EP0881958A1 - Materiau s'utilisant en metallurgie des poudres pour produire des pieces moulees, notamment des sieges de soupape rapportes ou des guides de soupape tres resistants a l'usure - Google Patents

Materiau s'utilisant en metallurgie des poudres pour produire des pieces moulees, notamment des sieges de soupape rapportes ou des guides de soupape tres resistants a l'usure

Info

Publication number
EP0881958A1
EP0881958A1 EP97905071A EP97905071A EP0881958A1 EP 0881958 A1 EP0881958 A1 EP 0881958A1 EP 97905071 A EP97905071 A EP 97905071A EP 97905071 A EP97905071 A EP 97905071A EP 0881958 A1 EP0881958 A1 EP 0881958A1
Authority
EP
European Patent Office
Prior art keywords
weight
powder
material according
powder mixture
valve seat
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
Application number
EP97905071A
Other languages
German (de)
English (en)
Other versions
EP0881958B1 (fr
Inventor
Ekkehard KÖHLER
Kirit Dalal
Anil V. Nadkarni
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bleistahl Produktions-GmbH and Co KG
SCM Metal Products Inc
Original Assignee
Bleistahl Produktions-GmbH and Co KG
SCM Metal Products Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bleistahl Produktions-GmbH and Co KG, SCM Metal Products Inc filed Critical Bleistahl Produktions-GmbH and Co KG
Publication of EP0881958A1 publication Critical patent/EP0881958A1/fr
Application granted granted Critical
Publication of EP0881958B1 publication Critical patent/EP0881958B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C22C32/001—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 with only oxides
    • C22C32/0015—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 with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

