WO2004085099A1 - Cobalt-based metal powder and method for producing components thereof - Google Patents

Cobalt-based metal powder and method for producing components thereof Download PDF

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Publication number
WO2004085099A1
WO2004085099A1 PCT/SE2004/000379 SE2004000379W WO2004085099A1 WO 2004085099 A1 WO2004085099 A1 WO 2004085099A1 SE 2004000379 W SE2004000379 W SE 2004000379W WO 2004085099 A1 WO2004085099 A1 WO 2004085099A1
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weight
powder
powder metal
metal composition
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PCT/SE2004/000379
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French (fr)
Inventor
Owe MÅRS
Christophe Szabo
Original Assignee
Höganäs Ab
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Application filed by Höganäs Ab filed Critical Höganäs Ab
Priority to BRPI0408804-2A priority Critical patent/BRPI0408804A/en
Priority to MXPA05010291A priority patent/MXPA05010291A/en
Priority to EP04721416A priority patent/EP1606071A1/en
Priority to JP2006507961A priority patent/JP2006521472A/en
Publication of WO2004085099A1 publication Critical patent/WO2004085099A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals

Definitions

  • the present invention concerns powder metallurgy. More specifically the present invention concerns a cobalt-based powder metal composition and a method for producing components thereof, especially for heavy duty applications .
  • Cobalt-based alloys such as Stellite® (Trade Mark for Co-Cr-W alloys) are hard alloys that are extremely resistant to many forms of wear. Products of these alloys show high hardness over a wide temperature range and are resistant towards corrosion. These products are used for inter alia casting of various kinds of components such as machine parts (bearing shells, valve seat inserts etc) or other components where high density, high strength and wear resistance are required.
  • Cast material often suffers from micro structural defects and carbide segregation. Carbide segregation leads to inhomogenously distributed hard phases. Disadvantages with such materials are lack of fracture toughness and poor machinability .
  • Powder metallurgy (PM) products generally possess a more homogenous microstructure than cast products. Further advantages with the PM production method are that costly machining into final shape may be excluded or minimized in comparison with traditional casting methods and that the method is more suitable for producing large quantities of small articles. Attempts have been made over the years to produce cobalt-based products using the PM technology.
  • the US patent 4129444 discloses a process wherein atomised Co-based alloy powders are coated with a binder and then consolidated to produce discrete bodies that are dried, crushed and screened to obtain agglomerates. The agglomerates are pressed into green compacts which are sintered at high temperature.
  • US patent 5,462,572 discloses a powder metallurgy component prepared of a gas atomised Co-Cr-Mo alloy powder.
  • the alloy powder is filled in a canister and baked in vacuum to degas the powder and the powder filled canister is thereafter consolidated, preferably by hot isostatic pressing (HIP) .
  • HIP hot isostatic pressing
  • An object of the invention is to provide a new Co- based powder metal composition which can be used in conventional PM processes. Another object is to provide a Co-based powder metal composition with high compactibility which can be compacted to high green density and high green strength.
  • Still another object is to provide a green body of a cobalt based alloy which can be machined before sintering.
  • a further object is to provide a powder metal composition which can be compacted and sintered to high density without high sintering temperatures .
  • the composition comprises a Co-based pre-alloyed powder with irregularly shaped particles admixed with graphite.
  • the Co-based pre-alloyed powder should include less than 0.3% by weight of carbon and at least 15% by weight Car.
  • the Co-based pre-alloyed powder preferably comprises at least 30% by weight and preferably less than 80% by weight Co.
  • the invention also concerns a method comprising the steps of providing a powder metal composition according to the invention and compacting the composition in a die at a pressure of at least 400 MPa to a component of desired shape.
  • the Co-based pre-alloyed powder in the composition according to the invention may be produced by subjecting a melt having the desired composition to atomising by water .
  • the Co-based pre-alloyed powder according to the invention comprises less than 0.3% by weight carbon.
  • the carbon content of the powder is however preferably less than 0.1% by weight, and most preferably less than 0.05% by weight (i.e. essentially free from C except for inevitable impurities) .
  • the Co-based pre-alloyed powder comprises at least 15% by weight and preferably less than 35% by weight Cr .
  • the addition of Cr improves the strength of the Cobalt matrix by solution hardening and/or carbide formation. These effects are further improved by the addition of and/or Mo.
  • Co-based pre-alloyed powder may be chosen from Ni, Fe, Si, Mn, V and B .
  • a preferred pre-alloyed powder according to the invention comprise: 5-35% by weight Cr, 0-20% by weight , 0-25% by weight Ni, 0-5% by weight Si, 0-5% by weight Fe, 0-10% by weight Mo, balance Co and less than 0.3% by weight C.
  • a powder metal composition according to the invention comprises a pre-alloyed powder according to the invention admixed with graphite.
  • the amount of graphite addition depends on the desired content of carbides and on the content of carbide forming elements.
  • the graphite content is preferably at least 0.5% by weight, more preferably at least 0.7% by weight and preferably less than 3% by weight.
  • the powder metal composition may further comprise one ore more additives selected from the group consisting of alloying elements, lubricants, processing aids and binders .
  • Other elements may be added for improving properties or reducing costs.
  • the used lubricant plays an important role for the achieved green properties. Good results have been achieved with KenolubeTM (available from H ⁇ ganas AB, Sweden) , amide wax, metal stearates and other commonly used lubricants.
  • the processing aids used in the powder metal composition according to the invention may consist of talc, forsterite, manganese sulphide, sulphur, molybdenum disulphide, boron nitride, tellurium, selenium, barium difluoride and calcium difluoride, which are used either separately or in combination.
  • the powder metal composition according to the invention is filled in a die and compacted at a pressure of at least 400 MPa to a component of desired shape. This compaction yields a component with high green strength and green density and the component may even be green machined at this stage. This is an advantage as the material in the final sintered component are hard and difficult to machine.
  • the component is sintered at a temperature of at least 1080°C, preferably in protective atmosphere or vacuum.
  • the components produced of the powder according to the invention and according to the method of the invention are especially suited for heavy-duty applications, such as valve seat inserts for engines where the valve seats need to last the life time of the engine, without replacement or service.
  • test mixtures (mix 1-5) listed in table 2 and 3 were prepared from the water atomised pre-alloyed powders in table 1 (% by weight) .
  • the pre-alloyed powders were further admixed with lubricants, alloying elements and processing aids according to table 2 and 3.
  • lubricants e.g., talc, talc, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin, kaolin
  • the sintered mix 3 components exhibit a higher density and hardness (HvlO) than mix 5 components.
  • KenolubeTM gives a higher density than the mix of Polyethyleneoxide and Orgasol which enables better performance in the sintered state.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention concerns a powder metal composition for producing powder metal components comprising a Co-based pre-alloyed powder, with irregularly shaped particles comprising at least 15% by weight Cr and less than 0.3% by weight C, admixed with graphite. The invention also concerns a method for producing PM components by pressing of articles to shape from the powder metal composition according to the invention and sintering them.

