CN102839311B - Metal ceramic and preparation method thereof - Google Patents
Metal ceramic and preparation method thereof Download PDFInfo
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- CN102839311B CN102839311B CN201210311499.9A CN201210311499A CN102839311B CN 102839311 B CN102839311 B CN 102839311B CN 201210311499 A CN201210311499 A CN 201210311499A CN 102839311 B CN102839311 B CN 102839311B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
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- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
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Abstract
The invention discloses Ti (C, N)-based metal ceramic having good comprehensive mechanical properties, a cutting tool made of the metal ceramic and a preparation method for the strengthened and toughened Ti (C, N)-based metal ceramic. The metal ceramic comprises a hard phase, a bonding phase and a strengthening phase, wherein the hard phase consists of one or more kinds of compounds which are selected from carbides, nitrides, carbonitrides and carbonitride solid solution of metals in the fourth group, the fifth group and the sixth group of a periodic table, and the main metal element compounding the compounds is Ti; the bonding phase mainly comprises iron group metals; the strengthening phase comprises AlN nanowires and TiAlN compounds which are formed on bonding surfaces of the AlN nanowires and the hard phase compounds; the proportion that the total weight of the Al element in the AlN nanowires and the TiAlN compounds accounts for the weight of each unit of metal ceramic is more than 0 percent and is less than or equal to 5 percent. According to the metal ceramic, the hardness, the bending strength and the fracture toughness are improved, and good comprehensive mechanical properties are achieved.
Description
Technical field
The present invention relates generally to sintering metal and preparation method thereof, relates in particular to Ti(C, N) based ceramic metal and preparation method thereof.
Background technology
Ti(C, N) based ceramic metal is that a class is taking Ti(C, N) powder mix of powder or TiC and TiN is hard phase main raw material, taking metals such as Co, Ni, Mo as bonding phase raw material, and conventionally also add and have WC, TaC, NbC, Mo
2c, VC, Cr
3c
2the matrix material forming through pulverizing, mixing-mold pressing-sintering for additive Deng transition metal carbides, mainly for the manufacture of cutting tool.Wherein, the range of choice of bonding phase metal is wider, as CN102046823A(applicant: Sumitomo Electrics Industry Ltd) patent documentation in just propose in iron family metal, to choose arbitrarily.In fact, further combined with this patent documentation, can be by Ti(C, N) hard phase in based ceramic metal is summarised as: be to be made up of one or more compounds that are selected from carbide, nitride, carbonitride and the carbonitride sosoloid of the periodic table of elements the 4th family, the 5th family and the 6th family's metal, and the metallic element that forms these compounds is mainly Ti.At present, in order to improve Ti(C, N) hardness, fracture toughness property and the bending strength of based ceramic metal, the research direction of this area mainly concentrates on the interpolation aspect of transition metal carbides.
In reference 1-" add AlN to Ti(C, N) impact of based ceramic metal mechanical property and microstructure, Liu Ning etc.; physical and chemical inspection-physics fascicle, 1997 ", point out, at Ti(C, N) based ceramic metal adds after AlN micropowder, bondingly will produce Y ' [Ni in mutually
3(Al, Ti)] phase, Y ' has increased the obstruction of dislocation motion mutually, thereby makes bondingly to be strengthened mutually, can improve thus ceramic-metallic intensity and hardness.Reference 2-" nano TiN modified Ti(C; N) the based ceramic metal heat resistanceheat resistant performance of shaking; Zhang Xiaobo etc.; Wimet, the 24th the 3rd phase of volume, in September, 2007 " in point out, at Ti(C, N) in based ceramic metal, add nano TiN and can significantly improve sintering metal comprehensive mechanical property, major cause is 1, nano TiN is in bonding dissolving occupy-place in mutually and reduced hard phase in bonding solubleness in mutually, makes thus the crystal grain of hard phase obtain refinement; 2, nano TiN particle, to the pinning effect that misplaced, has increased the obstruction of dislocation motion; 3, nano TiN easily bonding mutually in dissolve, its Ti plays solution strengthening effect to bonding phase metal.
