EP3910086B1 - Copper manganese aluminium-iron wrought alloy - Google Patents

Copper manganese aluminium-iron wrought alloy Download PDF

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Publication number
EP3910086B1
EP3910086B1 EP21000110.3A EP21000110A EP3910086B1 EP 3910086 B1 EP3910086 B1 EP 3910086B1 EP 21000110 A EP21000110 A EP 21000110A EP 3910086 B1 EP3910086 B1 EP 3910086B1
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alloy
weight
iron
copper
manganese
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EP3910086A1 (en
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Igor Altenberger
Hans-Achim Kuhn
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Wieland Werke AG
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Wieland Werke AG
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    • 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
    • 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
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • 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
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the invention relates to a copper-manganese-aluminium-iron wrought alloy.
  • Alloy systems based on copper-manganese-aluminum alloys are characterized by high strength.
  • the yield strength Rp 0.2 is the more important parameter compared to the tensile strength, as it is used to dimension against over-elastic stress and only a few technical components are designed solely for high tensile strength.
  • the publication US 5,104,457 A discloses a golf club cast from a copper-aluminum alloy.
  • the alloy contains 4.5 to 12.0% by weight of Al and, in addition to copper, can contain iron, nickel and manganese as optional elements as well as small amounts of tin, lead, zinc and silicon. After casting, the alloy is heat treated but no longer formed.
  • the publication FR 1 358 505 A discloses a copper-aluminum alloy with 8.0 to 13.0% Al, to which up to 1.0% by weight of tin is added to improve the oxidation resistance. Further, the alloy may contain up to 15.0% Mn, up to 6.0% Fe and up to 6.0% Ni as optional elements.
  • the invention is based on the object of providing a copper alloy which, in the hot-formed state, has a tensile strength of at least 900 MPa, preferably at least 1000 MPa, and a 0.2% yield strength Rp 0.2 of at least 650 MPa, preferably at least 850 MPa, as well has acceptable ductility. Furthermore, the alloy should be inexpensive.
  • the invention includes a copper-manganese-aluminium-iron wrought alloy with the following composition in% by weight: Mn: 11.0 to 17.0% AI: 10.0 to 13.0% Fe: 5.0 to 8.0% optional Ti: 0.01 to 0.4% optional B: 0.002 to 0.3%
  • An alloy of the mentioned composition has a special combination of strength and ductility.
  • the tensile strength is at least 900 MPa, in selected areas at least 1000 MPa, and the 0.2% yield strength is at least 650 MPa, in selected areas at least 850 MPa.
  • the elongation at break as a measure of ductility is preferably between 0.5% and 5.0%, with the elongation at break decreasing in a known manner with increasing strength.
  • the lower limits of the elements Mn, Al and Fe as well as the additional condition that the sum of the aluminum content and iron content is at least 16.5% by weight are chosen so that the required strength is achieved.
  • the upper limits of the elements Mn, Al, and Fe are chosen to ensure minimum ductility. Exceeding these limits would lead to embrittlement and also to a decrease in tensile strength above certain element limits of the alloy. It should be noted that 1% by weight of aluminum has approximately the same effect on embrittlement as 5% by weight of manganese.
  • the optional elements Ti and B result in a grain refinement of the structure.
  • the alloy does not contain expensive elements such as nickel or tin.
  • the alloy also has excellent oil corrosion resistance and high vibration resistance.
  • the alloy is present throughout the entire composition range as an ⁇ - ⁇ alloy, with additional particles containing manganese and/or iron in its structure or such excretions are stored.
  • the iron-containing particles are available in different size classes: on the one hand as Fe particles with a diameter of more than 1 ⁇ m, which anchor the grain boundaries and counteract grain coarsening during hot forming, and on the other hand in the form of face-centered cubic precipitates containing iron and manganese of ⁇ IV phase (kappa IV phase), which are only approximately 20 to 100 nm in size and lead to the particularly high strength of this alloy. Due to the high Fe content of 5 - 8%, a particularly large number of ⁇ IV precipitates are formed.
  • the sum of Mn content and Fe content is preferably at least 18% by weight, particularly preferably at least 19% by weight.
  • the alloy does not contain a brittle ⁇ phase.
  • the copper content can be at most 70.0% by weight.
  • a minimum proportion of alloying elements in particular Mn, Al and Fe, is indirectly specified. This ensures that the required strength of the alloy is achieved. Limiting the copper content also has a positive effect on the price of the alloy.
  • the sum of the manganese content, the iron content and three times the aluminum content can be at least 52.0% by weight. In this way, alloys with a tensile strength of at least 1000 MPa are achieved.
  • the triple weighting of the aluminum content in total expresses the particularly strength-increasing effect of aluminum.
  • the manganese content in the alloy can be 12.0 to 16.0% by weight, particularly preferably 13.0 to 15.0% by weight.
  • Mn content particularly favorable results arise Property combinations.
