EP0080590B1 - Wear-resistant cast iron containing spheroidal graphite, and process for its manufacture - Google Patents

Wear-resistant cast iron containing spheroidal graphite, and process for its manufacture Download PDF

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Publication number
EP0080590B1
EP0080590B1 EP82109487A EP82109487A EP0080590B1 EP 0080590 B1 EP0080590 B1 EP 0080590B1 EP 82109487 A EP82109487 A EP 82109487A EP 82109487 A EP82109487 A EP 82109487A EP 0080590 B1 EP0080590 B1 EP 0080590B1
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cast iron
wear
iron alloy
fact
graphite
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EP0080590A3 (en
EP0080590A2 (en
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Hans Jochem Dr. Neuhäuser
Hans-Jürgen Veutgen
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Goetze GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/04—Cast-iron alloys containing spheroidal graphite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/06—Cast-iron alloys containing chromium
    • C22C37/08—Cast-iron alloys containing chromium with nickel

Definitions

  • the invention relates to a wear-resistant cast iron alloy of high strength with spherulitic graphite precipitation for the production of machine parts subject to wear, such as piston rings of internal combustion engines, in particular of small piston rings with a small radial and / or axial wall thickness, and their manufacturing process.
  • Cast iron alloys for the production of mechanically highly stressed machine parts are special alloys which, in addition to good running and wear properties, good elastic behavior, are also said to have higher strength properties.
  • small piston rings with small diameters of up to 60 mm have a lower absolute strength due to small axial wall thicknesses of usually only 1 to 2 mm, and ring fractures occur more frequently, even if they are made from cast iron alloys that are otherwise customary for piston rings with larger diameters are.
  • Special cast iron alloys with higher strength values must therefore be used for such small piston rings.
  • such cast iron alloys contain up to mostly 1.0% chromium, molybdenum, vanadium and copper.
  • the piston rings are cast in a solidifying, white-leather manner, and the desired graphite deposit and structure are obtained by subsequent annealing, quenching and tempering.
  • the annealed coal obtained during graphitization annealing is produced in a spherolithic form, and as a result the strength of the rings is significantly increased.
  • the running and wear properties of piston rings made from these alloys are not sufficient, so that the running surfaces of the rings must also be provided with wear protection layers.
  • such cast iron alloys are additionally alloyed with 4.5 to 5.5 percent by weight copper. Copper is then present at these levels in the form of inclusions, which take on the role of more compact graphite precipitates.
  • Piston rings cast from these alloys can therefore also be used without wear protection layers.
  • these special alloys are only suitable for large piston rings in diesel engines, and the strength properties for small piston rings are not sufficient.
  • a cast iron alloy for valve seat rings made of 3 to 3.8% carbon, 1.8 to 3% silicon, 0.4 to 1.8% manganese, 0 to 1.0% phosphorus, 1, 0 to 2.0% chromium, 1.0 to 2.0% molybdenum, 0.3 to 1.5% tungsten and optionally 0.1 to 1.2% nickel or copper, 0.1 to 0.4% titanium , 0.1 to 0.3% tin and / or 0.1 to 0.6% vanadium and iron as the rest are known.
  • a cast iron alloy for piston rings with normal spheroidal graphite precipitation achieved by special treatment measures which as alloying elements apart from 1.5 to 4.5% silicon to 3% manganese, up to 3.5% vanadium and up to 2.5 % Molybdenum can also contain up to 2.5% tungsten, up to 1% titanium, up to 2% copper, up to 1% nickel or cobalt or up to 2.5% niobium and / or tantalum.
  • the present invention is therefore based on the object of providing a cast iron alloy with both good wear resistance and good elasticity and high strength, so that it can be used for highly stressed machine parts.
  • the cast iron alloy should above all be used for the manufacture of shatterproof small piston rings without special wear protection of the running surfaces and flank surfaces.
  • this object is achieved by a cast iron alloy, the graphite precipitates of which are formed by an annealing process by the decomposition of ledeburite in an extremely fine form with a high number of spherulites (approximately 300,000 to 900,000 spherulites per cm 2 in a micrograph sample).
  • the alloy has the following composition:
  • Remainder iron including manufacturing-related impurities.
  • the cast iron alloy can contain up to 1.5% aluminum and / or up to 1.0% tin and / or antimony and optionally up to 0.5% of the elements boron, zirconium and / or bismuth, especially to increase the wear resistance.
  • the structure now appears as a remuneration structure with high martensite proportions.
  • the graphite is fine-grained and spherulitic, and the spherulite number is between 300,000 and 900,000 per cm 2 .
  • very fine graphite spherulites seem to have formed during solidification, but these are not visible, so that the cast iron appears to solidify in white.
  • these fine precipitates serve as nuclei for the spherulites that form in extremely high numbers.
  • the number of spherulites is 5 to 10 times higher than that of normal spheroidal graphite cast iron alloys.
  • the phosphide phases are not connected in a network, but are distributed in a dot pattern in the matrix.
  • Small piston rings with outer diameters of approximately 60 mm, radial wall thicknesses of 50 mm and axial ring heights of 1.5 mm were cast from the alloy according to the invention, thermally treated and machined into usable piston rings.
  • the rings were subjected to engine test runs without prior wear-resistant tread coating. They showed both good wear resistance and good strength, and no rings had broken due to ring breakage or wear damage after running.
  • the alloy according to the invention should preferably be used for the production of small piston rings with a small radial wall thickness, it can also be used for similarly stressed and / or dimensioned machine parts. These can also be sealing strips for rotary piston engines or extremely thin-walled and / or extremely loaded medium and large piston rings.
  • micrographs show the graphite excretion and the tempering structure of the alloy.
  • the micrograph 1 shows a 10-fold enlargement of the graphite excretion in a very fine spherulitic form with a spherulite number of about 600,000 per square centimeter.
  • Cross section 2 shows the remuneration structure with predominantly martensitic components.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)