Definitions

  • the invention relates to a material for the powder-metallurgical production of molded parts with high thermal conductivity and high wear and corrosion resistance by pressing, sintering and optionally post-compression of a powder mixture with a copper content of at least about 50% by weight.
  • Sintered materials of this type are required for molded parts which are exposed to hot gases or gas mixtures, for example for the production of valve seat rings and valve guides for internal combustion engines which are exposed to high mechanical loads on the one hand and at the same time to the action of hot combustion gases. They must therefore be made from materials that are not only wear and corrosion resistant, but also have a high thermal conductivity. Thermal conductivity is becoming increasingly important, as the temperature level at the valves increases due to the expansion of the stoichiometric mixture required for emission reasons, and a continuing trend towards more powerful engines can be seen. It is known to reduce the temperature difference between the head of the valve and the cylinder head into which the valve seat ring is incorporated by transporting heat in the valve.
  • the valve stem is provided with a hollow bore and cooled.
  • the diameters of the valve stems have been reduced in recent years to such an extent that in most cases it is no longer possible to provide them with a hollow bore, so that the use of hollow-bore valves, for example filled with sodium, in Future will no longer be possible.
  • the aim is therefore to improve the thermal conductivity of the material from which the valve seat, in particular the valve seat ring, is made, in order in this way to dissipate the heat more quickly, to lower the temperature level, in order to improve the tribological conditions and the system technologically and improve in cost.
  • Powder-metallurgically produced molded parts made of sintered materials based on iron with infiltrated copper are known which have sufficient wear resistance for use as a valve seat ring or valve guide, the thermal conductivity of which is not high enough compared to sintered materials without a copper content.
  • a sintered material is known from DE-PS 21 14 160, which consists of an iron-based material to which carbon and lead and other alloy components have been added.
  • Valve seat rings made from this material do have sufficient heat and wear resistance, but their thermal conductivity is not sufficient to overcome the problem in particular in the outlet area of a modern one
  • PCT-EP 89/01343 discloses a sintered material for the powder metallurgical production of valve seat rings which are said to have increased thermal conductivity with high wear resistance.
  • the sintered material consists of a base metal powder with a copper content of approximately 70 to 100% by weight of copper and an alloy content.
  • the alloy fraction can consist, for example, of 1 to 3% by weight of cobalt or a high-alloy additional metal powder which is mixed into the basic metal powder as a hard phase, the proportion of which then amounts to a maximum of 30% by weight.
  • the invention has for its object to provide a sintered material for powder metallurgical production, in particular of valve seats or valve guides, the wear resistance of which is very high and which at the same time has a significantly high thermal conductivity compared to known sintered materials used for this purpose.
  • the invention consists in that the starting powder mixture consists of a base powder containing the Cu content in an amount of 50 to 90% by weight and a powdery alloy additive containing molybdenum in an amount of 10 to 50% by weight and that the base powder is a dispersion-strengthened copper powder.
  • the dispersion-strengthened copper powder is preferably solidified by Al2O3, contains from 0.1 to 1.1% by weight of Al2O3 and less than 0.5% by weight of impurities and 97/30808 PC17EP97 / 00837
  • the invention is based on the surprising finding that the use of a Cu-Al ⁇ Os powder, preferably dispersion-strengthened by means of Al2O3, as a material for the powder-metallurgical production of moldings leads to products which, on the one hand, have high wear and corrosion resistance and, on the other hand, high thermal conductivity have, so that they are particularly suitable for the production of valve seat rings or valve guides for internal combustion engines.
  • the applicant attributes this to the fact that the distance between the dispersed AbO 3 particles in the copper matrix in the Cu-Al 2 O 3 powder produced by means of internal oxidation is of the order of 3 to 12 nm, whereas it is approximately the same in the case of the powder produced without internal oxidation Is 40 ⁇ m.
  • dispersion-strengthened metals as base powder for the powder-metallurgical production of molded parts, in particular valve seat rings or valve guides.
  • the alloy surcharge consists of a powdery, preferably water-thinned, intermetallic hard phase of 28 to 32, preferably 30,% by weight.
  • Molybdenum 9 to 1 1, preferably 10% by weight of chromium, 2.5 to 3.5, pre- preferably 3% by weight silicon, the rest cobalt, the intermetallic hard phase being present in the powder mixture in an amount of about 10% by weight and the base powder in an amount of about 90% by weight.
  • the intermetallic hard phase consists of 28 to 32, preferably 30% by weight molybdenum, 9 to 11, preferably 10% by weight chromium, 2.5 to 3.5, preferably 3% by weight. % Silicon, balance iron, the intermetallic phase being present in the powder mixture in an amount of about 10% by weight and the base powder in an amount of about 90% by weight.
  • the alloy surcharge can also consist of a hard phase consisting of a high-speed steel powder of approximately 6% by weight of tungsten, approximately 5% by weight of molybdenum, approximately 2% by weight of vanadium, approximately 4% by weight of chromium, the rest being iron Hard phase is present in the powder mixture in an amount of up to about 30% by weight and the base powder in an amount of about 70% by weight or higher.
  • a hard phase consisting of a high-speed steel powder of approximately 6% by weight of tungsten, approximately 5% by weight of molybdenum, approximately 2% by weight of vanadium, approximately 4% by weight of chromium, the rest being iron Hard phase is present in the powder mixture in an amount of up to about 30% by weight and the base powder in an amount of about 70% by weight or higher.
  • the alloy surcharge can also consist of a hard phase from a Mo-PC powder composed of approximately 11% by weight molybdenum, approximately 0.6% by weight phosphorus, approximately 1.2% by weight carbon, the rest being iron, the Hard phase and the base powder are present in the powder mixture in an amount of approximately 50% by weight.
  • the invention further relates to a material which consists of a starting powder mixture of approximately 80% by weight of base powder, approximately 10% by weight of molybdenum powder and approximately 10% by weight of copper powder or approximately 79% by weight of base powder, approximately 10% by weight of molybdenum powder, approximately 10% by weight of copper powder and approximately 1% by weight of powdered molybdenum trioxide.
