the preparation of cermet material, and the sintered alloy has submicron crystal grain structure, and high hardness, toughness and strength. The cermet is prepared through mixing IVB, VB, VIB, Ti, one or more metal carbide, nitride or complex solid solution carbide-nitride ceramic powder and iron family element Ni, Co, etc.; high-energy ball milling, drying, pressing to form, vacuum sintering, hot isostatic pressing and other steps. The cermet has hard crystal phase reaches submicron granularity of 0.6-1.0 micron. Under scanning electronic microscope, four kinds of metal structure may be observed including black core phase, white core phase, gray ring phase and white adhesion phase. Compared with available cermet, the present invention has obviously improved hardness and toughness, and may be used in cutter and other wear resistant parts.
Description
Technical field
The present invention relates to cermet material, particularly sub-micron grain Ti (C, N) based ceramic metal and preparation method thereof.
Background technology
Sintering metal has that density is low, hardness and red hardness are higher than Wimet, chemical stability and good in oxidation resistance,, thermal expansivity little to the frictional coefficient of steel is higher than performance characteristics such as WC-Co Wimet, is suitable for as cutting tool, measurer, mould, wear part etc.Early stage sintering metal composition is TiC-Mo-Ni, and its wear resistance is better than the WC-Co Wimet, but intensity and toughness is far inferior to the WC-Co Wimet, and this has limited ceramic-metallic range of application.Rudy finds to add an amount of TiN and improves ceramic-metallic toughness effectively in sintering metal, can be applicable to the High Speed Machining of steel, described in No. 3971656, United States Patent (USP), its micro-metallographic structure mainly is made up of three parts: titanium carbonitride core phase, on every side for containing the carbonitride annular phase of Mo, Ti, all the other are the bonding phase to core mutually.After this relevant Ti (C, N) research of based ceramic metal rolls up, the carbide of IVB, VB, VIB transiting group metal elements, nitride ceramics join in the alloy as additive, and to the optimization of bonding phase alloy composition, the use properties that makes sintering metal be applied to cutting tool constantly improves, and the application of polynary compound sosoloid carbonitride powder has also improved ceramic-metallic use properties.Chinese patent 88107079.3 provides a kind of cermet cutting tool, and its composition comprises Ti, Mo, W, Ta, Nb, Cr, Co, Ni, C, N etc., and the grain fineness number of carbonitride hard phase is a micron order in the alloy.Chinese patent 94102287.0 provides a kind of sintering metal and preparation method thereof, used starting material are the (Ti of grain-size＜1.5 μ m, W, Ta, Nb) C, Ti (C, N) and WC powder, they and Ni, the pulverizing together of Co powder, compacting sintering are made, and the sintered alloy hard has core phase-annular phase structure mutually, and core is its composition Ti (C mutually, N), annular is mutually for containing the carbonitride of Ti, W, Ta, Nb.Hard phase average crystal grain diameter＜1.5 μ m.Chinese patent 96121920.3 provides a kind of Ti (C, N) based ceramic metal, it has core phase-annular phase structure, be distributed in around the core phase but annular is mutually discontinuous, so that core partly be exposed to mutually metal bonding mutually in, and described discontinuous geminus hard phase volume umber is 30% or more, and this sintering metal cutting tip presents superior resistance to fracture.Chinese patent 01133646.3 a kind of grain refining is provided Ti (C, N) based ceramic metal, but its main preparation technology's characteristics are for to prepare powder mix with the mechanical alloying method.Generally speaking, ceramic-metallic obdurability awaits further raising.Table 1 is the trade mark and the performance of domestic and international several common metal ceramals.
The common metal pottery trade mark and performance on table 1 domestic and international market
| Alloy designations | Major ingredient | Hardness (HRA) | Bending strength (MPa) | Use properties |
| Japan N302 | Ti(C，N)，WC，TaC， Ni/Co | ?93.0～94.0 | 1200～1400 | High-wearing feature |
| Japan N308 | Ti(C，N)，WC，TaC， Ni/Co | ?91.0～92.0 | 1600～1800 | High tenacity |
| Japan N310 | Ti(C，N)，WC，TaC， Ni/Co | ?91.0～92.0 | 1700～1900 | High tenacity more |
| Japan N350 | (Ti，W，Ta)(C，N)，Ni/Co | ?91.5～92.5 | 1700～1900 | High tenacity more |
| China YN05 | TiC，Mo，Ni | ?≥93.0 | ≥950 | High-wearing feature |
| China YN10 | Ti(C，N)，Mo，Ni | ?≥92.5 | ≥1200 | Toughness is higher than YN05 |
| China YN20 | Ti(C，N)，Mo，Ni | ?≥91.5 | ≥1400 | Toughness preferably |
| China YN30 | Ti(C，N)，Mo，Ni | ?≥90.5 | ≥1550 | High tenacity |
Summary of the invention
(C, N) based ceramic metal is so that its hardness and obdurability have clear improvement than present sintering metal performance to the invention provides a kind of sub-micron grain Ti.Another task of the present invention provide described sub-micron grain Ti (C, the N) preparation method of based ceramic metal, thereby make sintered alloy have the sub-micron crystal kernel structure, have higher hardness and toughness concurrently, have very low porosity, thereby improve the intensity of alloy.