  • a tensile strength of at least 1100 MPa can be achieved.
  • the ductility of the alloy is favorably influenced.
  • the aluminum content can be 11.0 to 12.0% by weight.
  • Aluminum has a major influence on strength, but also on brittleness. At the same time, aluminum reduces the density of the alloy. The range between 11.0 and 12.0% by weight has proven to be particularly favorable with regard to these properties.
  • the iron content in the alloy can preferably be 6.0 to 7.0% by weight.
  • a minimum proportion of iron in combination with manganese is important to achieve a high-strength alloy because the yield strength is positively influenced by the formation of Mn- and Fe-rich ⁇ IV precipitates. It is therefore advantageous to provide at least 6.0% by weight of iron in the alloy.
  • the strength-increasing effect of iron is slightly smaller than that of aluminum. Above an iron content of 7% by weight, iron does not further improve the tensile strength. However, the iron content should be as large as possible, as iron reduces the density of the alloy and lowers the price of the metal. Iron also has a grain-refining effect.
  • compositions with manganese from 13.0 to 15.0% by weight in combination with aluminum from 11.0 to 12.0% by weight and iron from 6.0 to 7.0% by weight offer the advantage that the material has a low density of approximately 6900 kg/m 3 and thus a significant weight saving, for example 25% compared to pure copper or low-alloy copper and approximately 13% compared to steel, can be achieved.
  • the alloy composition can be chosen particularly advantageously that the alloy has Mn and Fe-rich ⁇ IV precipitates with a volume fraction of at least 20%. This can be achieved by choosing the proportions of Mn and Fe to be sufficiently high.
  • the face-centered cubic Mn and Fe-rich ⁇ IV precipitates have a positive effect on the yield strength of the alloy. With a volume fraction of at least 20%, the yield strength Rp 0.2 is at least 1000 MPa.
  • the copper-manganese-aluminum-iron wrought alloy can preferably have a combination of properties in which the 0.2% yield strength Rp 0.2 , depending on the elongation at break x in%, satisfies the following relation: Rp 0.2 ⁇ 920 MPa ⁇ x ⁇ 0.17 where the elongation at break x assumes values of 0.5 to 5.0%.
  • the 0.2% yield strength and elongation at break are determined using a tensile test at room temperature.
  • Table 1 shows alloy examples with their properties in the hot-formed state.
  • the composition of the respective alloy is documented in the first column.
  • the alloys were melted in a Tammann furnace and cast as a plate measuring 90 x 50 x 20 mm using the conventional chill casting process without inert gas.
  • the alloying elements Fe, Mn and Al were added in the form of binary CuX master alloys, where X stands for the respective alloying element.
  • the porosity after casting was less than 2% by volume for all variants, and usually even less than 1% by volume.
  • the plates were then hot rolled between 750 and 800 °C.
  • the unavoidable impurities were less than 0.05% by weight in all examples.
  • Table 1 shows nine alloy examples according to the invention and three comparative examples.
  • the sum of the alloying elements Al and Fe is at least 17% by weight, whereas in the comparative examples it is only approximately 14 to 15% by weight.
  • the sum of the manganese content, the iron content and three times the aluminum content is entered in the fifth column.
  • the sum of the proportions of the alloying elements Mn and Fe is entered in the sixth column. In the examples in the first nine lines this is at least 18% by weight; in the comparative examples it is less than 15% by weight.
  • All examples according to the invention have a tensile strength of over 900 MPa and a 0.2% yield strength of at least 650 MPa. Alloys in which the sum of the manganese content, the iron content and three times the aluminum content is at least 53% by weight have a tensile strength of over 1000 MPa and a 0.2% yield strength of over 850 MPa on. As the yield strength increases, the elongation at break decreases continuously. Particularly favorable combinations of properties arise for alloys in which the sum of the manganese content, the iron content and three times the aluminum content is at least 54.0 and at most 56.0% by weight.
  • the alloys CuMn13Al10Fe7 and CuMn12Al10Fe7 have a 0.2% yield strength between 650 and 700 MPa and therefore the lowest yield strengths of the first nine examples. On the other hand, they are characterized by a high elongation at break of 4.6% or 6% and therefore greater ductility than the other alloy examples.
  • the alloys can be adjusted after hot forming. Their density is approximately 7100 kg/m 3 .
  • comparative example 1 has an acceptable tensile strength and a sufficient yield strength, its elongation at break is comparatively low: the CuMn14Al11 Fe6 alloy is characterized by a significantly higher strength and even slightly better yield strength compared to comparison alloy 1. This shows that the Cu-Mn-Al-Fe quaternary alloy system is sensitive to a change in composition.
  • Comparative example 2 corresponds to that from the publication GB 762 235 A well-known nickel-free example. The mechanical characteristics were determined after hot forming. The alloy of Comparative Example 2 is inferior to the alloys according to the invention in terms of strength.
  • Comparative example 3 corresponds to one from the publication FR 1 177 060 A known alloy. The mechanical characteristics were determined after hot forming. Although the alloy of Comparative Example 3 has a sufficient tensile strength of 950 MPa, the yield strength is below the requirements.