Description

Die Erfindung betrifft eine verachleißfeste Gußeisenlegierung hoher Festigkeit mit sphärolithischer Graphitausscheidung für die Herstellung von auf Verschleiß beanspruchten Maschinenteilen, wie Kolbenringe von Verbrennungskraftmaschinen, und zwar insbesondere von Kleinkolbenringen mit geringer radialer und/oder axialer Wandstärke, und ihr Herstellungsverfahren.The invention relates to a wear-resistant cast iron alloy of high strength with spherulitic graphite precipitation for the production of machine parts subject to wear, such as piston rings of internal combustion engines, in particular of small piston rings with a small radial and / or axial wall thickness, and their manufacturing process.

Gußeisenlegierungen zur Herstellung mechanisch hoch beanspruchter Maschinenteile, wie Kolbenringe von Verbrennungskraftmaschinen, sind Speziallegierungen, die neben guten Lauf- und Verschleißeigenschaften, einem guten elastichen Verhalten zusätzlich auch höhere Festigkeitseigenschaften besitzen sollen. Insbesondere Kleinkolbenringe mit kleinen Durchmessern von beispielsweise bis zu 60 mm haben aufgrund von geringen axialen Wandstärken von meist nur 1 bis 2 mm eine geringere absolute Festigkeit, und es kommt bei ihnen häufiger zu Ringbrüchen, auch wenn sie aus sonst für Kolbenringe größerer Durchmesser üblichen Gußeisenlegierungen hergestellt sind. Für solche Kleinkolbenringe müssen daher spezielle Gußeisenlegierungen mit höheren Festigkeitswerten eingesetzt werden.Cast iron alloys for the production of mechanically highly stressed machine parts, such as piston rings of internal combustion engines, are special alloys which, in addition to good running and wear properties, good elastic behavior, are also said to have higher strength properties. In particular, small piston rings with small diameters of up to 60 mm, for example, have a lower absolute strength due to small axial wall thicknesses of usually only 1 to 2 mm, and ring fractures occur more frequently, even if they are made from cast iron alloys that are otherwise customary for piston rings with larger diameters are. Special cast iron alloys with higher strength values must therefore be used for such small piston rings.

