EP0881958B1 - Werkstoff zur pulvermetallurgischen herstellung von formteilen, insbesondere von ventilsitzringen oder ventilführungen mit hoher verschleissfestigkeit - Google Patents

Werkstoff zur pulvermetallurgischen herstellung von formteilen, insbesondere von ventilsitzringen oder ventilführungen mit hoher verschleissfestigkeit Download PDF

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Publication number
EP0881958B1
EP0881958B1 EP97905071A EP97905071A EP0881958B1 EP 0881958 B1 EP0881958 B1 EP 0881958B1 EP 97905071 A EP97905071 A EP 97905071A EP 97905071 A EP97905071 A EP 97905071A EP 0881958 B1 EP0881958 B1 EP 0881958B1
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EP
European Patent Office
Prior art keywords
weight
powder
material according
powder mixture
molybdenum
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.)
Expired - Lifetime
Application number
EP97905071A
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German (de)
English (en)
French (fr)
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EP0881958A1 (de
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
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Publication of EP0881958A1 publication Critical patent/EP0881958A1/de
Application granted granted Critical
Publication of EP0881958B1 publication Critical patent/EP0881958B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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 powder metallurgical production of molded parts with high thermal conductivity and high wear and tear Corrosion resistance through pressing, sintering and, if necessary, recompression a powder mixture with a copper content of at least about 50% by weight.
  • Such sintered materials are used for molded parts, the hot gases or Exposed to gas mixtures are required, for example for production of valve seat rings and valve guides for internal combustion engines, the on the one hand high mechanical loads and on the other hand at the same time are exposed to hot combustion gases.
  • Valve seat ring or valve guide There are molded parts made of sintered materials based on powder metallurgy Iron base with infiltrated copper known to be used as a Valve seat ring or valve guide have sufficient wear resistance, its thermal conductivity compared to sintered materials without Copper content is not high enough.
  • a sintered material is known, which is made of an iron-based material consists of carbon and lead, as well as other alloy components are clogged.
  • Valve seat rings made from this material have sufficient heat and wear resistance, their However, thermal conductivity is not enough, especially around this upcoming problem in the outlet area of a modern Solve internal combustion engine.
  • PCT-EP 89/01343 describes a sintered material for powder metallurgy Manufacture of valve seat rings known to increase Should have thermal conductivity with high wear resistance.
  • the Sintered material consists of a base metal powder with a Copper content of about 70 to 100 wt .-% copper and one Proportion of alloy.
  • the alloy content can be, for example, from 1 to 3 % By weight of cobalt or a high-alloy additional metal powder, which the base metal powder is mixed as a hard phase, the proportion of which is then is a maximum of 30% by weight.
  • a powder mixture consisting of copper powder solidified by 0.1-1.1% by weight of Al 2 O 3 with at least 50% by weight of Cu is generally known from EP-A-144959.
  • the invention has for its object a sintered material for the powder metallurgical production, in particular of valve seat rings or To create valve guides whose wear resistance is very high and at the same time 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 being strengthened by Al 2 O 3 , containing 0.1 to 1.1% by weight of Al 2 O 3 and less than 0.5% by weight of impurities and by Spraying a Cu-Al melt and then heating it in an oxidizing atmosphere selective oxidation of the aluminum is made.
  • the invention is based on the surprising finding that the use of a Cu-Al 2 O 3 powder which has been strengthened by means of Al 2 O 3 dispersion as a material for the powder-metallurgical production of molded parts leads to products which on the one hand have high wear and corrosion resistance and on the other hand have a high thermal conductivity, 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 in the case of the Cu-Al 2 O 3 powder produced by means of internal oxidation, the distance between the dispersed Al 2 O 3 particles in the copper matrix is of the order of 3 to 12 nm, while in the case of the without inside oxidation produced powder is about 40 ⁇ m.
  • dispersion-strengthened metals as base powder for the powder-metallurgical production of molded parts, in particular valve seat rings or valve guides.
  • a preferred embodiment of the invention provides that the alloy surcharge from a powdered, preferably water atomized intermetallic hard phase from 28 to 32, preferably 30% by weight Molybdenum, 9 to 11, preferably 10% by weight of chromium, 2.5 to 3.5, preferably 3 wt .-% silicon, the rest of cobalt, the intermetallic Hard phase in the powder mixture in an amount of about 10% by weight and the base powder is present in an amount of about 90% by weight.
  • intermetallic Hard phase of 28 to 32, preferably 30% by weight of molybdenum, 9 to 11, preferably 10 wt .-% chromium, 2.5 to 3.5, preferably 3 wt .-% silicon, balance iron, the intermetallic phase in the Powder mixture in an amount of about 10 wt .-% and the base powder in an amount of about 90 wt .-% are present.
  • the alloy surcharge can also consist of a hard phase from a high-speed steel powder of about 6% by weight of tungsten, about 5% by weight Molybdenum, about 2 wt% vanadium, about 4 wt% chromium, balance Iron exist, the hard phase in the powder mixture in an amount up to about 30% by weight and the base powder in an amount of about 70 wt .-% or higher.
  • the alloy surcharge can also consist of a hard phase from a Mo-P-C powder of about 11% by weight molybdenum, about 0.6% by weight Phosphorus, about 1.2 wt .-% carbon, balance iron, the Hard phase and the base powder in the powder mixture in an amount of each about 50 wt .-% are present.