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Description

Die Erfindung betrifft eine Kupfer-Mangan-Aluminium-Eisen-Knetlegierung.The invention relates to a copper-manganese-aluminium-iron wrought alloy.

Legierungssysteme auf Basis von Kupfer-Mangan-Aluminium-Legierungen zeichnen sich durch eine hohe Festigkeit aus. Die Dehngrenze Rp0,2 ist dabei im Vergleich zur Zugfestigkeit die wichtigere Kenngröße, da sie zur Dimensionierung gegen überelastische Beanspruchung verwendet wird und nur wenige technische Bauteile lediglich auf hohe Zugfestigkeit ausgelegt sind.Alloy systems based on copper-manganese-aluminum alloys are characterized by high strength. The yield strength Rp 0.2 is the more important parameter compared to the tensile strength, as it is used to dimension against over-elastic stress and only a few technical components are designed solely for high tensile strength.

In der Literatur sind bereits ternäre Cu-Al-Mn, quaternäre Cu-Al-Mn-X und quinäre Cu-AI-Mn-X-Y Legierungen beschrieben. Beispielsweise ist eine Shape-Memory-Legierung mit der ungefähren Zusammensetzung CuMn11Al8 bekannt. Die Zugfestigkeit und 0,2 %-Dehngrenze dieser Legierung liegen deutlich unter 1000 MPa. Des Weiteren existiert eine eisenfreie, genormte Cu-Al-Mn Legierung mit der Zusammensetzung CuAI9Mn2. Verschiedene sogenannte Heusler-Legierungen sind ebenfalls vom Typ Cu-Al-Mn.Ternary Cu-Al-Mn, quaternary Cu-Al-Mn-X and quinary Cu-Al-Mn-X-Y alloys have already been described in the literature. For example, a shape memory alloy with the approximate composition CuMn11Al8 is known. The tensile strength and 0.2% yield strength of this alloy are well below 1000 MPa. There is also an iron-free, standardized Cu-Al-Mn alloy with the composition CuAl9Mn2. Various so-called Heusler alloys are also of the Cu-Al-Mn type.

Aus der Druckschrift GB 762 235 A sind eine Legierung der Zusammensetzung CuMn6,2Al9,7Fe4,6Zn0,5 sowie nickelhaltige Legierungen ähnlicher Zusammensetzung mit maximal 8 Gew.-% Mn bekannt. Die Zugfestigkeit der Legierungen liegt im Gusszustand zwischen 600 und 700 MPa, die Dehngrenze bei ungefähr 250 MPa.From the publication GB 762 235 A An alloy with the composition CuMn6.2Al9.7Fe4.6Zn0.5 and nickel-containing alloys of similar composition with a maximum of 8% by weight of Mn are known. The tensile strength of the alloys in the cast state is between 600 and 700 MPa, the yield strength at approximately 250 MPa.

Des Weiteren ist aus der Druckschrift FR 1 177 060 A eine Kupferlegierung mit 8,5 bis 9,5 Gew.-% Mn, 8 bis 10,5 Gew.-% AI, 2,5 bis 5 Gew.-% Fe und 2 bis 3 Gew.-% Ni bekannt. Die Zugfestigkeit der Legierung beträgt im Gusszustand ungefähr 600 MPa und die Dehngrenze ungefähr 260 MPa.Furthermore, it is from the publication FR 1 177 060 A a copper alloy with 8.5 to 9.5% by weight of Mn, 8 to 10.5% by weight of Al, 2.5 to 5% by weight of Fe and 2 to 3% by weight of Ni is known. The as-cast tensile strength of the alloy is approximately 600 MPa and the yield strength is approximately 260 MPa.

Ferner sind aus der Druckschrift US 2 715 577 A Legierung mit 10 bis 15 Gew.-% Mn, 6,5 bis 9 % Al, 2 bis 4 % Fe und 1,5 bis 6 % Nickel bekannt. Ein Beispiel mit der Zusammensetzung CuMn11,7Al7,2Fe3,3Ni2,2 weist im Gusszustand eine Zugfestigkeit von 600 bis 700 MPa und eine Dehngrenze von ungefähr 280 MPa auf.Further are from the publication US 2,715,577 A Alloy with 10 to 15% by weight of Mn, 6.5 to 9% of Al, 2 to 4% of Fe and 1.5 to 6% of nickel is known. An example with the composition CuMn11.7Al7.2Fe3.3Ni2.2 has a tensile strength of 600 to 700 MPa and a yield strength of approximately 280 MPa in the as-cast state.

Die Druckschrift US 5 104 457 A offenbart einen Golfschläger, der aus einer Kupfer-Aluminium-Legierung gegossen wurde. Die Legierung enthält 4,5 bis 12,0 Gew.-% Al und kann neben Kupfer als optionale Elemente Eisen, Nickel und Mangan sowie geringe Mengen an Zinn, Blei, Zink und Silicium enthalten. Die Legierung wird nach dem Gießen wärmebehandelt, aber nicht mehr umgeformt. Die Druckschrift FR 1 358 505 A offenbart eine Kupfer-Aluminium-Legierung mit 8,0 bis 13,0 % Al, der zur Verbesserung der Oxidationsbeständigkeit bis zu 1,0 Gew.-% Zinn hinzu legiert werden. Ferner kann die Legierung bis zu 15,0 % Mn, bis zu 6,0 % Fe und bis zu 6,0 % Ni als optionale Elemente enthalten.The publication US 5,104,457 A discloses a golf club cast from a copper-aluminum alloy. The alloy contains 4.5 to 12.0% by weight of Al and, in addition to copper, can contain iron, nickel and manganese as optional elements as well as small amounts of tin, lead, zinc and silicon. After casting, the alloy is heat treated but no longer formed. The publication FR 1 358 505 A discloses a copper-aluminum alloy with 8.0 to 13.0% Al, to which up to 1.0% by weight of tin is added to improve the oxidation resistance. Further, the alloy may contain up to 15.0% Mn, up to 6.0% Fe and up to 6.0% Ni as optional elements.