  • the invention further provides that the base powder additionally molybdenum disulfide (M0S2) and / or manganese sulfide (MnS) and / or tungsten disulfide (WS2) and / or calcium fluoride (CaF2) and / or tellurium (Te) and / or calcium carbonate (CaC03 > in a total amount of at least 1% by weight to a maximum of 3% by weight based on the amount of the base powder.
  • M0S2 molybdenum disulfide
  • MnS manganese sulfide
  • WS2 tungsten disulfide
  • CaF2 calcium fluoride
  • Te tellurium
  • CaC03 calcium carbonate
  • the invention further relates to a process for the powder-metallurgical production of molded parts with high wear and corrosion resistance and high thermal conductivity, in particular for the production of valve seat rings or valve guides for internal combustion engines, in which an initial powder mixture having one of the compositions described above with about 0.3% by weight of a pressure-relieving agent, e.g. B. wax, mixed, molded and pressed into a molded part with a density of about 8.0 g / cm 3 and subjected to a subsequent sintering under protective gas; the sintering is preferably carried out under a protective gas atmosphere of approximately 80% by weight of nitrogen and approximately 20% by weight of hydrogen for a period of approximately 45 minutes at a temperature of approximately 1,040 ° C. If necessary, the sintered molded part can be subjected to post-compression to a density of approximately 8.8 g / cm 3 .
  • a pressure-relieving agent e.g. B. wax
  • An alternative embodiment of the invention provides that the starting memever according to claim 1 contains one or more of the substances or substance mixtures listed below:
  • the proportion should not exceed 5-20% by weight, typically 10% by weight.
  • the materials of group b) do not alloy with the copper matrix and therefore have no noticeable influence on the thermal conductivity. They are however relatively expensive. However, it has been found that a proportion of 5-10% by weight is sufficient.
  • group c) cause the intermetallic components to be excreted and in this way superimpose the hardness effect in addition to the hardening by the Al2O3 particles in the dispersion-strengthened copper. While the aluminum oxide particles effectively harden the copper matrix at high temperatures (> 500 ° C), the precipitation phases result in more effective hardening in the medium temperature range (200 - 500 ° C), which are the typical operating temperatures to which the valve seat rings are concerned are exposed. The higher warm hardness generally leads to higher wear resistance.
  • the wear of the valve seat rings is also caused by the addition of solid lubricants such as graphite, M0S2, MnS, h-BN, CaF ⁇ and the like, as well as metal additives such as Mo, Co, W or the like, which form oxide skins at the operating temperatures, which have a smear effect.
  • solid lubricants such as graphite, M0S2, MnS, h-BN, CaF ⁇ and the like
  • metal additives such as Mo, Co, W or the like
  • the oxidation resistance i. H. Corrosion resistance in operation
  • Zn is the preferred alloy component.
  • an addition of 5-30% by weight is not critical.
  • the starting powder preferably contains one or more of the following powdery substances with an irregular particle shape: 5 - 25 wt .-% Cu high green strength, electrolyte Cu, oxide-reduced Cu, Mo, or the like.
  • the unsintered, green parts made of this material have only a low strength.
  • the green strength can be increased considerably by adding the aforementioned components.
  • the "Cu of high green strength" is powder with long, thin, fiber-like particles that intertwine when pressed together and in this way bring about a high strength of the green body.
  • the addition of pure Cu does not increase the thermal conductivity touched so that 5-25% by weight can be added, the preferred range being 10-15% by weight.
  • the machinability, in particular the machinability, of dispersion-strengthened copper is improved by adding one or more of the substances mentioned below:
  • the radial breaking strength of the valve seat rings which must be given in particular when pressed into the cylinder head, is increased by adding one or more of the following substances:
  • the starting powder mixture can be optimally coordinated with regard to the properties required for the valve seat ring by a corresponding combination of the aforementioned alloy additives.
  • the main advantage with regard to the production of valve seat rings in all of the aforementioned starting powder mixtures according to the invention is that the thermal conductivity is particularly high, ie at least 100 W / m • k.
  • a medium-internal oxidation-strengthened Cu-Al ⁇ Os powder with a content of 0.5% by weight of Al2O3 was mixed with 0.3% by weight of a conventional press-serifying agent and with a press pressure of 800 MN / mm 2 to form valve seat rings the dimensions 36.6 x 30, 1 x 9 mm pressed.
  • the green compacts, which had a pressed density of 8.4 g / cm 3 were then sintered for 45 minutes at a temperature of 1,040 ° C. under a protective gas atmosphere of 80% N2 and 20% hydrogen.
  • the sintered density was 8.4 g / cm 3 .
  • the sintered rings were then subjected to post-compression to a density of 8.8 g / cm 3 at a pressure of 1,600 MN / mm 2 .
  • Table 1 shows the measured densities and hardness values
  • Table 2 the thermal conductivity values, which were determined by the laser flash method.
  • the rings were then sintered for 45 minutes at a temperature of 1,040 ° C. in a protective gas atmosphere composed of 80% N2 and 20% H2; the sintered density was 8.2 g / cm 3 .
  • the densification to a density of 8.7 g / cm 3 was carried out with a pressure of 1,600 MN / mm 2 .
  • Table 3 shows the density and hardness values
  • Table 4 the thermal conductivity values determined by the laser flash method.
  • valve seat rings produced according to Examples 1 and 2 showed an unexpected improvement in thermal conductivity compared to commercially available valve seat rings based on Fe with and without copper infiltration. This is shown in Figure 1.
  • Curve 1 shows the Thermal conductivity values of a valve seat ring according to Example 1
  • curve 2 the values for a ring according to Example 2
  • curve 3 the values of a valve seat ring based on Fe with copper infiltration
  • curve 4 the values of a commercially available valve seat ring from the applicant.
  • the rings produced according to Example 1 have a hardness which permits their use in the inlet area of an internal combustion engine, while the valve seat rings according to Example 2 can be used in the outlet area and have excellent running behavior here. This was determined by tests, the conditions of which are summarized in Table 5.
  • the results of the engine test are summarized in Table 6 and shown graphically in Figure 2.
  • the sinking depth is the sum of the wear of the valve and the valve seat ring.
  • the valve seat ring according to the invention according to Example 2 was compared with the Series material Como1 2 by the applicant, which is used on a large scale.
  • the sinking depth of the valve seat ring according to the invention with a significantly increased thermal conductivity of the material is less than that of a commercially available valve seat ring.

