EP0924310A1 - Aluminium alloy containing silicon for use as pistons in automobiles - Google Patents

Aluminium alloy containing silicon for use as pistons in automobiles Download PDF

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Publication number
EP0924310A1
EP0924310A1 EP98123801A EP98123801A EP0924310A1 EP 0924310 A1 EP0924310 A1 EP 0924310A1 EP 98123801 A EP98123801 A EP 98123801A EP 98123801 A EP98123801 A EP 98123801A EP 0924310 A1 EP0924310 A1 EP 0924310A1
Authority
EP
European Patent Office
Prior art keywords
alloy
piston
pistons
aluminium
percent
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
EP98123801A
Other languages
German (de)
French (fr)
Other versions
EP0924310B1 (en
Inventor
Simon Thomas Gazzard
Jonathan David Philby
Simon Barnes
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.)
Federal Mogul Bradford Ltd
Original Assignee
Federal Mogul Bradford Ltd
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 Federal Mogul Bradford Ltd filed Critical Federal Mogul Bradford Ltd
Publication of EP0924310A1 publication Critical patent/EP0924310A1/en
Application granted granted Critical
Publication of EP0924310B1 publication Critical patent/EP0924310B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04Modified aluminium-silicon alloys
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00Pistons 
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F7/00Casings, e.g. crankcases or frames
    • F02F7/0085Materials for constructing engines or their parts
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02FCYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F2200/00Manufacturing
    • F02F2200/04Forging of engine parts
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05CINDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00Metals
    • F05C2201/02Light metals
    • F05C2201/021Aluminium
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05CINDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2251/00Material properties
    • F05C2251/04Thermal properties
    • F05C2251/042Expansivity

Definitions

  • the present invention relates to a aluminium-silicon alloy.
  • the alloy has use in the manufacture of pistons, in particular for pistons for use in internal combustion engines.
  • pistons are exposed to both static and dynamic stresses, while operating in bulk temperatures from sub-zero to up to 400°C. These stresses will also differ in different regions of the piston; for example a combustion bowl in a piston will be subject to different thermal and mechanical stresses than piston pin bosses.
  • the piston must also have low thermal expansion, and possess good bearing characteristics with marginal lubrication over the noted range of temperatures. Also, the piston material must lend itself to being formed into a piston, for example by casting with subsequent working.
  • Known casting alloys for piston manufacture include those disclosed in Japanese Patent Application J01108339-A.
  • the alloys disclosed therein is an aluminium based alloy including silicon from 9 to 12 percent, copper from 0.5 to 2.5 percent, magnesium from 0.8 to 2.0 percent, cobalt from 0.5 to 3 percent, nickel from 1 to 3 percent, iron from 0.3 to 1.0 percent, manganese from 0.1 to 1.0 percent and titanium from 0.01 to 0.15 percent with the balance being aluminium and unavoidable impurities.
  • This alloy is said to provide high strength from 150 to 250 °C.
  • the alloy comprises from 8.0 to 10.9 percent silicon, from 0.8 to 2.0 percent magnesium, from 4.0 to 5.9 percent copper, from 1.0 to 3.0 percent nickel, from 0.2 to 0.4 percent manganese, less than 0.5 percent iron and at least one element from the group including antimony, zirconium, titanium, strontium, cobalt, chrome and vanadium whereby at least one element is present in an amount greater than 0.8 percent and the sum of the elements in this group is no more than 0.8 percent, with the balance of the alloy being aluminium and unavoidable impurities.
  • the present invention has as an advantage that it provides good strength over the range of temperatures in which a piston made from the alloy operates.
  • the alloy of the present invention is selected from a group of aluminium alloys with each alloy component element being present in weight percent as follows:
  • Zinc, Lead and Tin may also be present up to 0.15 weight percent. More preferably, the total amount of Lead and Tin may not exceed 0.15 weight percent.
  • the Copper allows age hardening of the alloy. An increase the amount of Copper beyond the limit stated reduces the high temperature fatigue strength of the alloy due to the generation of larger Copper-Nickel rich intermetallic crystals. An increase in the Copper level can also lead to shrinkage porosity problems in larger castings.
  • the Magnesium is present to contribute to the strength of the alloy. However, increasing the amount of Magnesium will lead to larger intermetallics in the as cast condition, but after aging these will be removed.
  • the Magnesium is added at a level where it provides good strengthening after aging through the formation of Mg 2 Si. Higher Magnesium levels lead to greater oxidation losses during the casting process, and thus a greater tendency for the cast metal to contain oxide defects.
  • the Nickel contributes to the high temperature strength of the alloy by the formation of thermally stable intermetallic crystals. However, exceeding the limits stated will reduce the high temperature fatigue strength of the alloy due to the precipitation of coarse intermetallic crystals. This tendancy is made worse by the low cooling rates associated with the casting of large pistons.
  • the Cobalt content is chosen to allow the formation of a large number of small intermetallics. This is believed to improve the mechanical properties of the alloy at 350°C.
  • the presence of the Cobalt in the Aluminium alloy at the levels stated is believed to reduce the diffusivity of the Copper in Aluminium, thereby slowing the overaging mechanism of the alloy. This has particular importance when considering the operation of a piston pin boss operating at around 200°C.
  • the presence of the Cobalt is believed also to lead to an increase in fatigue strength of the alloy at 350°C. This is of particular importance when considering the operation of a combustion bowl of a piston which is typically subject to such temperatures.
  • Titanium or Zirconium and/or Vanadium are each present as a grain refining addition.
  • the alloy may optionally include at least one of the following
  • alloys of the present invention in addition to their use in the manufacture of forged pistons, may be used in the manufacture of gravity die cast pistons.