Der Erfindung liegt die Aufgabe zugrunde, eine Kupferlegierung bereitzustellen, die im warmumgeformten Zustand eine Zugfestigkeit von mindestens 900 MPa, vorzugsweise mindestens 1000 MPa, und eine 0,2 %-Dehngrenze Rp0,2 von mindestens 650 MPa, vorzugsweise mindestens 850 MPa, sowie eine akzeptable Duktilität aufweist. Ferner sollte die Legierung kostengünstig sein.The invention is based on the object of providing a copper alloy which, in the hot-formed state, has a tensile strength of at least 900 MPa, preferably at least 1000 MPa, and a 0.2% yield strength Rp 0.2 of at least 650 MPa, preferably at least 850 MPa, as well has acceptable ductility. Furthermore, the alloy should be inexpensive.

Die Erfindung wird durch die Merkmale des Anspruchs 1 wiedergegeben. Die weiteren rückbezogenen Ansprüche betreffen vorteilhafte Aus- und Weiterbildungen der Erfindung.The invention is represented by the features of claim 1. The Further related claims relate to advantageous training and further developments of the invention.

Die Erfindung schließt eine Kupfer-Mangan-Aluminium-Eisen-Knetlegierung mit folgender Zusammensetzung in Gew.-% ein: Mn: 11,0 bis 17,0 % AI: 10,0 bis 13,0 % Fe: 5,0 bis 8,0 % optional Ti: 0,01 bis 0,4 % optional B: 0,002 bis 0,3 % The invention includes a copper-manganese-aluminium-iron wrought alloy with the following composition in% by weight: Mn: 11.0 to 17.0% AI: 10.0 to 13.0% Fe: 5.0 to 8.0% optional Ti: 0.01 to 0.4% optional B: 0.002 to 0.3%

Rest Kupfer sowie unvermeidbare Verunreinigungen,
wobei die Summe aus Aluminium-Anteil und Eisen-Anteil mindestens 16,5 Gew.-% beträgt.residual copper and unavoidable impurities,
where the sum of the aluminum content and iron content is at least 16.5% by weight.

Eine Legierung der genannten Zusammensetzung weist eine besondere Kombination von Festigkeit und Duktilität auf. Die Zugfestigkeit beträgt mindestens 900 MPa, in ausgewählten Bereichen mindestens 1000 MPa, und die 0,2 %-Dehngrenze mindestens 650 MPa, in ausgewählten Bereichen mindestens 850 MPa. Die Bruchdehnung als Maß für die Duktilität liegt bevorzugt zwischen 0,5 % und 5,0 %, wobei die Bruchdehnung in bekannter Weise mit zunehmender Festigkeit abnimmt.An alloy of the mentioned composition has a special combination of strength and ductility. The tensile strength is at least 900 MPa, in selected areas at least 1000 MPa, and the 0.2% yield strength is at least 650 MPa, in selected areas at least 850 MPa. The elongation at break as a measure of ductility is preferably between 0.5% and 5.0%, with the elongation at break decreasing in a known manner with increasing strength.

Die Untergrenzen der Elemente Mn, AI und Fe sowie die Zusatzbedingung, dass die Summe aus Aluminium-Anteil und Eisen-Anteil mindestens 16,5 Gew.-% beträgt, sind so gewählt, dass die erforderliche Festigkeit erreicht wird. Die Obergrenzen der Elemente Mn, Al, und Fe sind so gewählt, dass eine Mindestduktilität gewährleistet wird. Eine Überschreitung dieser Grenzen würde zu einer Versprödung und auch zu einer Abnahme der Zugfestigkeit oberhalb bestimmter Elementgrenzen der Legierung führen. Dabei ist zu beachten, dass 1 Gew.-% Aluminium hinsichtlich der Versprödung ungefähr den gleichen Effekt wie 5 Gew.-% Mangan hat.The lower limits of the elements Mn, Al and Fe as well as the additional condition that the sum of the aluminum content and iron content is at least 16.5% by weight are chosen so that the required strength is achieved. The upper limits of the elements Mn, Al, and Fe are chosen to ensure minimum ductility. Exceeding these limits would lead to embrittlement and also to a decrease in tensile strength above certain element limits of the alloy. It should be noted that 1% by weight of aluminum has approximately the same effect on embrittlement as 5% by weight of manganese.

Die optionalen Elemente Ti und B bewirken eine Kornfeinung des Gefüges.The optional elements Ti and B result in a grain refinement of the structure.

Die Legierung enthält keine teuren Elemente wie Nickel oder Zinn. Die Legierung weist ferner eine exzellente Ölkorrosionsbeständigkeit und eine hohe Schwingfestigkeit auf.The alloy does not contain expensive elements such as nickel or tin. The alloy also has excellent oil corrosion resistance and high vibration resistance.