  • the invention also relates to a material which consists of a starting powder mixture from about 80% by weight of base powder, about 10% by weight Molybdenum powder and about 10% by weight copper powder or about 79% by weight Base powder, about 10% by weight molybdenum powder, about 10% by weight copper powder and about 1% by weight of powdered molybdenum trioxide.
  • the invention further provides that the base powder additionally molybdenum disulfide (MoS 2 ) and / or manganese sulfide (MnS) and / or tungsten disulfide (WS 2 ) and / or calcium fluoride (CaF 2 ) and / or tellurium (Te) and / or calcium carbonate ( CaCO 3 ) in a total amount of at least 1 wt .-% to a maximum of 3 wt .-% based on the amount of the base powder.
  • MoS 2 molybdenum disulfide
  • MnS manganese sulfide
  • WS 2 tungsten disulfide
  • CaF 2 calcium fluoride
  • Te tellurium
  • CaCO 3 calcium carbonate
  • the invention further relates to a method 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 a starting powder mixture with one of the compositions described above with about 0.3 wt .-% 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 about 80% by weight of nitrogen and about 20% by weight of hydrogen for a period of about 45 minutes at a temperature of about 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
  • the starting powder according to claim 1 contains one or more of the substances or substance mixtures listed below: a) 5 - 30% by weight tool steel type M35 or type T15, Ni-Cr-Si-Fe-B-Cu-Mo; b) 5-10% by weight of W, Mo, Nb, WC, TiC, B 4 C, TiN, c-BN, TiB 2 ; c) 0.5-5% by weight of Ti, Cr, Zr, Cr + Zr, Be, Ni + P.
  • the substances or substance mixtures listed below a) 5 - 30% by weight tool steel type M35 or type T15, Ni-Cr-Si-Fe-B-Cu-Mo; b) 5-10% by weight of W, Mo, Nb, WC, TiC, B 4 C, TiN, c-BN, TiB 2 ; c) 0.5-5% by weight of Ti, Cr, Zr, Cr + Zr, Be, Ni + P.
  • the proportion should keep the thermal conductivity above 100 W / m ⁇ k Do not exceed 5-20% by weight, typically 10% by weight.
  • the materials of group b) do not alloy with the copper matrix and have therefore no noticeable influence on the thermal conductivity. They are however relatively expensive. However, it has been found that a Share of 5 - 10 wt .-% is sufficient.
  • group c) cause the intermetallic constituents to be excreted and in this way superimpose the hardness effect in addition to the hardening by the Al 2 O 3 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, MoS 2 , MnS, h-BN, CaF 2 and the like, as well as metal additives such as Mo, Co, W or the like, which form oxide skins at operating temperatures that have a lubricating effect .
  • solid lubricants such as graphite, MoS 2 , MnS, h-BN, CaF 2 and the like, as well as metal additives such as Mo, Co, W or the like, which form oxide skins at operating temperatures that have a lubricating effect .
  • 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 green parts made of this material only have green low strength.
  • the green strength can be achieved by adding the aforementioned Components can be increased significantly.
  • the "Cu high green strength” are powders with fibrous, long, thin particles, which intertwine with each other when pressed together in this way cause a high strength of the green body.
  • the Thermal conductivity is not affected by the addition of pure Cu, so that 5-25% by weight can be added, the preferred one Range is 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: a). 0.2-2% by weight of chemical elements such as C (graphite), Te, Se; b). 0.5-5% by weight sulfides such as MoS 2 , MnS, etc .; c). 0.5-5 wt% oxides such as MoO 3 , WO 3 , Co 3 O 4, etc .; d). 0.5 - 5% by weight of compounds such as hexagonal BN, CaF 2 .
  • 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: a) 5-20% by weight of Zn, 0.1-5% by weight of Al or Sn, etc .; b) 5 - 30% by weight tool steel type M35 or type T15, Ni-Cr-Si-Fe-B-Cu-Mo
  • valve seat ring manufacturing lies in all of the aforementioned starting powder mixtures according to the invention in that the thermal conductivity is particularly high, d. H. at least 100 W / m ⁇ k.
  • a Cu-Al 2 O 3 powder which had been dispersion-strengthened by means of internal oxidation and had a content of 0.5% by weight of Al 2 O 3 was mixed with 0.3% by weight of a customary pressure-relieving agent and at a pressure of 800 MN / mm 2 pressed into valve seat rings with the dimensions 36.6 x 30.1 x 9 mm.
  • the green compacts, which had a compression 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% N 2 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
  • the green compacts had a compression density of 8.2 g / cm 3 .
  • the rings were then sintered for 45 minutes at a temperature of 1,040 ° C. in a protective gas atmosphere composed of 80% N 2 and 20% H 2 ; 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
  • valve seat rings manufactured according to Examples 1 and 2 had one compared to unexpected improvement in thermal conductivity commercially available valve seat rings based on Fe with and without Copper infiltration. This results from 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 die 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. Test duration 125 h Number of cylinders 4th Number of valves / cylinders 4th Displacement 1998 cm 3 power 100 kW at 5500 rpm Torque 190 Nm at 4000 rpm fuel Super lead-free - RON 95 Engine oil Shell Super 3 - 10 W 40 Valve disc, inlet Valve disc, outlet uncoated Armored stellite
  • 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 Example 2 according to the invention was compared with the series material Como12 from the applicant, which is used on a large scale.
  • the sinking depth of the valve seat ring according to the invention with 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)
EP97905071A 1996-02-21 1997-02-21 Werkstoff zur pulvermetallurgischen herstellung von formteilen, insbesondere von ventilsitzringen oder ventilführungen mit hoher verschleissfestigkeit Expired - Lifetime EP0881958B1 (de)