Abstract

An improved aluminium - silicon alloy for use in the manufacture of pistons is disclosed. The improved alloy is of the following composition in which the component elements are
  • 10.5 to 13.5 silicon
  • 2.0 to less than 4.0 copper
  • 0.8 to 1.5 magnesium
  • 0.5 to 2.0 nickel
  • 0.3 to 0.9 cobalt
  • at least 20 ppm phosphorous
    and either
  • (i) 0.05 to 0.2 titanium; or
  • (ii)at least one of the following
  • up to 0.2 zirconium
  • up to 0.2 vanadium;
    in either case with the balance Aluminium and unavoidable impurities.
  • Description

    • The present invention relates to a aluminium-silicon alloy. The alloy has use in the manufacture of pistons, in particular for pistons for use in internal combustion engines.
    • A satisfactory piston material must meet many differing requirements. In use, pistons are exposed to both static and dynamic stresses, while operating in bulk temperatures from sub-zero to up to 400°C. These stresses will also differ in different regions of the piston; for example a combustion bowl in a piston will be subject to different thermal and mechanical stresses than piston pin bosses. The piston must also have low thermal expansion, and possess good bearing characteristics with marginal lubrication over the noted range of temperatures. Also, the piston material must lend itself to being formed into a piston, for example by casting with subsequent working.
    • Known casting alloys for piston manufacture include those disclosed in Japanese Patent Application J01108339-A. Among the alloys disclosed therein is an aluminium based alloy including silicon from 9 to 12 percent, copper from 0.5 to 2.5 percent, magnesium from 0.8 to 2.0 percent, cobalt from 0.5 to 3 percent, nickel from 1 to 3 percent, iron from 0.3 to 1.0 percent, manganese from 0.1 to 1.0 percent and titanium from 0.01 to 0.15 percent with the balance being aluminium and unavoidable impurities. This alloy is said to provide high strength from 150 to 250 °C.
    • Another alloy is disclosed in DE 44 04 420 which may have application as an alloy for use in the manufacture of pistons for an automotive vehicle. The alloy comprises from 8.0 to 10.9 percent silicon, from 0.8 to 2.0 percent magnesium, from 4.0 to 5.9 percent copper, from 1.0 to 3.0 percent nickel, from 0.2 to 0.4 percent manganese, less than 0.5 percent iron and at least one element from the group including antimony, zirconium, titanium, strontium, cobalt, chrome and vanadium whereby at least one element is present in an amount greater than 0.8 percent and the sum of the elements in this group is no more than 0.8 percent, with the balance of the alloy being aluminium and unavoidable impurities.
    • The present invention has as an advantage that it provides good strength over the range of temperatures in which a piston made from the alloy operates.
    • The alloy of the present invention is selected from a group of aluminium alloys with each alloy component element being present in weight percent as follows:
    • 10.5 to 13.5 silicon
    • 2.0 to less than 4.0 copper
    • 0.8 to 1.5 magnesium
    • 0.5 to 2.0 nickel
    • 0.3 to 0.9 cobalt
    • at least 20 ppm phosphorous
      and either
    • (i) 0.05 to 0.2 titanium; or
    • (ii) at least one of the following
    • up to 0.2 zirconium
    • up to 0.2 vanadium;
      in either case with the balance Aluminium and unavoidable impurities.
    • Preferably Zinc, Lead and Tin may also be present up to 0.15 weight percent. More preferably, the total amount of Lead and Tin may not exceed 0.15 weight percent.
    • The Copper allows age hardening of the alloy. An increase the amount of Copper beyond the limit stated reduces the high temperature fatigue strength of the alloy due to the generation of larger Copper-Nickel rich intermetallic crystals. An increase in the Copper level can also lead to shrinkage porosity problems in larger castings.