(C, N) based ceramic metal are made of with bonding hard sub-micron grain Ti of the present invention mutually mutually, the expression formula of hard phase composition is (Ti, M) (C, N), M is one or more among metallic element Cr, the Mo except that Ti, W, Nb, the Ta in IVB, VB, the VIB transition group; Bonding phase composition is Ni, Co or its mixture; It is characterized in that: its moiety atomic percent is: Ti24～42, Mo 0～7.0, W 0～16.0, Ta 0～3.0, Nb 0～5.0, Cr 0～4.0, Co 0～13, Ni 0～30, all the other compositions are C and N; Hard phase grain fineness number reaches submicron order, is 0.6～1.0 μ m; Can be observed four kinds of metallographic structures under scanning electronic microscope: black core phase, white core phase, grey annular bond mutually with white mutually; The black core be mutually Ti (C, N), white core mutually for the sintering commitment form (Ti, M) (C, N) phase, grey annular are (Ti, M) (C, the N) phase, but the content of M is lower in mutually than white core of sintering later stage formation mutually.
(it is further characterized in that for C, N) based ceramic metal: hard phase C, N content ratio are described sub-micron grain Ti: N/ (C+N)=0.1～0.7; The volume parts of white core phase is greater than the volume parts of black core phase.
(according to preparation technology's difference, white can contain other metallic element of 1～20% in boning mutually to described sub-micron grain Ti for C, N) based ceramic metal.
Sub-micron grain Ti of the present invention (C, the N) preparation method of based ceramic metal may further comprise the steps successively:
(1) can satisfy Ti of the present invention (C, N) carbon of based ceramic metal composition, nitride ceramics powder mix with metal-powder, adopt high energy ball mill to carry out wet-milling, make powder mix refine to submicron order; Described ceramic powder is binary carbide, nitride or its polynary carbonitride sosoloid of IVB, VB, VIB magnesium-yttrium-transition metal, and metal-powder adopts Ni, Co or its mixture;
(2) powder mix adds forming agent, drying, granulation compression moulding;
(3) rolled-up stock is carried out degreasing and sintering in vacuum sintering furnace, in the hot isostatic pressing stove, carry out HIP again and handle; Perhaps rolled-up stock carries out sintering in sintering-hot isostatic pressing stove, and its degreasing, sintering and hot isostatic pressing are finished in a heat-processed.
(C, the N) preparation method of based ceramic metal is characterized in that the granularity Fsss≤20 μ m of the ceramic powder in the described starting material, metal-powder Fsss≤3 μ m to described sub-micron grain Ti; Described forming agent is paraffin or polyvinyl alcohol.
Described sub-micron grain Ti (C, N) preparation method of based ceramic metal, carry out high energy ball mill that wet-milling is adopted and to be agitating ball mill or planetary ball mill, make powder mix refine to submicron order by the control milling parameters, stirring ball-milling technology must guarantee the linear velocity＞0.5m/s of ball-milling medium.
Ti (C, N) fracture toughness property of based ceramic metal is a face-centred cubic structure, as Ti (C, when N) particle is thick, transgranular fracture very easily takes place, and also significant deflection or bifurcated can not take place during the expansion of the continuous transcrystalline of crackle, sintering metal presents stronger brittle rupture feature; And when Ti (C, the transgranular fracture probability reduced greatly when N) particle was thin, crackle more easily (C, N) expand with bonding interface mutually, causes minimizing of brittle rupture phenomenon and crack deflection and toughness reinforcing along Ti by particle.In addition, because black Ti (C, N) core and the annular composition difference between mutually, make and have tensile stress in the black core mutually, make the black core be easy to take place transgranular fracture (96121920.3) mutually, therefore reduce black Ti (C, N) granularity of core phase and reduction black Ti (C, N) ratio of core phase all helps reducing the microtexture stress of alloy, thereby improves the obdurability of alloy.
