EP0563203A1 - Method of producing a sintered carbonitride alloy for intermittent machining of materials difficult to machine. - Google Patents
Method of producing a sintered carbonitride alloy for intermittent machining of materials difficult to machine.Info
- Publication number
- EP0563203A1 EP0563203A1 EP92901893A EP92901893A EP0563203A1 EP 0563203 A1 EP0563203 A1 EP 0563203A1 EP 92901893 A EP92901893 A EP 92901893A EP 92901893 A EP92901893 A EP 92901893A EP 0563203 A1 EP0563203 A1 EP 0563203A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- raw material
- metals
- carbon
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 title abstract description 6
- 238000003754 machining Methods 0.000 title abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 229910021480 group 4 element Inorganic materials 0.000 claims abstract 2
- 230000000737 periodic effect Effects 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 5
- 238000005256 carbonitriding Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005056 compaction Methods 0.000 description 4
- 229960005419 nitrogen Drugs 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- -1 nitro- Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229940045605 vanadium Drugs 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C22C29/04—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 based on carbonitrides
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
Definitions
- the present invention relates to a method of produ ⁇ cing a sintered carbonitride alloy with titanium as main constituent particularly suited for intermittent machining of materials difficult to machine.
- Sintered carbonitride alloys based on mainly titanium usually referred to as cermets have during the last years increased their use at the expense of more tra ⁇ ditional cemented carbide i.e. tungsten carbide based alloys.
- US 3,971,656 discloses the production of an alloy with a duplex hard constituent where the core has a high content of Ti and N and the surrounding rim has a lower content of these two elements which is com- pensated for by a higher content of group VI metals i.e. in principle Mo and and by higher carbon con ⁇ tent.
- group VI metals i.e. in principle Mo and and by higher carbon con ⁇ tent.
- the higher content of Mo, and C has inter alia the advantage that the wetting against the bin- derphase is improved i.e. the sintering is facili- tated.
- As a raw material a carbonitride of titanium and a group VI metal is used.
- EP-A-259192 discloses a sintered alloy comprising a mixed carbonitride of titanium and at least one ele ⁇ ment from the group consisting of group IV, V and VI elements except titanium in a binder phase based on Co and/or Ni.
- the alloy is produced by mixing powders of the hard constituents, heating the mixture in a nitrogen atmosphere at a temperature of at least the sintering temperature to form a solid solution, mil ⁇ ling said solid solution to obtain a carbonitride powder which is mixed with Co and/or Ni and sintered.
- tita ⁇ nium and tantalum shall be present in the raw mate ⁇ rial according to the invention.
- SUBSTITUTE SHEET nium are present if they are part of the finished sintered alloy.
- the raw material accordinging to the invention is produ ⁇ ced directly by carbonitriding of the oxides of the metals or the metals themselves.
- a carbo ⁇ nitride powder with essentially equiaxial grains and a narrow grain size distribution is obtained with a mean grain size of 0.8 - 3 ⁇ m, preferably 1 - 2 ⁇ m.
- the invention thus relates to a method of producing a titanium based carbonitride alloy with 3-25 % by weight binderphase based on Co, Ni and/or Fe using the above mentioned complex raw material.
- This raw material is milled together with carbides from group VI, if any, and binderphase elements and carbon addi ⁇ tion, if any, and minor additions of e.g. TiC, TiN, TaC, VC or combinations thereof due to small devia- tions in composition of the complex raw material whe ⁇ reafter compaction and sintering, preferably in an inert atmosphere, is performed according to known technique.
- Fig 1 shows the 'window' in the composition diagram for Group IV-Group V - C-N, expressed in molar ratio, of the complex raw material which shows the above mentioned advantages in high magnification, whereas fig 2 shows where in the total molar ratio diagram this small area is situated.
- Group IV metals are Ti, Zr and/or Hf and Group V me ⁇ tals are V, b and/or Ta.
- the window comprises the composition area:
- the latter restricted window can be divided into two, one without other group V metals than Ta:
- oxygen may be present i.e. sub ⁇ stitute carbon and nitrogen even if it is desirable to keep such amounts of oxygen low ⁇ 0.8 %, preferably ⁇ 0.5 %.