    • The Magnesium is present to contribute to the strength of the alloy. However, increasing the amount of Magnesium will lead to larger intermetallics in the as cast condition, but after aging these will be removed. The Magnesium is added at a level where it provides good strengthening after aging through the formation of Mg2Si. Higher Magnesium levels lead to greater oxidation losses during the casting process, and thus a greater tendency for the cast metal to contain oxide defects.
    • The Nickel contributes to the high temperature strength of the alloy by the formation of thermally stable intermetallic crystals. However, exceeding the limits stated will reduce the high temperature fatigue strength of the alloy due to the precipitation of coarse intermetallic crystals. This tendancy is made worse by the low cooling rates associated with the casting of large pistons.
    • The Cobalt content is chosen to allow the formation of a large number of small intermetallics. This is believed to improve the mechanical properties of the alloy at 350°C. In addition, the presence of the Cobalt in the Aluminium alloy at the levels stated is believed to reduce the diffusivity of the Copper in Aluminium, thereby slowing the overaging mechanism of the alloy. This has particular importance when considering the operation of a piston pin boss operating at around 200°C. However, the presence of the Cobalt is believed also to lead to an increase in fatigue strength of the alloy at 350°C. This is of particular importance when considering the operation of a combustion bowl of a piston which is typically subject to such temperatures.
    • The Titanium or Zirconium and/or Vanadium are each present as a grain refining addition.
    • Preferably, the alloy may optionally include at least one of the following
    • up to 0.5 iron
    • up to 0.25 manganese
    • up to 0.05 chrome, and
    • up to 15 ppm each of calcium, sodium, strontium and lithium.
    • The present invention will now be described, by way of example only, with reference to the following Illustrative Examples.
    • Example 1
    • The use of a specific alloy composition in the manufacture of forged pistons has proven to be particularly advantageous. The metal alloy compositions of this alloy with the component elements being indicated in weight percent are as follows:
    • 10.5 to 13.5 silicon
    • 2.0 to less than 4.0 copper
    • 0.8 to 1.5 magnesium
    • 0.5 to 2.0 nickel
    • to 0.9 cobalt
    • 0.05 to 0.2 titanium
    • at least 20 ppm phosphorous
      with the balance Aluminium and unavoidable impurities.
    • Example 2
    • Another alloy within the scope of the present invention also found to have utilty in the manufacture of pistons has the following composition with the component elements being indicated in weight percent as follows:
    • 10.5 to 13.5 silicon
    • 2.0 to less than 4.0 copper
    • 0.8 to 1.5 magnesium
    • 0.5 to 2.0 nickel
    • 0.3 to 0.9 cobalt
    • at least 20 ppm phosphorous; and
      at least one of the following
    • up to 0.2 zirconium
    • up to 0.2 vanadium;
      with the balance Aluminum and unavoidable impurities.
    • Example 3
    • Another alloy within the scope of the present invention found to have utilty in the manufacture of pistons has the following composition with the component elements being indicated in weight percent as follows:
    • 10.5 to 11.5 silicon
    • 2.5 to 3.5 copper
    • 0.8 to 1.5 magnesium
    • 0.5 to 1.5 nickel
    • 0.3 to 0.7 cobalt
    • up to 0.20 titanium
    • up to 0.2 zirconium
    • up to 0.2 vanadium
    • up to 0.50 iron
    • up to 0.25 manganese
    • up to 0.05 chrome
    • up to 0.15 zinc
    • up to 0.15 lead
    • up to 0.15 tin; the total of lead and tin not to exceed 0.15
    • at least 20 ppm phosphorous
    • up to 15 ppm each of calcium, sodium, strontium and lithium
      with the balance Aluminium and unavoidable impurities
    • The alloys of the present invention, in addition to their use in the manufacture of forged pistons, may be used in the manufacture of gravity die cast pistons.