Cermet material weave construction provided by the invention is different from Chinese patent 96121920.3, but can reduce the structural stress between black core phase and the annular phase equally, and hard phase grain fineness number is a submicron order, so its hardness and obdurability had clear improvement than former sintering metal performance.
Fig. 1 is that (C, the N) scanning electron photomicrograph of based ceramic metal have only three kinds of metallographic structures: black core phase, grey annular bond mutually with white micron order Ti mutually.Fig. 2 is a kind of sub-micron grain Ti (C provided by the invention, N) scanning electron photomicrograph of based ceramic metal, its hard phase grain fineness number reaches submicron order, be 0.6～1.0 μ m, structure can be observed four kinds of metallographic structures under scanning electronic microscope: black core phase, white core phase, grey annular bond mutually with white mutually, the black core be mutually Ti (C, N); The white core mutually for sintering commitment formation (Ti, M) (M is one or more IVB, VB, VIB transition group other metal except that Ti for C, N) phase.The grey annular mutually for the sintering later stage form (Ti, M) (its hardness and obdurability had clear improvement than former sintering metal performance for C, N) phase, but the content of M is lower in mutually than white core.
The preparation method of cermet material of the present invention, in its step, high-energy ball milling technology and sintering process are crucial, high-energy ball milling makes powder be crushed to submicron order, thereby makes sintered alloy have the sub-micron crystal kernel structure, makes alloy have higher hardness and toughness concurrently; Hot isostatic pressing makes sintered alloy have very low porosity, thereby improves the intensity of alloy.
Description of drawings
Fig. 1 is micron order Ti (C, N) the ceramic-metallic scanning electron photomicrograph of basic technology;
Fig. 2 is sub-micron grain Ti of the present invention (C, N) scanning electron photomicrograph of based ceramic metal;
Fig. 3 is ceramic-metallic degreasing process;
Fig. 4 is ceramic-metallic vacuum sintering technology;
Fig. 5 is ceramic-metallic sintering-heat and other static pressuring processes.
Embodiment
Below in conjunction with example the present invention is further described.The used raw-material parameter of the present invention is as shown in table 2.
Table 2 starting powder granularity, composition (comprising foreign gas) content (wt%)
Foreign matter content
Powder title granularity (Fsss, μ m)
O
2(％)???N
2(％)????C(％)
TiC??????????????2.58??????????0.39??????0.035?????19.3
TiN??????????????8.1???????????0.34??????5.35??????0.31
WC???????????????2.1???????????0.3?????????????????5.92
Mo???????????????2.8???????????0.1?????????????????0.0012
(Ti，W)C?????????2.5???????????0.19??????0.32??????12.61
NbC??????????????2.37??????????0.24??????0.019?????11.2
TaC??????????????2.2???????????0.14??????0.037?????6.2
Ni???????????????2.8???????????0.15????????????????0.15
Co???????????????1.23??????????0.02
Cr???????????????11.3??????????0.13
Example 1:
Selecting TiC, TiN, WC, Mo, Ni in the table 2 for use is that starting material add an amount of carbon dust, make preparation Ti (C, N) each moiety atomic percent of based ceramic metal is approximately: Ti 38, and Mo 4.5, and W 1.3, and Ni 13, and N 6.5, all the other are C.Specimen preparation adopts stirring ball-milling, sintering-heat and other static pressuring processes or vacuum sintering.Stirring ball-milling must make the linear velocity of ball-milling medium motion reach more than the 0.5m/s; Ratio of grinding media to material is 5: 1; 2,6,12,24 hours respectively ball milling time.Add an amount of forming agent in the powder mix mechanical milling process, oven dry is after sintering is carried out in compression molding then.Sintering carries out in sintering-hot isostatic pressing all-in-one oven, and the sintering temperature sintering temperature is 1420 ℃, uses argon gas to make transmission medium, and atmosphere pressures is 1.7MPa.Powder to ball milling 24h also carries out the vacuum sintering ball milling.The performance of alloy is as shown in table 3.The vacuum sintering alloy is owing to the porosity height, and intensity is lower.Ball milling 6h alloy hard phase particle sizes is a micron order, and the scanning electron microscopy metallograph as shown in Figure 1.Reach 12h when above when the stirring ball-milling time, the hard phase particle sizes of alloy reaches submicron order, and Fig. 2 is the scanning electron microscopy metallograph of stirring ball-milling 12h alloy.
The compression moulding part carried out Tuo La and sintering in vacuum sintering furnace after, carrying out HIP again in the hot isostatic pressing stove handles, rolled-up stock also can carry out sintering in sintering-hot isostatic pressing stove, it takes off cured, sintering and hot isostatic pressing can be finished in a heat-processed, and corresponding sintering is shown in Fig. 3,4,5.