Nach C. Englisch, Kolbenringe, Band 1, Springer Verlag, Wien, 1958, Seiten 204 und 245, besitzen solche Gußeisenlegierungen bis zu meist je 1,0 % Chrom, Molybdän, Vanadin und Kupfer. Die Kolbenringe werden ledeburitisch weiß erstarrend gegossen, und die gewünschte Graphitausscheidung und das gewünschte Gefüge werden durch anschließendes Glühen, Abschrecken und Vergüten erhalten. Die beim Graphitisierungsglühen erhaltene Temperkohle fällt dabei in sphärolithischer Former an, und dadurch bedingt wird die Festigkeit der Ringe wesentlich gesteigert. Offensichtlich aber durch die Graphitausscheidung bedingt, sind die Lauf- und Verschleißeigenschaften von Kolbenringen aus diesen Legierungen nicht ausreichend, so daß die Laufflächen der Ringe zusätzlich mit Verschleißschutzschichten versehen werden müssen.According to C. Englisch, Kolbenringe, Volume 1, Springer Verlag, Vienna, 1958, pages 204 and 245, such cast iron alloys contain up to mostly 1.0% chromium, molybdenum, vanadium and copper. The piston rings are cast in a solidifying, white-leather manner, and the desired graphite deposit and structure are obtained by subsequent annealing, quenching and tempering. The annealed coal obtained during graphitization annealing is produced in a spherolithic form, and as a result the strength of the rings is significantly increased. Obviously, however, due to the graphite precipitation, the running and wear properties of piston rings made from these alloys are not sufficient, so that the running surfaces of the rings must also be provided with wear protection layers.

Nach der DE-AS 1.172.049 werden derartige Gußeisenlegierungen zusätzlich mit 4,5 bis 5,5 Gewichtsprozent Kupfer legiert. Kupfer liegt dann bei diesen Gehalten in der Form von Einschlüssen vor, die die Rolle von kompakteren Graphitausscheidungen übernehmen. Aus diesen Legierungen gegossene Kolbenringe können daher auch ohne Verschleißschutzschichten eingesetzt werden. Diese Speziallegierungen eigenen sich aber nur für Großkolbenringe von Dieselmotoren, und die Festigkeitseigenschaften für Kleinkolbenringe sind nicht ausreichend.According to DE-AS 1.172.049, such cast iron alloys are additionally alloyed with 4.5 to 5.5 percent by weight copper. Copper is then present at these levels in the form of inclusions, which take on the role of more compact graphite precipitates. Piston rings cast from these alloys can therefore also be used without wear protection layers. However, these special alloys are only suitable for large piston rings in diesel engines, and the strength properties for small piston rings are not sufficient.

Nach der GB-PA 1.339.919 ist eine Gußeisenlegierung für Ventilsitzringe aus 3 bis 3,8 % Kohlenstoff, 1,8 bis 3 % Silizium, 0,4 bis 1,8 % Mangan, 0 bis 1,0 % Phosphor, 1,0 bis 2,0 % Chrom, 1,0 bis 2,0 % Molybdän, 0,3 bis 1,5 % Wolfram und gegebenenfalls 0,1 bis 1,2 % Nickel oder Kupfer, 0,1 bis 0,4 % Titan, 0,1 bis 0,3 % Zinn und/oder 0,1 bis 0,6 % Vanadin und Eisen als Rest bekannt.According to GB-PA 1.339.919, a cast iron alloy for valve seat rings made of 3 to 3.8% carbon, 1.8 to 3% silicon, 0.4 to 1.8% manganese, 0 to 1.0% phosphorus, 1, 0 to 2.0% chromium, 1.0 to 2.0% molybdenum, 0.3 to 1.5% tungsten and optionally 0.1 to 1.2% nickel or copper, 0.1 to 0.4% titanium , 0.1 to 0.3% tin and / or 0.1 to 0.6% vanadium and iron as the rest are known.