Summary of the invention
The present invention aims to provide a kind of Ti(C, N with excellent comprehensive mechanical property) based ceramic metal, and adopt this ceramic-metallic cutting tool and can strengthen toughness reinforcing Ti(C, N) preparation method of based ceramic metal.
For this reason, sintering metal of the present invention comprises:
Hard phase, described hard phase is made up of one or more compounds that are selected from carbide, nitride, carbonitride and the carbonitride sosoloid of periodictable the 4th family, the 5th family and the 6th family's metal, and the metallic element that forms these compounds is mainly Ti;
Bonding phase, is describedly bondingly mainly made up of iron family metal mutually; And
Strengthening phase, described strengthening phase comprise AlN nano wire and be formed at described AlN nano wire and hard phase compound bonding surface on TiAlN compound; The gross weight of the Al element in described AlN nano wire and TiAlN compound account for per unit sintering metal weight ratio > 0% and≤5%.
Research is found, in sintering process, be formed at the compound that the TiAlN compound on AlN nano wire and hard phase compound bonding surface is a kind of high temperatures, it has Ti in effectively isolated hard phase, N, the effect of the outside diffusion of C atom, thereby effectively suppress Ti, N, C atom is in bonding dissolving in mutually and separate out, reduce titanium carbonitride in bonding solubleness in mutually, reduce titanium carbonitride and dissolve the N decomposition that separating out grows up again causes bonding in mutually, strengthen the stability of titanium carbonitride, make titanium carbonitride crystal grain obtain refinement, improve ceramic-metallic hardness and obdurability.Meanwhile, AlN nano wire has fibre-reinforced effect to sintering metal, can further improve ceramic-metallic intensity and toughness.Based on such mechanism, Ti(C, N of the present invention) based ceramic metal is all improved in hardness, bending strength and fracture toughness property, reaches excellent comprehensive mechanical property.But, test also shows, if the gross weight of the Al element in AlN nano wire and TiAlN compound accounts for the ratio of per unit sintering metal weight while being greater than 5%, in material, fragility increases mutually the bending strength and the fracture toughness property that cause material is reduced to unacceptable degree.
At Ti(C, N of the present invention) in based ceramic metal, the gross weight of the Al element in described AlN nano wire and TiAlN compound preferably accounts for 2%～4% of per unit sintering metal weight.Test shows, in the time that the gross weight of the Al element in AlN nano wire and TiAlN compound is in above-mentioned interval range, Ti(C, N) based ceramic metal is all obviously being better than existing sintering metal aspect hardness, bending strength and fracture toughness property; If Al content, lower than 2%, strengthens toughness reinforcing effect not fairly obvious, if Al content higher than 4%, fragility phase increase will cause bending strength and the fracture toughness property of material reduce.
Cutting tool of the present invention, has sintering metal matrix, and described sintering metal matrix comprises:
Hard phase, described hard phase is made up of one or more compounds that are selected from carbide, nitride, carbonitride and the carbonitride sosoloid of periodictable the 4th family, the 5th family and the 6th family's metal, and the metallic element that forms these compounds is mainly Ti;
Bonding phase, is describedly bondingly mainly made up of iron family metal mutually; And
Strengthening phase, described strengthening phase comprise AlN nano wire and be formed at described AlN nano wire and hard phase compound bonding surface on TiAlN compound, the ratio that the gross weight of the Al element in described AlN nano wire and TiAlN compound accounts for per unit sintering metal weight is less than 5%.
Based on alleged cause, in cutting tool of the present invention, the gross weight of the Al element in described AlN nano wire and TiAlN compound preferably accounts for 2%～4% of per unit ceramet group body weight.
A kind of ceramic-metallic preparation method, the step comprising is:
1) prepare powdered mixture
The component of raw material and proportioning (weight percent)
Ti(C, N) powder: 40%～60%
Iron family metal: 10%～20%
AlN nano wire: 3%～6%
Transition metal carbides: all the other
According to above-mentioned component and proportioning, by Ti(C, N) powder, iron family metal and transition metal carbides pulverize and mix, and then adds AlN nano wire, and mix and make powdered mixture;
2) moulding
By pressure forming, above-mentioned powdered mixture is made to pressed compact;
3) sintering
Above-mentioned pressed compact is placed in to vacuum or protective atmosphere carries out sintering, when sintering, at 1380 DEG C～1480 DEG C, is incubated 1 hour～3 hours, obtain described sintering metal after cooling.