Description

COBALT-BASED METAL POWDER AND METHOD FOR PRODUCING COMPONENTS THEREOF.
Field of the invention
The present invention concerns powder metallurgy. More specifically the present invention concerns a cobalt-based powder metal composition and a method for producing components thereof, especially for heavy duty applications .
Background of the invention
Cobalt-based alloys, such as Stellite® (Trade Mark for Co-Cr-W alloys) are hard alloys that are extremely resistant to many forms of wear. Products of these alloys show high hardness over a wide temperature range and are resistant towards corrosion. These products are used for inter alia casting of various kinds of components such as machine parts (bearing shells, valve seat inserts etc) or other components where high density, high strength and wear resistance are required.
Cast material often suffers from micro structural defects and carbide segregation. Carbide segregation leads to inhomogenously distributed hard phases. Disadvantages with such materials are lack of fracture toughness and poor machinability .
Powder metallurgy (PM) products generally possess a more homogenous microstructure than cast products. Further advantages with the PM production method are that costly machining into final shape may be excluded or minimized in comparison with traditional casting methods and that the method is more suitable for producing large quantities of small articles. Attempts have been made over the years to produce cobalt-based products using the PM technology. Thus the US patent 4129444 discloses a process wherein atomised Co-based alloy powders are coated with a binder and then consolidated to produce discrete bodies that are dried, crushed and screened to obtain agglomerates. The agglomerates are pressed into green compacts which are sintered at high temperature. Furthermore the US patent 5,462,572 discloses a powder metallurgy component prepared of a gas atomised Co-Cr-Mo alloy powder. The alloy powder is filled in a canister and baked in vacuum to degas the powder and the powder filled canister is thereafter consolidated, preferably by hot isostatic pressing (HIP) .
Objects of the invention
An object of the invention is to provide a new Co- based powder metal composition which can be used in conventional PM processes. Another object is to provide a Co-based powder metal composition with high compactibility which can be compacted to high green density and high green strength.
Still another object is to provide a green body of a cobalt based alloy which can be machined before sintering.
A further object is to provide a powder metal composition which can be compacted and sintered to high density without high sintering temperatures .
Summary of the invention
These object as well as other objects that will be apparent from the description below, have now been obtained according to the present invention by providing a new Co-based powder metal composition. Critical features of this composition are that the composition comprises a Co-based pre-alloyed powder with irregularly shaped particles admixed with graphite. Furthermore the Co-based pre-alloyed powder should include less than 0.3% by weight of carbon and at least 15% by weight Car. The Co-based pre-alloyed powder preferably comprises at least 30% by weight and preferably less than 80% by weight Co. The invention also concerns a method comprising the steps of providing a powder metal composition according to the invention and compacting the composition in a die at a pressure of at least 400 MPa to a component of desired shape.
Detailed description of the invention
The Co-based pre-alloyed powder in the composition according to the invention may be produced by subjecting a melt having the desired composition to atomising by water .
The Co-based pre-alloyed powder according to the invention comprises less than 0.3% by weight carbon. The carbon content of the powder is however preferably less than 0.1% by weight, and most preferably less than 0.05% by weight (i.e. essentially free from C except for inevitable impurities) .
The Co-based pre-alloyed powder comprises at least 15% by weight and preferably less than 35% by weight Cr . The addition of Cr improves the strength of the Cobalt matrix by solution hardening and/or carbide formation. These effects are further improved by the addition of and/or Mo.
Other elements which may be included in the Co-based pre-alloyed powder may be chosen from Ni, Fe, Si, Mn, V and B .