Nach der DE-OS 2428822 ist eine Gußeisenlegierung für Kolbenringe mit normaler und durch besondere Behandlungsmaßnahmen erzielter Kugelgraphitausscheidung bekannt, die als Legierungselemente außer 1,5 bis 4,5 % Silizium bis 3 % Mangan, bis 3,5 % Vanadin und bis 2,5 % Molybdän auch bis zu 2,5 % Wolfram, bis zu 1 % Titan, bis zu 2 % Kupfer, bis zu 1 % Nickel oder Kobalt oder bis zu 2,5 % Niob und/oder Tantal enthalten kann. Diese Legierungen erwiesen sich, insbesondere auch wegen der ausgewogenen Zusammensetzung der Legierungselemente, als ausreichend verschleißfest, der relativ kompakt vorliegende Kugelgraphit wiederum beeinflusste die Festigkeit jedoch derart nachteilig, daß diese Legierungen zur Herstellung von insbesondere Kleinkolbenringen mit geringen axialen Höhen nicht ausreichend bruchsicher waren.According to DE-OS 2428822, a cast iron alloy for piston rings with normal spheroidal graphite precipitation achieved by special treatment measures is known, which as alloying elements apart from 1.5 to 4.5% silicon to 3% manganese, up to 3.5% vanadium and up to 2.5 % Molybdenum can also contain up to 2.5% tungsten, up to 1% titanium, up to 2% copper, up to 1% nickel or cobalt or up to 2.5% niobium and / or tantalum. These alloys proved to be sufficiently wear-resistant, in particular because of the balanced composition of the alloy elements, but the relatively compact spheroidal graphite in turn influenced the strength to such an extent that these alloys were not sufficiently break-proof to produce small piston rings with low axial heights in particular.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, eine Gußeisenlegierung mit sowohl einer guten Verschleißfestigkeit als auch einer guten Elastizität und einer hohen Festigkeit zu schaffen, so daß sie für hoch belastete Maschinenteile eingesetzt werden kann. Die Gußeisenlegierung soll vor allem zur Herstellung bruchsicherer Kleinkolbenringe ohne besonderen Verschleißschutz der Laufflächen und Flankenflächen verwendet werden können.The present invention is therefore based on the object of providing a cast iron alloy with both good wear resistance and good elasticity and high strength, so that it can be used for highly stressed machine parts. The cast iron alloy should above all be used for the manufacture of shatterproof small piston rings without special wear protection of the running surfaces and flank surfaces.

Erfindungsgemäß wird diese Aufgabe durch eine Gußeisenlegierung gelöst, deren Graphitausscheidungen durch einen Glühprozeß durch Zerfall von Ledeburit in extrem feiner Form mit hoher Sphärolithzahl (etwa 300.000 bis 900.000 Sphärolithen pro cm2 in einer Schliffbildprobe) gebildet sind. Die Legierung hat die folgende Zusammensetzung :

Figure imgb0001
Figure imgb0002
 According to the invention, this object is achieved by a cast iron alloy, the graphite precipitates of which are formed by an annealing process by the decomposition of ledeburite in an extremely fine form with a high number of spherulites (approximately 300,000 to 900,000 spherulites per cm 2 in a micrograph sample). The alloy has the following composition:
Figure imgb0001
Figure imgb0002

Rest Eisen einschließlich herstellungsbedingter Verunreinigungen.Remainder iron including manufacturing-related impurities.

Vor allem zur Erhöhung der Verschleißfestigkeit kann die Gußeisenlegierung noch bis zu 1,5 % Aluminium und/oder bis zu 1,0 % Zinn und/oder Antimon sowie gegebenenfalls biz zu 0,5 % der Elemente Bor, Zirkon und/oder Wismuth enthalten.The cast iron alloy can contain up to 1.5% aluminum and / or up to 1.0% tin and / or antimony and optionally up to 0.5% of the elements boron, zirconium and / or bismuth, especially to increase the wear resistance.