Alloy hard phase particle sizes of different stirring ball-milling time of table 3 and performance
| Ball-milling technology | Sintering process | ?HRA | ?KIC(MNm -3/2) | ??TRS | Hard phase grain fineness number | Porosity |
| Stirring ball-milling 2h stirring ball-milling 6h stirring ball-milling 12h stirring ball-milling 24h stirring ball-milling 24h | Sintering-HIP sintering-HIP sintering-HIP sintering-high temperature insostatic pressing (HIP) vacuum-sintering | ? ?90.2 ? ? ?90.5 ? ? ?91.0 ? ? ?91.3 ? ? ?91.5 | ? ????8.6 ? ? ????8.93 ? ? ????9.48 ? ? ????9.53 ? ? ????9.13 | ? ??1736 ? ? ??1859 ? ? ??1931 ? ? ??2008 ? ? ??1156 | ? ????2.01 ? ? ????1.40 ? ? ????0.90 ? ? ????0.68 ? ? ????0.70 | ???A02， ? ???B00 ???A02， ? ???B00 ???A02， ? ???B00 ???A02， ? ???B00 ???A06， ? ???B06 |
Example 2:
Select for use the starting material in the table 2 to prepare burden, (C, N) each moiety atomic percent of based ceramic metal is as shown in table 4 to make the various Ti of preparation.Specimen preparation adopts stirring ball-milling, sintering-heat and other static pressuring processes.Stirring ball-milling must make the linear velocity of ball-milling medium motion reach more than the 0.5m/s; Ratio of grinding media to material is 5: 1; 12 hours respectively stirring ball-milling time.Add an amount of forming agent in the powder mix mechanical milling process, oven dry is after sintering is carried out in compression molding then.Sintering carries out in sintering-hot isostatic pressing all-in-one oven, and the sintering temperature sintering temperature is 1420 ℃, uses argon gas to make transmission medium, and atmosphere pressures is 1.7MPa.The performance and the hard phase particle sizes of each alloy are as shown in table 5.
The various ceramic-metallic compositions of table 4
| The prescription sequence number | Adopt starting material | Ti (C, N) based ceramic metal alloy ingredient (atm.%) | |||||||||
| ?Ti | ?Mo | ?W | ?Ta | ?Nb | ?Ni | ?Co | ?Cr | ?N | C | ||
| ????1 | ?TiC，TiN，Mo，WC，Ni，C | ?42 | ?4.5 | ?1.2 | ?6.1 | ?5.8 | All the other | ||||
| ????2 | ?TiC，TiN，Mo，WC，Ni，C | ?37 | ?4.5 | ?1.3 | ?13 | ?6.5 | All the other | ||||
| ????3 | ?TiC，TiN，Mo，WC，Ni，Co， ?C | ?32 | ?7.0 | ?1.4 | ?21 | ?5.0 | ?6.8 | All the other | |||
| ????4 | ?TiC，TiN，Mo，WC，NbC，Ni， ?C | ?27 | ?6.2 | ?1.5 | ?5.0 | ?30 | ?7.1 | All the other | |||
| ????5 | ?TiC，TiN，Mo，WC，Co，C | ?37 | ?4.5 | ?1.3 | ?13 | ?6.5 | All the other | ||||
| ????6 | ?TiC，TiN，Mo，WC，NbC，Ni， ?C | ?40 | ?3.3 | ?12 | ?5.6 | All the other | |||||
| ????7 | ?TiC，TiN，Mo，WC，TaC，Ni， ?C | ?41 | ?1.8 | ?12 | ?5.6 | All the other | |||||
| ????8 | ?(Ti，W)C，TiN，Ni，TaC，C | ?24 | ?16 | ?3.0 | ?20 | ?9 | All the other | ||||
| ????9 | ?TiC，TiN，Mo，WC，Ni，Cr，C | ?37 | ?4.5 | ?1.3 | ?9 | ?4 | ?6.5 | All the other | |||
Various ceramic-metallic performance and alloy hard phase particle sizes that table 5 prepares with the stirring ball-milling method
Material prescription
Porosity
HRA KIC (MNm
-3/2) TRS hard phase grain fineness number
Sequence number
1???????????92.0???????8.06????????1789???????0.92????????A02，B00
2???????????91.0???????9.48????????1931???????0.90????????A02，B00
3???????????88.6???????13.67???????2259???????0.86????????A02，B00
4???????????84.7???????????????????2261???????0.82????????A02，B00
5???????????91.8???????8.57????????1724???????0.94????????A04，B00
6???????????90.6???????9.08????????1771???????0.88????????A02，B00
7???????????90.0???????9.53????????2109???????0.92????????A02，B00
8???????????88.5???????9.70????????2024???????0.98????????A02，B00
9???????????92.0???????7.82????????1634???????0.96????????A02，B00
Example 3:
Selecting TiC, TiN, WC, Mo, Ni in the table 2 for use is that starting material add an amount of carbon dust, make preparation Ti (C, N) each moiety atomic percent of based ceramic metal is approximately: Ti 38, and Mo 4.5, and W 1.3, and Ni 13, and N 6.5, all the other are C.Specimen preparation adopts planetary ball mill, sintering-heat and other static pressuring processes.Planetary ball mill rotating disk revolution speed is set at 450rpm.The ball milling time is respectively 12; 24h.Add an amount of forming agent behind the powder mix ball milling, oven dry is after sintering is carried out in compression molding then.Sintering carries out in sintering-hot isostatic pressing all-in-one oven, and the sintering temperature sintering temperature is 1420 ℃, uses argon gas to make transmission medium, and atmosphere pressures is 1.7MPa.The performance and the hard phase grain fineness number of 12,24 hours alloys of ball milling are as shown in table 6.