Die Legierung liegt im gesamten Bereich der Zusammensetzung als α-β-Legierung vor, in deren Gefüge zusätzlich mangan- und/oder eisenhaltige Partikel oder derartige Ausscheidungen eingelagert sind. Die eisenhaltigen Partikel liegen in unterschiedlichen Größenklassen vor: Einerseits als Fe-Partikel mit einem Durchmesser von mehr als 1 µm, welche die Korngrenzen verankern und einer Kornvergröberung bei der Warmumformung entgegenwirken, und andererseits auch in Form von kubisch-flächenzentrierten, eisen- und manganhaltigen Ausscheidungen von κIV-Phase (kappa-IV-Phase), welche nur ungefähr 20 bis 100 nm groß sind und zur besonders hohen Festigkeit dieser Legierung führen. Durch den hohen Fe-Gehalt von 5 - 8 % bilden sich besonders viele κIV-Ausscheidungen. Bevorzugt beträgt die Summe aus Mn-Anteil und Fe-Anteil mindestens 18 Gew.-%, besonders bevorzugt mindestens 19 Gew.-%. Die Legierung enthält im Gegensatz zu konventionellen Aluminiumbronzen, wie beispielsweise CuAl10Ni5Fe4, keine spröde γ-Phase.The alloy is present throughout the entire composition range as an α-β alloy, with additional particles containing manganese and/or iron in its structure or such excretions are stored. The iron-containing particles are available in different size classes: on the one hand as Fe particles with a diameter of more than 1 µm, which anchor the grain boundaries and counteract grain coarsening during hot forming, and on the other hand in the form of face-centered cubic precipitates containing iron and manganese of κ IV phase (kappa IV phase), which are only approximately 20 to 100 nm in size and lead to the particularly high strength of this alloy. Due to the high Fe content of 5 - 8%, a particularly large number of κ IV precipitates are formed. The sum of Mn content and Fe content is preferably at least 18% by weight, particularly preferably at least 19% by weight. In contrast to conventional aluminum bronzes, such as CuAl10Ni5Fe4, the alloy does not contain a brittle γ phase.

In bevorzugter Ausgestaltung der Erfindung kann der Kupfer-Anteil höchstens 70,0 Gew.-% betragen. Indem der Maximalanteil von Kupfer in der Legierung beschränkt wird, wird indirekt ein Mindestanteil von Legierungselementen, insbesondere von Mn, AI und Fe, spezifiziert. Dadurch wird sichergestellt, dass die erforderliche Festigkeit der Legierung erreicht wird. Die Begrenzung des Kupfer-Anteils wirkt sich ferner positiv auf den Preis der Legierung aus.In a preferred embodiment of the invention, the copper content can be at most 70.0% by weight. By limiting the maximum proportion of copper in the alloy, a minimum proportion of alloying elements, in particular Mn, Al and Fe, is indirectly specified. This ensures that the required strength of the alloy is achieved. Limiting the copper content also has a positive effect on the price of the alloy.

In weiterer bevorzugter Ausgestaltung der Erfindung kann die Summe aus dem Mangan-Anteil, dem Eisen-Anteil und dem Dreifachen des Aluminium-Anteils mindestens 52,0 Gew.-% betragen. Auf diese Weise werden Legierungen mit einer Zugfestigkeit von mindestens 1000 MPa erreicht. Die dreifache Gewichtung des Aluminium-Anteils in der Summe bringt die besonders festigkeitssteigernde Wirkung des Aluminiums zum Ausdruck.In a further preferred embodiment of the invention, the sum of the manganese content, the iron content and three times the aluminum content can be at least 52.0% by weight. In this way, alloys with a tensile strength of at least 1000 MPa are achieved. The triple weighting of the aluminum content in total expresses the particularly strength-increasing effect of aluminum.

Vorteilhafterweise kann der Mangan-Anteil in der Legierung 12,0 bis 16,0 Gew.-%, besonders bevorzugt 13,0 bis 15,0 Gew.-% betragen. In diesem enger gefassten Bereich für den Mn-Anteil ergeben sich besonders günstige Eigenschaftskombinationen. Bei einem Mn-Anteil von mindestens 12,0 Gew.-% kann eine Zugfestigkeit von mindestens 1100 MPa erreicht werden. Durch eine Beschränkung der Obergrenze wird die Duktilität der Legierung günstig beeinflusst.Advantageously, the manganese content in the alloy can be 12.0 to 16.0% by weight, particularly preferably 13.0 to 15.0% by weight. In this narrower range for the Mn content, particularly favorable results arise Property combinations. With an Mn content of at least 12.0% by weight, a tensile strength of at least 1100 MPa can be achieved. By limiting the upper limit, the ductility of the alloy is favorably influenced.

Bei einer vorteilhaften Ausführungsform der Erfindung kann der Aluminium-Anteil 11,0 bis 12,0 Gew.-% betragen. Aluminium hat einen großen Einfluss auf die Festigkeit, aber auch auf die Versprödung. Gleichzeitig reduziert Aluminium die Dichte der Legierung. Der Bereich zwischen 11,0 und 12,0 Gew.-% hat sich als besonders günstig hinsichtlich dieser Eigenschaften erwiesen.In an advantageous embodiment of the invention, the aluminum content can be 11.0 to 12.0% by weight. Aluminum has a major influence on strength, but also on brittleness. At the same time, aluminum reduces the density of the alloy. The range between 11.0 and 12.0% by weight has proven to be particularly favorable with regard to these properties.

Bevorzugt kann der Eisen-Anteil in der Legierung 6,0 bis 7,0 Gew.-% betragen.The iron content in the alloy can preferably be 6.0 to 7.0% by weight.