Through inspection, by above-mentioned preparation method, on AlN nano wire and hard phase compound bonding surface by formation TiAlN compound.And, the Ti(C, the N that are preparing) and in based ceramic metal, the gross weight of the Al element in described AlN nano wire and TiAlN compound accounts for 2%～4% of per unit sintering metal weight.
Concrete, described iron family metal is selected from one or more in Co, Ni, Fe, Cu.
Concrete, described transition metal carbides is selected from WC, TaC, NbC, Mo
2one or more in C.
Further, described transition metal carbides is by WC, TaC, NbC and Mo
2c composition, wherein, WC, TaC and NbC weight sum account for 10%～20% of described powdered mixture, and all the other are WC.
Pressure forming can select mold pressing, etc. the methods such as static pressure, extruding and rolling.
Than reference paper 1, Ti(C, N of the present invention) position, form and the structure of the strengthening phase that forms in based ceramic metal be not all identical, and to Ti(C, N) strengthening mechanism of based ceramic metal is also different.In addition, the concrete enforcement that will provide, also can find out Ti(C, N of the present invention below this specification sheets) based ceramic metal in hardness and bending strength all apparently higher than Ti(C, N in reference paper 1) hardness and the bending strength of based ceramic metal.
Than reference paper 2, Ti(C of the present invention, N) based ceramic metal is the object that reaches refinement hard phase crystal grain by being formed at Ti, N, the outside diffusion of C atom in the isolated hard phase of TiAlN compound on AlN nano wire and hard phase compound bonding surface, reference paper 2 is to reach the object of refinement hard phase crystal grain by nano TiN in bonding dissolving occupy-place in mutually, therefore both also exist essential difference.
Brief description of the drawings
Fig. 1 is the material hardness of the application's test example 1-8 change curve to Al nano wire addition.
Fig. 2 is the material bending strength of the application's test example 1-8 change curve to Al nano wire addition.
Fig. 3 is the material bending strength of the application's test example 1-8 change curve to Al nano wire addition.
The longitudinal axis unit of Fig. 1 is HRA, and the longitudinal axis unit of Fig. 2 is Mpa, and the longitudinal axis unit of Fig. 3 is Mpam
1/2.
Fig. 1, Fig. 2 and Tu3Zhong transverse axis unit are weight percentage.
Embodiment
< test example >
Manufacture Ti(C, N) based ceramic metal, then to these Ti(C, N) hardness, fracture toughness property and the bending strength of based ceramic metal detect.
The basic step of test is:
1) prepare powdered mixture
Take raw material by component and the proportioning set, in roller milling machine with ratio of grinding media to material (6～8): the speed of 1,20～40 revs/min, carry out the mixing and ball milling of 60～90 hours, prepare powdered mixture.
The initial time of last 10 hours that is arranged in ball milling that adds of AlN nano wire completes.
2) moulding
In powdered mixture, add the forming agent such as paraffin, PEG, stir, after sieving, in mould, pressed compact is made in mold pressing, and molding pressure is 100Mpa～300Mpa.
3) sintering
Above-mentioned pressed compact is placed in to vacuum or protective atmosphere carries out sintering, when sintering, at 1380 DEG C～1480 DEG C, is incubated 1 hour～3 hours, obtain Ti(C, N after cooling) based ceramic metal.
[table 1]
The component of raw material and proportioning (weight percent).
Table 1
Illustrate:
1, test number 1-8 is corresponding with the test number 1-8 in each table below respectively.
2, in the test of numbering 1-8, the add-on of AlN nano wire increases progressively 1% successively from 0%, finally reaches 7%.
3,, for ease of comparing, in the test of numbering 1-8, transition metal carbides is all selected from WC, NbC and Mo
2c.But in addition those skilled in the art obviously can determine, such as TaC, VC, Cr
3c
2all can be used as additive Deng other transition metal carbides.
4,, for ease of comparing, in the test of numbering 1-8, bonding phase raw material is all selected from Co, Ni.But those skilled in the art obviously can determine except Co, Ni, all can be used as bonding phase metal such as the iron family metal such as Fe, Cu.