    Claims (7)

    1. An aluminium alloy in which the component elements are present in weight percent as follows:
      10.5 to 13.5 silicon
      2.0 to less than 4.0 copper
      0.8 to 1.5 magnesium
      0.5 to 2.0 nickel
      0.3 to 0.9 cobalt
      at least 20 ppm phosphorous
      and either
      (i) 0.05 to 0.2 titanium; or
      (ii) at least one of the following
      up to 0.2 zirconium
      up to 0.2 vanadium;
      in either case with the balance Aluminium and unavoidable impurities.
    2. An alloy according to claim 1, characterised in that Zinc, Lead and Tin may also be present up to 0.15 wt% as unavoidable impurities.
    3. An alloy according to claim 2, characterised in that the total amount of Lead and Tin does not exceed 0.15 wt%.
    4. An alloy according to any of claims 1 to 3, characterised in that the alloy may optionally include at least one of the following
      up to 0.5 iron
      up to 0.25 manganese
      up to 0.05 chrome, and
      up to 15 ppm each of calcium, sodium, strontium and lithium.
    5. A piston manufactured from an alloy according to any previous claim.
    6. A piston according to claim 5, characterised in that the piston is manufactured by forging.
    7. A piston according to claim 5, characterised in that the piston is manufactured by gravity die casting.
    EP19980123801 1997-12-20 1998-12-15 Aluminium alloy containing silicon for use as pistons in automobiles Expired - Lifetime EP0924310B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    GB9726840 1997-12-20
    GB9726840A GB2332448B (en) 1997-12-20 1997-12-20 Aluminium alloy

    Publications (2)

    Publication Number Publication Date
    EP0924310A1 true EP0924310A1 (en) 1999-06-23
    EP0924310B1 EP0924310B1 (en) 2001-09-12

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    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP19980123801 Expired - Lifetime EP0924310B1 (en) 1997-12-20 1998-12-15 Aluminium alloy containing silicon for use as pistons in automobiles

    Country Status (3)

    Country Link
    EP (1) EP0924310B1 (en)
    DE (1) DE69802017T2 (en)
    GB (1) GB2332448B (en)

    Cited By (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1253210A1 (en) * 2001-03-28 2002-10-30 Honda Giken Kogyo Kabushiki Kaisha Heat resistant Al die cast material
    EP1690953A1 (en) * 2003-12-02 2006-08-16 Sumitomo Electric Sintered Alloy, Ltd. Heat-resistant and highly tough aluminum alloy and method for production thereof and engine parts
    WO2013050357A1 (en) * 2011-10-04 2013-04-11 Federal-Mogul Nürnberg GmbH Method for producing an engine component and engine component
    WO2014076174A1 (en) * 2012-11-14 2014-05-22 Federal-Mogul Nürnberg GmbH Method for producing an engine component, engine component, and use of an aluminium alloy
    WO2014137690A1 (en) * 2013-03-05 2014-09-12 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    US9163579B2 (en) 2011-11-28 2015-10-20 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    US9169800B2 (en) 2011-11-28 2015-10-27 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    DE102014209102A1 (en) * 2014-05-14 2015-11-19 Federal-Mogul Nürnberg GmbH Method for producing an engine component, engine component and use of an aluminum alloy
    WO2020207829A1 (en) * 2019-04-09 2020-10-15 Ks Kolbenschmidt Gmbh Piston for an internal combustion engine
    US20210222271A1 (en) * 2018-06-20 2021-07-22 Federal-Mogul Nurnberg Gmbh Aluminum alloy, method for producing an engine component, engine component, and use of an aluminum alloy to produce an engine component
    US11391238B2 (en) 2019-05-16 2022-07-19 Mahel International GmbH Process for producing an engine component, engine component and the use of an aluminum alloy

    Families Citing this family (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US7682469B2 (en) 2002-07-22 2010-03-23 Kabushiki Kaisha Toyota Chuo Kenkyusho Piston made of aluminum cast alloy and method of manufacturing the same
    JP6103382B2 (en) * 2013-10-31 2017-03-29 スズキ株式会社 Aluminum alloy
    CN108913961A (en) * 2018-08-13 2018-11-30 文登皇利压铸化工材料有限公司 The piston aluminium ingot used for turbocharging automobile