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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

L'invention concerne un matériau s'utilisant en métallurgie des poudres pour produire à partir d'un mélange pulvérulent comprenant au moins approximativement 50 % en poids de cuivre, notamment des sièges de soupape rapportés ou des guides de soupape très résistants à l'usure et à la corrosion, et à haute conductibilité thermique. Le mélange pulvérulent initial comprend entre 50 et 90 % en poids de poudre de base contenant la proportion de cuivre et entre 10 et 50 % en poids d'adjuvant d'alliage pulvérulent contenant du molybdène. La poudre de base est du cuivre pulvérulent durci par phase dispersée à l'aide d'Al2O3, avec une teneur en Al2O3 comprise entre 0,1 et 1,1 % en poids, et est obtenue par atomisation de Cu-Al en fusion, puis par chauffage en atmosphère oxydante. L'invention concerne en outre l'utilisation d'une poudre durcie par dispersion de ce type utilisée en métallurgie des poudres pour produire notamment des sièges de soupape rapportés ou des guides de soupape résistant à l'usure et à la corrosion, et à haute conductibilité thermique. L'invention concerne en outre un procédé de production de sièges de soupape rapportés ou de guides de soupape de ce type.
EP97905071A 1996-02-21 1997-02-21 Materiau s'utilisant en metallurgie des poudres pour produire des pieces moulees, notamment des sieges de soupape rapportes ou des guides de soupape tres resistants a l'usure Expired - Lifetime EP0881958B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19606270A DE19606270A1 (de) 1996-02-21 1996-02-21 Werkstoff zur pulvermetallurgischen Herstellung von Formteilen, insbesondere von Ventilsitzringen mit hoher Wärmeleitfähigkeit und hoher Verschleiß- und Korrosionsfestigkeit
DE19606270 1996-02-21
PCT/EP1997/000837 WO1997030808A1 (fr) 1996-02-21 1997-02-21 Materiau s'utilisant en metallurgie des poudres pour produire des pieces moulees, notamment des sieges de soupape rapportes ou des guides de soupape tres resistants a l'usure