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 (de) 1996-02-21 1997-02-21 Werkstoff zur pulvermetallurgischen herstellung von formteilen, insbesondere von ventilsitzringen oder ventilführungen mit hoher verschleissfestigkeit

Publications (2)

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

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EP97905071A Expired - Lifetime EP0881958B1 (de) 1996-02-21 1997-02-21 Werkstoff zur pulvermetallurgischen herstellung von formteilen, insbesondere von ventilsitzringen oder ventilführungen mit hoher verschleissfestigkeit

Country Status (5)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012013226A1 (de) * 2012-07-04 2014-01-09 Bleistahl-Produktions Gmbh & Co Kg Hochwärmeleitender Ventilsitzring
DE102016109539A1 (de) * 2016-05-24 2017-12-14 Bleistahl-Produktions Gmbh & Co Kg. Ventilsitzring

Families Citing this family (12)

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DE19925300A1 (de) * 1999-06-02 2000-12-07 Mahle Ventiltrieb Gmbh Gußwerkstoff mit hohen Warmhärte
DE102013021059A1 (de) * 2013-12-18 2015-06-18 Bleistahl-Produktions Gmbh & Co Kg. Double/Triple layer Ventilführung
WO2015118924A1 (ja) 2014-02-10 2015-08-13 日産自動車株式会社 摺動機構
WO2015198932A1 (ja) 2014-06-27 2015-12-30 株式会社リケン 焼結バルブシート及びその製造方法
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
JP6386676B2 (ja) * 2015-10-02 2018-09-05 株式会社リケン 焼結バルブシート
EP3406865B1 (en) 2017-03-28 2020-01-29 Kabushiki Kaisha Riken Sintered valve seat
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012013226A1 (de) * 2012-07-04 2014-01-09 Bleistahl-Produktions Gmbh & Co Kg Hochwärmeleitender Ventilsitzring
DE102016109539A1 (de) * 2016-05-24 2017-12-14 Bleistahl-Produktions Gmbh & Co Kg. Ventilsitzring

Also Published As

Publication number Publication date
DE19606270A1 (de) 1997-08-28
JP2001500567A (ja) 2001-01-16
EP0881958A1 (de) 1998-12-09
US6039785A (en) 2000-03-21
JP4272706B2 (ja) 2009-06-03
WO1997030808A1 (de) 1997-08-28
DE59703672D1 (de) 2001-07-05

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