A preferred pre-alloyed powder according to the invention comprise: 5-35% by weight Cr, 0-20% by weight , 0-25% by weight Ni, 0-5% by weight Si, 0-5% by weight Fe, 0-10% by weight Mo, balance Co and less than 0.3% by weight C.
Another preferred powder according to the invention further comprise 0-3% by weight Mn, 0-4% by weight V and 0-4% by weight B. A powder metal composition according to the invention comprises a pre-alloyed powder according to the invention admixed with graphite. The amount of graphite addition depends on the desired content of carbides and on the content of carbide forming elements. The graphite content is preferably at least 0.5% by weight, more preferably at least 0.7% by weight and preferably less than 3% by weight.
The powder metal composition may further comprise one ore more additives selected from the group consisting of alloying elements, lubricants, processing aids and binders . Other elements may be added for improving properties or reducing costs.
The used lubricant plays an important role for the achieved green properties. Good results have been achieved with Kenolube™ (available from Hδganas AB, Sweden) , amide wax, metal stearates and other commonly used lubricants.
The processing aids used in the powder metal composition according to the invention may consist of talc, forsterite, manganese sulphide, sulphur, molybdenum disulphide, boron nitride, tellurium, selenium, barium difluoride and calcium difluoride, which are used either separately or in combination.
The powder metal composition according to the invention is filled in a die and compacted at a pressure of at least 400 MPa to a component of desired shape. This compaction yields a component with high green strength and green density and the component may even be green machined at this stage. This is an advantage as the material in the final sintered component are hard and difficult to machine.
The component is sintered at a temperature of at least 1080°C, preferably in protective atmosphere or vacuum.
The components produced of the powder according to the invention and according to the method of the invention are especially suited for heavy-duty applications, such as valve seat inserts for engines where the valve seats need to last the life time of the engine, without replacement or service.
The following example, which is not intended to be limiting, present certain embodiments of the present invention .
Example
The test mixtures (mix 1-5) listed in table 2 and 3 were prepared from the water atomised pre-alloyed powders in table 1 (% by weight) .
Table 1
Figure imgf000006_0001
The pre-alloyed powders were further admixed with lubricants, alloying elements and processing aids according to table 2 and 3. In test mix 1, 3 and 4, 1.7% by weight graphite was further included. TRS-samples, according to ISO 3995, were moulded. The compacting operation was performed with the three different types of samples at 600 and 800 MPa respectively.
The resulting components were tested for green density (GD) and green strength (GS) . After sintering at 1120°C for 30 minutes in a 90% N2/10% H2 atmosphere the components were tested for sintered density (SD) and hardness (HvlO) . Table 4 and 5 discloses the results of the tests. Table 2
Figure imgf000007_0001
'40% Polyethyleneoxide: 60% Orgasol
TABLE 3
Figure imgf000007_0002
40% Polyethyleneoxide: 60% Orgasol TABLE 4
Figure imgf000008_0001
*Bars Fractured on ejection
TABLE 5
Figure imgf000008_0002
nm=not measured
Compaction of mix 2 and to some extent mix 5 did not work, the components exhibited bad surfaces and frequent edge cracks and were too fragile to handle.
Compaction of mix 1, 3 and 4, without C in the pre- alloyed powder, showed a great improvement of the compressibility, as can be seen in table 4 and 5, and high green strengths and green densities were achieved for the resulting components. Components with thin walls normally require a green strength of at least 7 MPa to enable handling. Green strengths above 20 MPa normally enable green machining.
The sintered mix 3 components exhibit a higher density and hardness (HvlO) than mix 5 components.
Metallographic studies of the sintered components showed that components made from mix 3 and 5 have similar structures. It is thus possible to create the desired carbide structures in mix 3 components during sintering,
A comparison between mix 3 and mix 4 in table 5 demonstrates the influence of lubricants on the green strength and green density of the compacted components . Kenolube™ gives a higher density than the mix of Polyethyleneoxide and Orgasol which enables better performance in the sintered state.