- the invention comprises ⁇ toichiometric as well as usually substoichiometric carbonitrides.
- Titanium-based carbonitride alloys with 17.5 % Ni+Co binder phase were produced with the use of a complex raw material according to the invention
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
According to the invention there now is provided a method of producing a sintered titanium based carbonitride alloy with 3-25 weight-% binder phase with extremely good properties at intermittent machining of materials difficult to machine. The method relates to the use of a raw material comprising a complex cubic carbonitride containing the main part of the metals from groups IV and V of the periodic system and carbon and nitrogen to be found in the finished alloy whereby said alloy has the composition 0.86 </= XIV </= 0.97, 0.44 </= XC </= 0.55, where XIV is the molar ratio of the group IV elements of the alloy and XC is the molar ratio of carbon.
Description
Method of producing a sintered carbonitride allσv for intermittent machining of materials difficult to machine.
The present invention relates to a method of produ¬ cing a sintered carbonitride alloy with titanium as main constituent particularly suited for intermittent machining of materials difficult to machine.
Sintered carbonitride alloys based on mainly titanium usually referred to as cermets have during the last years increased their use at the expense of more tra¬ ditional cemented carbide i.e. tungsten carbide based alloys.
US 3,971,656 discloses the production of an alloy with a duplex hard constituent where the core has a high content of Ti and N and the surrounding rim has a lower content of these two elements which is com- pensated for by a higher content of group VI metals i.e. in principle Mo and and by higher carbon con¬ tent. The higher content of Mo, and C has inter alia the advantage that the wetting against the bin- derphase is improved i.e. the sintering is facili- tated. As a raw material a carbonitride of titanium and a group VI metal is used.
By changing the raw material it is possible to vary the core-rim-composition. In e.g. Swedish Patent Spe- cification 459 862 it is shown how it is possible to use (Ti,Ta)C as a raw material to get a duplex struc¬ ture with cores with a high content of titanium and tantalum but low content of nitrogen. The surrounding rims have higher contents of group VI-metals, i.e. molybdenum and tungsten and higher contents of nitro-
SUBSTITUTE SHEET
gen than the cores. This leads inter alia to an im¬ proved resistance against plastic deformation.
Furthermore, it has in Swedish Patent Application 8902306-3 been shown how by mixing various types of core-rim structures in one and the same alloy advan¬ tages and drawbacks can be balanced out in such a way that optimized alloys are obtained.
EP-A-259192 discloses a sintered alloy comprising a mixed carbonitride of titanium and at least one ele¬ ment from the group consisting of group IV, V and VI elements except titanium in a binder phase based on Co and/or Ni. The alloy is produced by mixing powders of the hard constituents, heating the mixture in a nitrogen atmosphere at a temperature of at least the sintering temperature to form a solid solution, mil¬ ling said solid solution to obtain a carbonitride powder which is mixed with Co and/or Ni and sintered.
It has now turned out that if sintered titaniumbased carbonitride alloys are produced using complex cubic carbonitride raw material which contains the main part, preferably >90%, most preferably >95% of the metals at least two preferably at least three from the groups IV and V in addition to carbon and nitro¬ gen being part of the finished sintered carbonitride alloy unique structures as well as unique properties are obtained. Preferably all of the nitrogen shall be present in the mentioned carbonitride raw material.
In particular of the above-mentioned metals all tita¬ nium and tantalum shall be present in the raw mate¬ rial according to the invention. Preferably also va- nadium, niobium and suitably also zirconium and haf-
SUBSTITUTE SHEET
nium are present if they are part of the finished sintered alloy. Metals from group VI, Cr, Mo and W, shall, if they are present, be added as multiple car¬ bides, single carbides and/or as metal+carbon, but they may also be part of the raw material according to the invention provided that the raw material re¬ mains cubic.