5, in the interval that in the test of numbering 1-8, the content of each component all limits in the present invention, choose.
6, Ti(C, N in above-mentioned table) powder, WC powder, NbC powder, Mo
2c powder, Co powder, Ni powder and AlN nano wire are all from commercially available prod.
[table 2]
Roller milling machine operation parameter
Table 2
[table 3]
Sintering condition
Table 3
[table 4]
Test-results
Table 4
And, detect and find by x-ray photoelectron power spectrum (XPS), in the sample of test number 1-3,5-8, on AlN nano wire and hard phase compound bonding surface, be formed with TiAlN compound.
Test explanation:
1, as calculated, the ratio that in numbering 4 test gained sintering metal, the gross weight of the Al element in AlN nano wire and TiAlN compound accounts for per unit sintering metal weight is about 2%; The ratio that the gross weight of the Al element in the test gained sintering metal of numbering 7 in AlN nano wire and TiAlN compound accounts for per unit sintering metal weight is about 4%, and the ratio that the gross weight of the Al element in the test gained sintering metal of numbering 8 in AlN nano wire and TiAlN compound accounts for per unit sintering metal weight is about 4.6%.
2, in Fig. 1, numbering 6 the ceramic-metallic hardness of test gained declines suddenly, this and Ti(C, N) powder addition reduces relevant; In Fig. 3, the ceramic-metallic fracture toughness property of test gained of numbering 5 declines suddenly, and this reduces relevant with the addition of bonding phase metal.Get rid of the impact of these factors, increase progressively 5% process from 0% in the add-on of AlN nano wire, hardness, bending strength and the fracture toughness property of material are all rising trend.The add-on of the preferred AlN nano wire of the present invention is 3%～6%, and in this section of interval, the hardness of material, bending strength and fracture toughness property are obviously better than existing sintering metal.
Claims (6)
1. sintering metal, comprising:
Hard phase, described hard phase is made up of the multiple compounds being selected from carbide, nitride, carbonitride and the carbonitride sosoloid of the periodic table of elements the 4th family, the 5th family and the 6th family's metal, and the metallic element that forms these compounds is mainly Ti;
Bonding phase, is describedly bondingly mainly made up of iron family metal mutually; And
Strengthening phase, described strengthening phase comprise AlN nano wire and be formed at described AlN nano wire and hard phase compound bonding surface on TiAlN compound, the gross weight of the Al element in described AlN nano wire and TiAlN compound accounts for 2%～4% of per unit sintering metal weight; And
Prepare this ceramic-metallic raw material powder, the Ti (C that is 40%～60% by weight percent, N) powder, 10%～20% iron family element ting, > 3% and≤6% AlN nano wire and 26%～35% transition metal carbides composition, wherein, described > 3% and≤6% AlN nano wire is the source of AlN nano wire and TiAlN compound in the sintering metal strengthening phase sintering into; Described transition metal carbides is selected from WC, TaC, NbC, Mo
2one or more in C.
2. sintering metal as claimed in claim 1, is characterized in that: described iron family metal is selected from one or more in Co, Ni, Fe.
3. cutting tool, has sintering metal matrix, and described sintering metal matrix comprises:
Hard phase, described hard phase is made up of one or more compounds that are selected from carbide, nitride, carbonitride and the carbonitride sosoloid of the periodic table of elements the 4th family, the 5th family and the 6th family's metal, and the metallic element that forms these compounds is mainly Ti;
Bonding phase, is describedly bondingly mainly made up of iron family metal mutually; And
Strengthening phase, described strengthening phase comprise AlN nano wire and be formed at described AlN nano wire and hard phase compound bonding surface on TiAlN compound, the gross weight of the Al element in described AlN nano wire and TiAlN compound accounts for 2%～4% of per unit sintering metal weight, and
Prepare this ceramic-metallic raw material powder, the Ti (C that is 40%～60% by weight percent, N) powder, 10%～20% iron family element ting, > 3% and≤6% AlN nano wire and 26%～35% transition metal carbides composition, wherein, described > 3% and≤6% AlN nano wire is the source of AlN nano wire and TiAlN compound in the sintering metal strengthening phase sintering into; Described transition metal carbides is selected from WC, TaC, NbC, Mo
2one or more in C.