Claims

1. A powder metal composition for producing powder metal components comprising a Co-based pre-alloyed powder, with irregularly shaped particles comprising at least 15% by weight Cr and less than 0.3% by weight C, admixed with graphite.
2. A powder metal composition according to claim 1 further comprising at least one element selected from the group consisting of and Mo.
3. A powder metal composition according to claim 1 or 2, further comprising at least one alloying element selected from Ni, Fe, Si, Mn, V and B.
4. A powder metal composition according to any one of the claims 1-3, wherein the content of C in the pre- alloyed powder preferably is less than 0.1% by weight, and most preferably less than 0.05% by weight.
5. A powder metal composition according to any one of the above claims comprising: 15-35% by weight Cr, 0- 20% by weight , 0-25% by weight Ni, 0-5% by weight Si, 0-5% by weight Fe, 0-10% by weight Mo, the balance being Co.
6. A powder metal composition according to any one of the above claims, wherein the content of admixed graphite is preferably at least 0.5% by weight, more preferably at least 0.7% by weight.
7. A composition according to any one of the above claims further comprising one or more additives selected from the group consisting of lubricants, processing aids alloying elements and binders .
8. A method for producing a component of a Co-based alloy with high green strength and high green density comprising the steps: a) providing a powder metal composition comprising a
Co-based pre-alloyed powder, with irregularly shaped particles comprising at least 15% by weight Cr and less than 0.3% by weight C, admixed with graphite; b) compacting the composition in a die at a pressure of at least 400 MPa to a component of desired shape.
9. Method according to claim 8, wherein the pre- alloyed powder contains less than 0.1% by weight C, preferably less than 0.05% by weight C.
10. Method according to claims 8 or 9, wherein the content of admixed graphite is at least 0.5% by weight, preferably at least 0.7% by weight.
11. Method for producing a sintered component of a Co-based powder metal composition comprising, in addition to step a) and b) according to claim 8 the step: c) sintering the component.
12. Method according to claim 11, wherein the sintering is performed at a temperature of at least 1080°C in a protective atmosphere or vacuum.
13. A Co-based pre-alloyed powder with irregularly shaped particles comprising at least 15% by weight Cr and less than 0.3% by weight C.
PCT/SE2004/000379 2003-03-27 2004-03-17 Cobalt-based metal powder and method for producing components thereof WO2004085099A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BRPI0408804-2A BRPI0408804A (en) 2003-03-27 2004-03-17 cobalt-based metal powder and method for producing them
MXPA05010291A MXPA05010291A (en) 2003-03-27 2004-03-17 Cobalt-based metal powder and method for producing components thereof.
EP04721416A EP1606071A1 (en) 2003-03-27 2004-03-17 Cobalt-based metal powder and method for producing components thereof
JP2006507961A JP2006521472A (en) 2003-03-27 2004-03-17 Cobalt-based metal powder and method for producing the same