Table 6 planetary ball mill Ti (C, N) performance of based ceramic metal and hard phase grain fineness number
Ball-milling technology HRA KIC (MNm
-3/2) TRS hard phase grain fineness number porosity
Planetary ball mill 12h 90.8 9.06 1,856 1.20 A02, B00
Planetary ball mill 24h 91.1 9.47 1,973 0.80 A02, B00
Claims (6)
1. (C, N) based ceramic metal are made of with bonding hard sub-micron grain Ti mutually mutually, the expression formula of hard phase composition is (Ti, M) (C, N), M is one or more among metallic element Cr, the Mo except that Ti, W, Nb, the Ta in IVB, VB, the VIB transition group; Bonding phase composition is Ni, Co or its mixture; It is characterized in that: its moiety atomic percent is: Ti24～42, Mo0～7.0, W0～16.0, Ta0～3.0, Nb0～5.0, Cr0～4.0, Co0～13, Ni0～30, all the other compositions are C and N; Hard phase grain fineness number reaches submicron order, is 0.6～1.0 μ m; Can be observed four kinds of metallographic structures under scanning electronic microscope: black core phase, white core phase, grey annular bond mutually with white mutually; The black core be mutually Ti (C, N), white core mutually for the sintering commitment form (Ti, M) (C, N) phase, grey annular are (Ti, M) (C, the N) phase, but the content of M is lower in mutually than white core of sintering later stage formation mutually.
Sub-micron grain Ti 2. as claimed in claim 1 (C, N) based ceramic metal is characterized in that: hard phase C, N content ratio are: N/ (C+N)=0.1～0.7; The volume parts of white core phase is greater than the volume parts of black core phase.
3. (C, N) based ceramic metal is characterized in that: white contains other metallic element of 1～20% in boning mutually to sub-micron grain Ti as claimed in claim 1 or 2.
4. described sub-micron grain Ti (C, the N) preparation method of based ceramic metal may further comprise the steps successively:
(1) can satisfy Ti of the present invention (C, N) carbon of based ceramic metal composition, nitride ceramics powder mix with metal-powder, adopt high energy ball mill to carry out wet-milling, make powder mix refine to submicron order; Described ceramic powder is binary carbide, nitride or its polynary carbonitride sosoloid of IVB, VB, VIB magnesium-yttrium-transition metal, and metal-powder adopts Ni, Co or its mixture;
(2) powder mix adds forming agent, drying, granulation compression moulding;
(3) rolled-up stock is carried out degreasing and sintering in vacuum sintering furnace, in the hot isostatic pressing stove, carry out HIP again and handle; Perhaps rolled-up stock carries out sintering in sintering-hot isostatic pressing stove, and its degreasing, sintering and hot isostatic pressing are finished in a heat-processed.
5. (C, the N) preparation method of based ceramic metal is characterized in that the granularity Fsss≤20 μ m of the ceramic powder in the described starting material, metal-powder Fsss≤3 μ m to sub-micron grain Ti as claimed in claim 4; Described forming agent is paraffin or polyvinyl alcohol.
6. according to claim 4 or 5 described sub-micron grain Ti (C, N) preparation method of based ceramic metal, it is characterized in that carrying out high energy ball mill that wet-milling is adopted is agitating ball mill or planetary ball mill, make powder mix refine to submicron order by the control milling parameters, stirring ball-milling technology must guarantee the linear velocity＞0.5m/s of ball-milling medium.
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