Bei der Herstellung verzichtet man bewußt auf eines der zur Kugelgraphitbildung üblicherweise verwendeten Verfahren und impft lediglich die Gußeisenschmelze mit handelsüblichem Ferrosilizium, welches bis zu 0,5 bis 2,0 % Magnesium enthält. Gegebenenfalls ist das Magnesium ganz oder teilweise durch die seltenen Erden, wie Cer, Yttrium, Lanthan, Neodym und/oder Praseodym, ersetzt. Es wird mit einer Impfmittelmenge von nur 0,1 bis 1.0% geimpft, so daß die Gußeisenlegierung weiß und ledeburitisch erstarrt. Anschließend erfolgt das Graphitisierungsglühen von bevorzugt 15 Minuten oberhalb 950 °C, die Abschreckvergütung auf die gewünschte Härte oberhalb 700 °C und das Anlassen oberhalb 300 °C.During production, one deliberately does without one of the methods commonly used for spheroidal graphite formation and only inoculates the cast iron melt with commercially available ferrosilicon, which contains up to 0.5 to 2.0% magnesium. If necessary, all or part of the magnesium is replaced by the rare earths, such as cerium, yttrium, lanthanum, neodymium and / or praseodymium. It is vaccinated with an inoculant amount of only 0.1 to 1.0%, so that the cast iron alloy solidifies white and ledeburitic. This is followed by graphitization annealing, preferably 15 minutes above 950 ° C, quenching to the desired hardness above 700 ° C and tempering above 300 ° C.

Im Schliffbild erscheint das Gefüge jetzt als Vergütungsgefüge mit hohen Martensitanteilen. Der Graphit ist feinkörnig und sphärolithisch, und die Sphärolithenzahl liegt zwischen 300 000 und 900 000 pro cm2. Beim Empfen mit dem geringen magnesiumhaltigen Ferrosilizium scheinen sich beim Erstarren schon sehr feine Graphitsphärolithen gebildet zu haben, die jedoch nicht sichtbar sind, so daß das Gußeisen weiß erstarrend erscheint. Beim Glühprozeß dienen diese feinen Ausscheidungen als Keime für die in extrem hoher Zahl sich bildenden Sphärolithen. Die Sphärolithenzahl ist somit 5 bis 10-fach höher als bei normalen kugelgraphithischen Gußeisenlegierungen. Die Phosphidphasen sind nicht netzförmig zusammenhängend, sondern sind punktförmig in der Matrix verteilt.In the micrograph, the structure now appears as a remuneration structure with high martensite proportions. The graphite is fine-grained and spherulitic, and the spherulite number is between 300,000 and 900,000 per cm 2 . When receiving with the low magnesium-containing ferrosilicon, very fine graphite spherulites seem to have formed during solidification, but these are not visible, so that the cast iron appears to solidify in white. In the annealing process, these fine precipitates serve as nuclei for the spherulites that form in extremely high numbers. The number of spherulites is 5 to 10 times higher than that of normal spheroidal graphite cast iron alloys. The phosphide phases are not connected in a network, but are distributed in a dot pattern in the matrix.

Aus der erfindungsgemäßen Legierung wurden Kleinkolbenringe mit Außendurchmessern von etwa 60mm, radialen Wanddicken von 50 mm und axialen Ringhöhen von 1,5 mm gegossen, thermisch behandelt und zu einsatzfähigen Kolbenringen bearbeitet. Die Ringe wurden Motortestläufen ohne vorherige verschleißfeste Laufflächenbeschichtung unterzogen. Sie zeigten sowohl eine gute Verschleißfestigkeit als auch eine gute Festigkeit, und es waren nach dem Laufen keine Ringe durch Ringbruch oder durch Verschleißschäden ausgefallen.Small piston rings with outer diameters of approximately 60 mm, radial wall thicknesses of 50 mm and axial ring heights of 1.5 mm were cast from the alloy according to the invention, thermally treated and machined into usable piston rings. The rings were subjected to engine test runs without prior wear-resistant tread coating. They showed both good wear resistance and good strength, and no rings had broken due to ring breakage or wear damage after running.