Publications (2)

Publication Number Publication Date
EP0881958A1 true EP0881958A1 (fr) 1998-12-09
EP0881958B1 EP0881958B1 (fr) 2001-05-30

Family

ID=7785898

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97905071A Expired - Lifetime EP0881958B1 (fr) 1996-02-21 1997-02-21 Materiau s'utilisant en metallurgie des poudres pour produire des pieces moulees, notamment des sieges de soupape rapportes ou des guides de soupape tres resistants a l'usure

Country Status (5)

Country Link
US (1) US6039785A (fr)
EP (1) EP0881958B1 (fr)
JP (1) JP4272706B2 (fr)
DE (2) DE19606270A1 (fr)
WO (1) WO1997030808A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN108026800A (zh) * 2015-10-02 2018-05-11 株式会社理研 烧结阀座

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DE19925300A1 (de) * 1999-06-02 2000-12-07 Mahle Ventiltrieb Gmbh Gußwerkstoff mit hohen Warmhärte
DE102012013226A1 (de) 2012-07-04 2014-01-09 Bleistahl-Produktions Gmbh & Co Kg Hochwärmeleitender Ventilsitzring
DE102013021059A1 (de) 2013-12-18 2015-06-18 Bleistahl-Produktions Gmbh & Co Kg. Double/Triple layer Ventilführung
US10590812B2 (en) 2014-02-10 2020-03-17 Nissan Motor Co., Ltd. Sliding mechanism
WO2015198932A1 (fr) 2014-06-27 2015-12-30 株式会社リケン Siège de soupape fritté et procédé pour la fabrication de celui-ci
CN104561638B (zh) * 2015-01-04 2016-06-08 河南科技大学 一种Al2O3弥散强化铜基复合材料的制备方法
DE102016109539A1 (de) * 2016-05-24 2017-12-14 Bleistahl-Produktions Gmbh & Co Kg. Ventilsitzring
EP3406865B1 (fr) 2017-03-28 2020-01-29 Kabushiki Kaisha Riken Siège de soupape fritté
DE102018209682A1 (de) * 2018-06-15 2019-12-19 Mahle International Gmbh Verfahren zum Herstellen eines pulvermetallurgischen Erzeugnisses
CN109825733B (zh) * 2019-03-11 2021-02-19 中南大学 一种弥散强化铜合金的短流程制备方法
KR20210104418A (ko) * 2020-02-17 2021-08-25 현대자동차주식회사 가변 오일 펌프용 아우터링 및 이의 제조방법
US11473456B2 (en) * 2020-09-15 2022-10-18 GM Global Technology Operations LLC Cylinder head valve seat with high thermal conductivity and multiple material cross-section
DE102020213651A1 (de) * 2020-10-29 2022-05-05 Mahle International Gmbh Verschleißfeste, hochwärmeleitfähige Sinterlegierung, insbesondere für Lageranwendungen und Ventilsitzringe

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108026800A (zh) * 2015-10-02 2018-05-11 株式会社理研 烧结阀座
EP3358156A4 (fr) * 2015-10-02 2019-07-31 Kabushiki Kaisha Riken Siège de soupape fritté

Also Published As

Publication number Publication date
JP4272706B2 (ja) 2009-06-03
WO1997030808A1 (fr) 1997-08-28
JP2001500567A (ja) 2001-01-16
US6039785A (en) 2000-03-21
DE19606270A1 (de) 1997-08-28
DE59703672D1 (de) 2001-07-05
EP0881958B1 (fr) 2001-05-30

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