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SE0300881A SE0300881D0 (en) 2003-03-27 2003-03-27 Powder metal composition and method for producing components thereof
SE0300881-0 2003-03-27

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MX (1) MXPA05010291A (en)
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SE (1) SE0300881D0 (en)
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EP3050647A4 (en) * 2013-09-25 2017-05-24 Shimane Prefectural Government Method for producing cobalt alloy material, cobalt alloy material and cutting member

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ES2646789T3 (en) * 2008-06-06 2017-12-18 Höganäs Ab (Publ) Prealloyed Iron Powder
IT1395649B1 (en) * 2009-07-31 2012-10-16 Avio Spa PROCESS OF MANUFACTURE OF COMPONENTS OBTAINED BY SINTERING CO-CR-MO ALLOYS WITH IMPROVED DUCTILITY AT HIGH TEMPERATURES
US8038760B1 (en) * 2010-07-09 2011-10-18 Climax Engineered Materials, Llc Molybdenum/molybdenum disulfide metal articles and methods for producing same
CN104080933B (en) * 2011-11-18 2016-03-30 土耳其科学技术研究理事会 High temperature instrument alloy
CN103952596B (en) * 2014-05-12 2016-03-23 四川省有色冶金研究院有限公司 A kind of vitallium powder preparation method increasing material manufacture for metal
CN104195548A (en) * 2014-09-11 2014-12-10 王晓飚 Zinc-corrosion-resistant coating cobalt-based alloy powder for laser cladding
JP6372512B2 (en) * 2016-04-06 2018-08-15 セイコーエプソン株式会社 Metal powder for powder metallurgy, compound, granulated powder, sintered body and heat-resistant parts
JP7116495B2 (en) * 2017-03-14 2022-08-10 ヴァンベーエヌ コンポネンツ アクチエボラグ High carbon cobalt alloy
KR102025798B1 (en) * 2019-06-25 2019-09-26 주식회사 유승 PREPARING METHOD OF HIGH-DENSITY SINTERED Co-Cr-Mo ALLOYS FOR BIOMATERIALS

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US4129444A (en) * 1973-01-15 1978-12-12 Cabot Corporation Power metallurgy compacts and products of high performance alloys
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
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US5462575A (en) * 1993-12-23 1995-10-31 Crs Holding, Inc. Co-Cr-Mo powder metallurgy articles and process for their manufacture

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US3846126A (en) * 1973-01-15 1974-11-05 Cabot Corp Powder metallurgy production of high performance alloys
US4129444A (en) * 1973-01-15 1978-12-12 Cabot Corporation Power metallurgy compacts and products of high performance alloys
US4668290A (en) * 1985-08-13 1987-05-26 Pfizer Hospital Products Group Inc. Dispersion strengthened cobalt-chromium-molybdenum alloy produced by gas atomization
US5002731A (en) * 1989-04-17 1991-03-26 Haynes International, Inc. Corrosion-and-wear-resistant cobalt-base alloy
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Publication number Priority date Publication date Assignee Title
EP3050647A4 (en) * 2013-09-25 2017-05-24 Shimane Prefectural Government Method for producing cobalt alloy material, cobalt alloy material and cutting member

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SE0300881D0 (en) 2003-03-27
BRPI0408804A (en) 2006-03-28
MXPA05010291A (en) 2005-11-17
JP2006521472A (en) 2006-09-21
RU2005132992A (en) 2006-02-20
CN1777485A (en) 2006-05-24
EP1606071A1 (en) 2005-12-21
TW200426226A (en) 2004-12-01

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