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    Cited By (22)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1253210A1 (en) * 2001-03-28 2002-10-30 Honda Giken Kogyo Kabushiki Kaisha Heat resistant Al die cast material
    EP1690953A1 (en) * 2003-12-02 2006-08-16 Sumitomo Electric Sintered Alloy, Ltd. Heat-resistant and highly tough aluminum alloy and method for production thereof and engine parts
    EP1690953A4 (en) * 2003-12-02 2008-02-13 Sumitomo Electric Sintered Aly Heat-resistant and highly tough aluminum alloy and method for production thereof and engine parts
    WO2013050357A1 (en) * 2011-10-04 2013-04-11 Federal-Mogul Nürnberg GmbH Method for producing an engine component and engine component
    US9163579B2 (en) 2011-11-28 2015-10-20 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    US9169800B2 (en) 2011-11-28 2015-10-27 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    JP2016505382A (en) * 2012-11-14 2016-02-25 フェデラル−モーグル ニュルンベルグ ゲゼルシャフト ミット ベシュレンクテル ハフツング Method for manufacturing engine components, use of engine components and aluminum alloys
    WO2014076174A1 (en) * 2012-11-14 2014-05-22 Federal-Mogul Nürnberg GmbH Method for producing an engine component, engine component, and use of an aluminium alloy
    CN104812921A (en) * 2012-11-14 2015-07-29 菲特尔莫古纽伦堡公司 Method for producing an engine component, engine component, and use of an aluminium alloy
    JP2018114556A (en) * 2012-11-14 2018-07-26 フェデラル−モーグル ニュルンベルグ ゲゼルシャフト ミット ベシュレンクテル ハフツング Method for manufacturing engine component, engine component, and use of aluminium alloy
    US10022788B2 (en) 2012-11-14 2018-07-17 Federal-Mogul Nurnberg Gmbh Method for producing an engine component, engine component, and use of an aluminium alloy
    CN104812921B (en) * 2012-11-14 2018-01-19 菲特尔莫古纽伦堡公司 Manufacture the application of the methods of engine components, engine components and aluminium alloy
    WO2014137690A1 (en) * 2013-03-05 2014-09-12 Federal-Mogul Corporation Piston with anti-carbon deposit coating and method of construction thereof
    CN105190000A (en) * 2013-03-05 2015-12-23 费德罗-莫格尔公司 Piston with anti-carbon deposit coating and method of construction thereof
    CN106795591A (en) * 2014-05-14 2017-05-31 菲特尔莫古纽伦堡有限公司 Application for producing method, engine components and the aluminium alloy of engine components
    JP2017519105A (en) * 2014-05-14 2017-07-13 フェデラル−モーグル ニュルンベルグ ゲゼルシャフト ミット ベシュレンクテル ハフツング Method for manufacturing engine components, use of engine components and aluminum alloys
    WO2015173172A1 (en) * 2014-05-14 2015-11-19 Federal-Mogul Nürnberg GmbH Method for producing an engine component, engine component, and use of an aluminum alloy
    DE102014209102A1 (en) * 2014-05-14 2015-11-19 Federal-Mogul Nürnberg GmbH Method for producing an engine component, engine component and use of an aluminum alloy
    US11280292B2 (en) 2014-05-14 2022-03-22 Federal-Mogul Nurnberg Gmbh Method for producing an engine component, engine component, and use of an aluminum alloy
    US20210222271A1 (en) * 2018-06-20 2021-07-22 Federal-Mogul Nurnberg Gmbh Aluminum alloy, method for producing an engine component, engine component, and use of an aluminum alloy to produce an engine component
    WO2020207829A1 (en) * 2019-04-09 2020-10-15 Ks Kolbenschmidt Gmbh Piston for an internal combustion engine
    US11391238B2 (en) 2019-05-16 2022-07-19 Mahel International GmbH Process for producing an engine component, engine component and the use of an aluminum alloy

    Also Published As

    Publication number Publication date
    GB2332448A (en) 1999-06-23
    EP0924310B1 (en) 2001-09-12
    GB9726840D0 (en) 1998-02-18
    GB2332448B (en) 2002-06-26
    DE69802017T2 (en) 2002-03-21
    DE69802017D1 (en) 2001-11-15

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