Ein Mindestanteil an Eisen in Kombination mit Mangan ist zur Erzielung einer hochfesten Legierung wichtig, weil die Dehngrenze durch die Ausbildung von Mn- und Fe-reichen κIV-Ausscheidungen positiv beeinflusst wird. Deshalb ist es vorteilhaft, mindestens 6,0 Gew.-% Eisen in der Legierung vorzusehen. Die festigkeitssteigernde Wirkung des Eisens ist etwas kleiner als die des Aluminiums. Oberhalb eines Eisenanteils von 7 Gew.-% erfolgt keine weitere Verbesserung der Zugfestigkeit durch Eisen. Dennoch sollte der Eisen-Anteil so groß wie möglich sein, da Eisen die Dichte der Legierung reduziert und den Metallpreis absenkt. Eisen wirkt zudem kornfeinend.A minimum proportion of iron in combination with manganese is important to achieve a high-strength alloy because the yield strength is positively influenced by the formation of Mn- and Fe-rich κ IV precipitates. It is therefore advantageous to provide at least 6.0% by weight of iron in the alloy. The strength-increasing effect of iron is slightly smaller than that of aluminum. Above an iron content of 7% by weight, iron does not further improve the tensile strength. However, the iron content should be as large as possible, as iron reduces the density of the alloy and lowers the price of the metal. Iron also has a grain-refining effect.

Insbesondere die Zusammensetzungen mit Mangan von 13,0 bis 15,0 Gew.-% in Kombination mit Aluminium von 11,0 bis 12,0 Gew.-% und Eisen von 6,0 bis 7,0 Gew.-% bieten den Vorteil, dass der Werkstoff eine geringe Dichte von ungefähr 6900 kg/m3 aufweist und somit eine deutliche Gewichtsersparnis, beispielsweise 25 % gegenüber Reinkupfer oder niedrig legiertem Kupfer und ungefähr 13 % gegenüber Stahl, erzielt werden kann.In particular, the compositions with manganese from 13.0 to 15.0% by weight in combination with aluminum from 11.0 to 12.0% by weight and iron from 6.0 to 7.0% by weight offer the advantage that the material has a low density of approximately 6900 kg/m 3 and thus a significant weight saving, for example 25% compared to pure copper or low-alloy copper and approximately 13% compared to steel, can be achieved.

Besonders vorteilhafterweise kann die Legierungszusammensetzung so gewählt werden, dass die Legierung Mn- und Fe-reiche κIV-Ausscheidungen mit einem Volumenanteil von mindestens 20 % aufweist. Dies kann erreicht werden, indem die Anteile an Mn und Fe ausreichend hoch gewählt werden. Die kubisch-flächenzentrierten Mn- und Fe-reichen κIV-Ausscheidungen haben einen positiven Effekt auf die Dehngrenze der Legierung. Bei einem Volumenanteil von mindestens 20 % beträgt die Dehngrenze Rp0,2 mindestens 1000 MPa.The alloy composition can be chosen particularly advantageously that the alloy has Mn and Fe-rich κ IV precipitates with a volume fraction of at least 20%. This can be achieved by choosing the proportions of Mn and Fe to be sufficiently high. The face-centered cubic Mn and Fe-rich κ IV precipitates have a positive effect on the yield strength of the alloy. With a volume fraction of at least 20%, the yield strength Rp 0.2 is at least 1000 MPa.

Bevorzugt kann die Kupfer-Mangan-Aluminium-Eisen-Knetlegierung eine Kombination von Eigenschaften aufweisen, bei der die 0,2 %-Dehngrenze Rp0.2 in Abhängigkeit von der Bruchdehnung x in % folgende Relation erfüllt: Rp 0,2 ≥ 920 MPa ⋅ x − 0,17

Figure imgb0001
wobei die Bruchdehnung x Werte von 0,5 bis 5,0 % annimmt. 0,2 %-Dehngrenze und Bruchdehnung werden dabei mittels eines Zugversuchs bei Raumtemperatur ermittelt.The copper-manganese-aluminum-iron wrought alloy can preferably have a combination of properties in which the 0.2% yield strength Rp 0.2 , depending on the elongation at break x in%, satisfies the following relation: Rp 0.2 ≥ 920 MPa ⋅ x − 0.17
Figure imgb0001
 where the elongation at break x assumes values of 0.5 to 5.0%. The 0.2% yield strength and elongation at break are determined using a tensile test at room temperature.

Durch diese Relation wird die vergleichsweise hohe Dehngrenze bei noch akzeptabler Bruchdehnung quantitativ beschrieben. Bei einer Bruchdehnung von beispielsweise 0,5 % erreicht die Legierung eine 0,2 %-Dehngrenze von ungefähr 1030 MPa.This relation quantitatively describes the comparatively high yield strength with still acceptable elongation at break. With an elongation at break of, for example, 0.5%, the alloy reaches a 0.2% yield strength of approximately 1030 MPa.

Die Erfindung wird anhand von Ausführungsbeispielen näher erläutert.The invention is explained in more detail using exemplary embodiments.