Durch die. Erfindung ist somit eine Gußeisenlegierung mit hoher Verschleißfestigkeit als auch hoher' Bruchfestigkeit geschaffen worden. In der Legierung sorgt einmal die ausgewogene Zusammensetzung der Legierungselemente für die guten Gleit- und Laufeigenschaften, obwohl der Graphit extrem feinkörnig vorliegt. Die extrem feine Verteilung der Sphärolithen verbessert wiederum die Festigkeits-und Dehnungseigenschaften der Werkstücke.Through the. Invention has thus been created a cast iron alloy with high wear resistance as well as high ' breaking strength. In the alloy, the balanced composition of the alloy elements ensures good sliding and running properties, even though the graphite is extremely fine-grained. The extremely fine distribution of the spherulites in turn improves the strength and elongation properties of the workpieces.

Obwohl die erfindungsgemäße Legierung bevorzugt zur Herstellung von Kleinkolbenringen mit geringer radialer Wandstärke verwendet werden soll, kann sie genauso für ähnlich beanspruchte und/oder dimensionierte Maschinenteile verwendet werden. Dies können auch Dichtleisten für Kreiskolbenmotoren oder extrem dünnwandige und/oder extrem belastete Mittel- und Großkolbenringe sein.Although the alloy according to the invention should preferably be used for the production of small piston rings with a small radial wall thickness, it can also be used for similarly stressed and / or dimensioned machine parts. These can also be sealing strips for rotary piston engines or extremely thin-walled and / or extremely loaded medium and large piston rings.

Die Schliffbilder zeigen die Graphitausscheidung und das Vergütungsgefüge der Legierung.The micrographs show the graphite excretion and the tempering structure of the alloy.

Das Schliffbild 1 zeigt in 10-facher Vergrößerung die Graphitausscheidung in sehr feiner sphörolithischer Form mit einer Sphärolithenzahl von etwa 600.000 pro Quadratzentimeter.The micrograph 1 shows a 10-fold enlargement of the graphite excretion in a very fine spherulitic form with a spherulite number of about 600,000 per square centimeter.

Schliffbild 2 zeigt das Vergütungsgefüge mit überwiegend martensitischen Anteilen.Cross section 2 shows the remuneration structure with predominantly martensitic components.

Claims (3)

1. Wear-resistant high strength cast iron alloy with spheroidal graphite separation for the manufacture especially of small-size piston rings with small radial and/or axial wall thickness, characterized by the fact that the cast iron alloy possesses a heat-treated structure in which the graphite has been formed by an annealing process by the disintegration of ledeburite and is present in extremely fine form in a large number of spherolites of about 300.000 to 900.000/cmz, and that the cast iron alloy obtains
Figure imgb0005
the remainder being iron with impurities stemming from the production process.
2. Process for manufacturing the coatings form the cast iron alloy according to Claim 1, characterized by the fact that the cast iron melt is inoculated with 0,1 to 1,0 % ferrosilicon containing 0,5 to 2,0 % magnesium, that the cast iron melt is cast with ledeburitic solidification, and that the coatings are then subjected to a graphitizing anneal with subsequent quenching above 700 °C and tempering above 300 °C.
3. Process according to Claim 2, characterized by the fact that all or some of the magnesium in the inoculant is replaced by at least one of the rare earth metallic elements such as cerrium, yttrium, lanthanum, neodynium and/or praseodynium.
EP82109487A 1981-12-01 1982-10-14 Wear-resistant cast iron containing spheroidal graphite, and process for its manufacture Expired EP0080590B1 (en)

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