The raw material acording to the invention is produ¬ ced directly by carbonitriding of the oxides of the metals or the metals themselves. As a result a carbo¬ nitride powder with essentially equiaxial grains and a narrow grain size distribution is obtained with a mean grain size of 0.8 - 3 μm, preferably 1 - 2 μm.
As mentioned interesting properties of a sintered carbonitride alloy are obtained if the special raw materials according to this invention are used. Thus, it has turned out that a carbonitride alloy with ex- tremely positive properties at intermittent machining of materials difficult to machine which materials have a tendency to clad if a raw material with e.g. the composition (Tig#93,TaQ.07^c0.48'N0.52^ ^s used. This effect is further increased if in addition vana- dium is added whereby the corresponding formula will be (τi0.88, a0.06'V0.06> (C0.51'N0.49> • Corresponding inserts made from simple raw materials and in exactly the same equipment give considerably decreased pro¬ perties in toughness inter alia greater scatter at the same wear resistance. This means that the relia¬ bility of such inserts is considerably decreased which means that they are not as efficient when pro¬ ducing with limited manning a production form with increased importance due to increasing labour costs.
SUB TlTUte SHEET
One of the reasons for this positive behaviour has turned out to be that _a considerably lower porosity level is obtained with this complex raw material com¬ pared to conventional raw materials without having to use any other means such as HIP and this with even lower compaction pressure than for conventional mate¬ rial. This is a great advantage from production point of view inter alia due to reduced tool wear and con¬ siderably lower risk for unfavourable pressing cracks.
The invention thus relates to a method of producing a titanium based carbonitride alloy with 3-25 % by weight binderphase based on Co, Ni and/or Fe using the above mentioned complex raw material. This raw material is milled together with carbides from group VI, if any, and binderphase elements and carbon addi¬ tion, if any, and minor additions of e.g. TiC, TiN, TaC, VC or combinations thereof due to small devia- tions in composition of the complex raw material whe¬ reafter compaction and sintering, preferably in an inert atmosphere, is performed according to known technique.
Fig 1 shows the 'window' in the composition diagram for Group IV-Group V - C-N, expressed in molar ratio, of the complex raw material which shows the above mentioned advantages in high magnification, whereas fig 2 shows where in the total molar ratio diagram this small area is situated.
Group IV metals are Ti, Zr and/or Hf and Group V me¬ tals are V, b and/or Ta.
SUBSTITUTE SHEET
As is evident from figure 1 the window comprises the composition area:
0.84< XIV < 0.97 0.44< Xc < 0.55
and in particular:
0.86< XIV < 0.95 0.46< Xc < 0.53
The latter restricted window can be divided into two, one without other group V metals than Ta:
0.905< XIV < 0.95
0.46< Xc < 0.53
and another one with other group V elements than Ta i.e. V and Nb:
0.86< XIV < 0.905
0.46< Xc < 0.53
Particularly good properties are obtained for the compositions
0.91< XIV < 0.95 0.46< Xc < 0.50
respectively
0.86< XIV < 0.90 0.49< Xc < 0.53
SUBSTITUTE SHEET
For titanium the following applies x>pj_>0.7 preferably
In the above given molar ratios for carbon and nitro- gen usual amounts of oxygen may be present i.e. sub¬ stitute carbon and nitrogen even if it is desirable to keep such amounts of oxygen low <0.8 %, preferably <0.5 %. The invention comprises εtoichiometric as well as usually substoichiometric carbonitrides.
Example
Titanium-based carbonitride alloys with 17.5 % Ni+Co binder phase were produced with the use of a complex raw material according to the invention
( in.βS'Tao.Oβ'Nko.Oβ) (C0.51'N0.49> as wel1 as wi h the use of simple raw material: TiN, TiC and VC. In both cases also C and M02C were added in addition to
Co and Ni. The following compaction pressure and po- rosity after milling and sintering to the same grain size were obtained:
Porosity Compaction pressure,
N/mm^ Alloy according to the invention A00 154 Simple raw materials A06-A08 206
BO4
SUBSTITUTE SHEET
Claims
1. Method of producing a sintered titanium based car¬ bonitride alloy with 3-25 weight-% binder phase by milling, pressing and sintering according to known technique c h a r a c t e r i z e d in that a raw ma¬ terial is used comprising a complex cubic carboni¬ tride containing the main part of the metals from groups IV and V of the periodic system and carbon and nitrogen to be found in the finished alloy whereby said alloy has the composition
0.86< XIV < 0.97
0.44< XC < 0.55
where X y is the molar ratio of the group IV elements of the alloy and Xc is the molar ratio of carbon.