Tabelle 1 zeigt Legierungsbeispiele mit ihren Eigenschaften im warmumgeformten Zustand. In der ersten Spalte ist die Zusammensetzung der jeweiligen Legierung dokumentiert. Die Legierungen wurden in einem Tammannofen erschmolzen und im konventionellen Kokillengussverfahren ohne Schutzgas als Platte der Abmessung 90 x 50 x 20 mm abgegossen. Die Legierungselemente Fe, Mn und Al wurden in Form von binären CuX-Vorlegierungen hinzuchargiert, wobei X für das jeweilige Legierungselement steht. Die Porosität nach dem Abguss betrug für alle Varianten weniger als 2 Vol.-%, meist sogar weniger als 1 Vol.-%. Die Platten wurden anschließend zwischen 750 und 800 °C warmgewalzt. Der Umformgrad, der als die relative Abnahme der Plattendicke definiert ist, betrug hierbei ungefähr 40 %. Die unvermeidbaren Verunreinigungen betrugen bei allen Beispielen weniger als 0,05 Gew.-%. Tabelle 1: Legierungsbeispiele mit Eigenschaften im warmumgeformten Zustand Legierung in Gew.-% Bruchdehnung in % Zugfestigkeit in MPa Dehngrenze Rp0,2 in MPa Mn+3Al+Fe in Gew.-% Mn+Fe in Gew-% CuMn15Al12Fe6 0,5 1060 1042 57 21 CuMn13Al12Fe6 0,7 1140 1005 55 19 CuMn14Al12Fe6 0,8 1120 977 56 20 CuMn12Al12Fe6 0,9 1100 971 54 18 CuMn16Al11Fe6 0,9 1060 980 55 22 CuMn17Al11Fe6 1,3 1080 910 56 23 CuMn14Al11Fe6 2,3 1060 862 53 20 CuMn13Al10Fe7 4,6 945 697 50 20 CuMn12Al10Fe7 6 923 651 49 19 Vergleichsbeispiel 1 CuMn10Al11Fe4 2 918 806 47 14 Vergleichsbeispiel 2 CuMn6,2Al9,7Fe4,6Zn 12,5 810 564 39,9 10,8 Vergleichsbeispiel 3 CuMn9,5Al10Fe5Ni2 6 950 500 44,5 14,5 Table 1 shows alloy examples with their properties in the hot-formed state. The composition of the respective alloy is documented in the first column. The alloys were melted in a Tammann furnace and cast as a plate measuring 90 x 50 x 20 mm using the conventional chill casting process without inert gas. The alloying elements Fe, Mn and Al were added in the form of binary CuX master alloys, where X stands for the respective alloying element. The porosity after casting was less than 2% by volume for all variants, and usually even less than 1% by volume. The plates were then hot rolled between 750 and 800 °C. The degree of deformation, which is defined as the relative decrease in plate thickness, was approximately 40%. The unavoidable impurities were less than 0.05% by weight in all examples. Table 1: Alloy examples with properties in the hot-formed state Alloy in wt.% Elongation at break in % Tensile strength in MPa Yield strength Rp 0.2 in MPa Mn+3Al+Fe in wt.% Mn+Fe in wt% CuMn15Al12Fe6 0.5 1060 1042 57 21 CuMn13Al12Fe6 0.7 1140 1005 55 19 CuMn14Al12Fe6 0.8 1120 977 56 20 CuMn12Al12Fe6 0.9 1100 971 54 18 CuMn16Al11Fe6 0.9 1060 980 55 22 CuMn17Al11Fe6 1.3 1080 910 56 23 CuMn14Al11Fe6 2.3 1060 862 53 20 CuMn13Al10Fe7 4.6 945 697 50 20 CuMn12Al10Fe7 6 923 651 49 19 Comparative example 1 CuMn10Al11Fe4 2 918 806 47 14 Comparative example 2 CuMn6.2Al9.7Fe4.6Zn 12.5 810 564 39.9 10.8 Comparative example 3 CuMn9.5Al10Fe5Ni2 6 950 500 44.5 14.5

Tabelle 1 zeigt neun erfindungsgemäße Legierungsbeispiele und drei Vergleichsbeispiele. Bei den Beispielen der ersten neun Zeilen beträgt die Summe der Legierungselemente Al und Fe mindestens 17 Gew.-%, bei den Vergleichsbeispielen hingegen nur ungefähr 14 bis 15 Gew.-%. In der fünften Spalte ist die Summe aus dem Mangan-Anteil, dem Eisen-Anteil und dem Dreifachen des Aluminium-Anteils eingetragen. In der sechsten Spalte ist die Summe der Anteile der Legierungselemente Mn und Fe eingetragen. Bei den Beispielen in den ersten neun Zeilen beträgt diese mindestens 18 Gew.-%, bei den Vergleichsbeispielen liegt sie unter 15 Gew.-%.Table 1 shows nine alloy examples according to the invention and three comparative examples. In the examples in the first nine lines, the sum of the alloying elements Al and Fe is at least 17% by weight, whereas in the comparative examples it is only approximately 14 to 15% by weight. The sum of the manganese content, the iron content and three times the aluminum content is entered in the fifth column. The sum of the proportions of the alloying elements Mn and Fe is entered in the sixth column. In the examples in the first nine lines this is at least 18% by weight; in the comparative examples it is less than 15% by weight.