4. cutting tool as claimed in claim 3, is characterized in that: described iron family metal is selected from one or more in Co, Ni, Fe.
5. the ceramic-metallic preparation method of claim 1, the step comprising is:
1) prepare powdered mixture
The component of raw material and proportioning (weight percent)
Ti (C, N) powder: 40%～60%
Iron family metal: 10%～20%
AlN nano wire: > 3% and≤6%
Transition metal carbides: 26%～35%
According to above-mentioned component and proportioning, Ti (C, N) powder, iron family metal and transition metal carbides are pulverized and mixed, then add AlN nano wire, mix and make powdered mixture; Described transition metal carbides is selected from WC, TaC, NbC, Mo
2one or more in C;
2) moulding
By pressure forming, above-mentioned powdered mixture is made to pressed compact;
3) sintering
Above-mentioned pressed compact is placed in to vacuum or protective atmosphere carries out sintering, when sintering, at 1380 DEG C～1480 DEG C, is incubated 1 hour～3 hours, obtain described sintering metal after cooling.
6. ceramic-metallic preparation method as claimed in claim 5, is characterized in that: described iron family metal is selected from one or more in Co, Ni, Fe.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210311499.9A CN102839311B (en) | 2012-08-29 | 2012-08-29 | Metal ceramic and preparation method thereof |
| PCT/CN2013/072020 WO2014032418A1 (en) | 2012-08-29 | 2013-02-28 | Cermet and method for preparing cermet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210311499.9A CN102839311B (en) | 2012-08-29 | 2012-08-29 | Metal ceramic and preparation method thereof |
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| CN102839311A CN102839311A (en) | 2012-12-26 |
| CN102839311B true CN102839311B (en) | 2014-07-16 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839311B (en) * | 2012-08-29 | 2014-07-16 | 成都美奢锐新材料有限公司 | Metal ceramic and preparation method thereof |
| CN108220735B (en) * | 2017-12-28 | 2020-10-16 | 成都美奢锐新材料有限公司 | Reinforced phase system for preparing metal ceramic and preparation method thereof |
| CN108220734B (en) * | 2017-12-28 | 2020-10-16 | 成都美奢锐新材料有限公司 | Raw material powder for producing cermet and method for producing cermet |
| WO2019220533A1 (en) * | 2018-05-15 | 2019-11-21 | 住友電気工業株式会社 | Cermet, cutting tool containing same, and method for producing cermet |
| CN111500948B (en) * | 2020-03-25 | 2021-06-29 | 成都美奢锐新材料有限公司 | Co-phase-free TiCN-based metal ceramic material and preparation method thereof |
| CN114231780B (en) * | 2021-11-08 | 2022-12-23 | 成都美奢锐新材料有限公司 | Cermet material special for cigar scissors and preparation method thereof |
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| CN102839311B (en) * | 2012-08-29 | 2014-07-16 | 成都美奢锐新材料有限公司 | Metal ceramic and preparation method thereof |
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2012
- 2012-08-29 CN CN201210311499.9A patent/CN102839311B/en active Active
-
2013
- 2013-02-28 WO PCT/CN2013/072020 patent/WO2014032418A1/en active Application Filing
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| US5281484A (en) * | 1992-02-11 | 1994-01-25 | Mercedes-Benz Ag | High stress capability, intermetallic phase titanium aluminide coated components |
| CN101100719A (en) * | 2007-07-28 | 2008-01-09 | 中国石油化工集团公司 | Cermet composition and method for preparing cermet coat on metal surface |
| CN102046823A (en) * | 2009-03-24 | 2011-05-04 | 住友电气工业株式会社 | Cermet |
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| CN102839311A (en) | 2012-12-26 |
| WO2014032418A1 (en) | 2014-03-06 |
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Denomination of invention: Cermet and its preparation method Effective date of registration: 20220630 Granted publication date: 20140716 Pledgee: Huishang Bank Co.,Ltd. Chengdu Jinsha sub branch Pledgor: CHENGDU MET-CERAMICS ADVANCED MATERIALS Co.,Ltd. Registration number: Y2022510000179 |