2. Method according to claim 1 c h a r a c t e r i z e d in that the carbonitride raw material comprises essentially equiaxial grains with a narrow grain size distribution with a mean grain size of 0.8 - 3 μm, preferably 1 - 2 μm.
3. Method according to claim 1 or 2 c h a r a c t e r i z e d in that the composition of the complex raw material is
0.86< XIV < 0.95 0.46< Xc < 0.53
4. Method according to any of the preceding claims c h a r a c t e r i z e d in that said raw material is produced directly by carbonitriding of the oxides of the metals or the metals themselves.
SUBSTITUTE SHEET
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9004119A SE9004119D0 (en) | 1990-12-21 | 1990-12-21 | PREPARED FOR PREPARATION OF A SINTERED CARBON NITROGEN ALLOY FOR INTERMITTENT PROCESSING OF REPLACED MATERIALS |
| SE9004119 | 1990-12-21 | ||
| PCT/SE1991/000888 WO1992011396A1 (en) | 1990-12-21 | 1991-12-19 | Method of producing a sintered carbonitride alloy for intermittent machining of materials difficult to machine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0563203A1 true EP0563203A1 (en) | 1993-10-06 |
| EP0563203B1 EP0563203B1 (en) | 1997-04-09 |
Family
ID=20381289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92901893A Expired - Lifetime EP0563203B1 (en) | 1990-12-21 | 1991-12-19 | Method of producing a sintered carbonitride alloy for intermittent machining of materials difficult to machine |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0563203B1 (en) |
| JP (1) | JPH06504588A (en) |
| AT (1) | ATE151473T1 (en) |
| DE (1) | DE69125626T2 (en) |
| SE (1) | SE9004119D0 (en) |
| WO (1) | WO1992011396A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338196A (en) * | 2018-11-30 | 2019-02-15 | 肖水清 | Ti (C, N) based ceramic metal and its preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002221127A1 (en) * | 2000-12-19 | 2002-07-01 | Honda Giken Kogyo Kabushiki Kaisha | Composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU501073B2 (en) * | 1974-10-18 | 1979-06-07 | Sumitomo Electric Industries, Ltd. | Cemented carbonitride alloys |
| US4769070A (en) * | 1986-09-05 | 1988-09-06 | Sumitomo Electric Industries, Ltd. | High toughness cermet and a process for the production of the same |
-
1990
- 1990-12-21 SE SE9004119A patent/SE9004119D0/en unknown
-
1991
- 1991-12-19 WO PCT/SE1991/000888 patent/WO1992011396A1/en active IP Right Grant
- 1991-12-19 AT AT92901893T patent/ATE151473T1/en not_active IP Right Cessation
- 1991-12-19 DE DE69125626T patent/DE69125626T2/en not_active Expired - Fee Related
- 1991-12-19 JP JP4501799A patent/JPH06504588A/en active Pending
- 1991-12-19 EP EP92901893A patent/EP0563203B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9211396A1 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109338196A (en) * | 2018-11-30 | 2019-02-15 | 肖水清 | Ti (C, N) based ceramic metal and its preparation method and application |
| CN109338196B (en) * | 2018-11-30 | 2020-12-11 | 岭南师范学院 | Ti (C, N) -based metal ceramic and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992011396A1 (en) | 1992-07-09 |
| EP0563203B1 (en) | 1997-04-09 |
| DE69125626D1 (en) | 1997-05-15 |
| SE9004119D0 (en) | 1990-12-21 |
| ATE151473T1 (en) | 1997-04-15 |
| DE69125626T2 (en) | 1997-07-24 |
| JPH06504588A (en) | 1994-05-26 |
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