Alle erfindungsgemäßen Beispiele weisen ein Zugfestigkeit von über 900 MPa und eine 0,2 %-Dehngrenze von mindestens 650 MPa auf. Legierungen, bei denen die Summe aus dem Mangan-Anteil, dem Eisen-Anteil und dem Dreifachen des Aluminium-Anteils mindestens 53 Gew.-% beträgt, weisen eine Zugfestigkeit von über 1000 MPa und eine 0,2 %-Dehngrenze von über 850 MPa auf. Mit zunehmender Dehngrenze nimmt die Bruchdehnung kontinuierlich ab. Besonders günstige Eigenschaftskombinationen ergeben sich für Legierungen, bei denen die Summe aus dem Mangan-Anteil, dem Eisen-Anteil und dem Dreifachen des Aluminium-Anteils mindestens 54,0 und höchstens 56,0 Gew.-% beträgt.All examples according to the invention have a tensile strength of over 900 MPa and a 0.2% yield strength of at least 650 MPa. Alloys in which the sum of the manganese content, the iron content and three times the aluminum content is at least 53% by weight have a tensile strength of over 1000 MPa and a 0.2% yield strength of over 850 MPa on. As the yield strength increases, the elongation at break decreases continuously. Particularly favorable combinations of properties arise for alloys in which the sum of the manganese content, the iron content and three times the aluminum content is at least 54.0 and at most 56.0% by weight.

Die Legierungen CuMn13Al10Fe7 und CuMn12Al10Fe7 weisen eine 0,2 %-Dehngrenze zwischen 650 und 700 MPa und somit die geringsten Dehngrenzen der ersten neun Beispiele auf. Andererseits zeichnen sie sich durch eine hohe Bruchdehnung von 4,6 % beziehungsweis 6 % und somit eine größere Duktilität als die übrigen Legierungsbeispiele aus. Die Legierungen lassen sich nach dem Warmumformen richten. Ihre Dichte beträgt ungefähr 7100 kg/m3. Diese beiden Beispiele zeigen, dass durch moderate Änderungen der Legierungszusammensetzung die Eigenschaften der Legierung zielgerichtet angepasst werden können.The alloys CuMn13Al10Fe7 and CuMn12Al10Fe7 have a 0.2% yield strength between 650 and 700 MPa and therefore the lowest yield strengths of the first nine examples. On the other hand, they are characterized by a high elongation at break of 4.6% or 6% and therefore greater ductility than the other alloy examples. The alloys can be adjusted after hot forming. Their density is approximately 7100 kg/m 3 . These two examples show that the properties of the alloy can be tailored in a targeted manner through moderate changes to the alloy composition.

Das Vergleichsbeispiel 1 weist zwar eine akzeptable Zugfestigkeit und eine ausreichende Dehngrenze auf, seine Bruchdehnung ist jedoch vergleichsweise gering: So zeichnet sich die Legierung CuMn14Al11 Fe6 gegenüber der Vergleichslegierung 1 durch eine deutlich höhere Festigkeit bei sogar etwas besserer Dehngrenze aus. Dies zeigt, dass das quaternäre Legierungssystem Cu-Mn-Al-Fe sensibel auf eine Änderung der Zusammensetzung reagiert.Although comparative example 1 has an acceptable tensile strength and a sufficient yield strength, its elongation at break is comparatively low: the CuMn14Al11 Fe6 alloy is characterized by a significantly higher strength and even slightly better yield strength compared to comparison alloy 1. This shows that the Cu-Mn-Al-Fe quaternary alloy system is sensitive to a change in composition.

Das Vergleichsbeispiel 2 entspricht dem aus der Druckschrift GB 762 235 A bekannten nickelfreien Beispiel. Die mechanischen Kennwerte wurden nach einer Warmumformung ermittelt. Die Legierung des Vergleichsbeispiels 2 ist hinsichtlich der Festigkeit den erfindungsgemäßen Legierungen unterlegen.Comparative example 2 corresponds to that from the publication GB 762 235 A well-known nickel-free example. The mechanical characteristics were determined after hot forming. The alloy of Comparative Example 2 is inferior to the alloys according to the invention in terms of strength.

Das Vergleichsbeispiel 3 entspricht einer aus der Druckschrift FR 1 177 060 A bekannten Legierung. Die mechanischen Kennwerte wurden nach einer Warmumformung ermittelt. Die Legierung des Vergleichsbeispiels 3 weist zwar eine ausreichende Zugfestigkeit von 950 MPa auf, die Dehngrenze liegt jedoch unter den Anforderungen.Comparative example 3 corresponds to one from the publication FR 1 177 060 A known alloy. The mechanical characteristics were determined after hot forming. Although the alloy of Comparative Example 3 has a sufficient tensile strength of 950 MPa, the yield strength is below the requirements.

Claims (8)

  1. Copper/manganese/aluminium/iron wrought alloy having the following composition in % by weight: Mn: from 11.0 to 17.0% Al: from 10.0 to 13.0% Fe: from 5.0 to 8.0% optionally Ti: from 0.01 to 0.4% optionally B: from 0.002 to 0.3%
    balance copper and inevitable impurities,
    wherein the sum of the aluminium proportion and iron proportion is at least 16.5% by weight.
  2. Copper/manganese/aluminium/iron wrought alloy according to claim 1, characterised in that the copper proportion is a maximum of 70.0% by weight.
  3. Copper/manganese/aluminium/iron wrought alloy according to claim 1 or claim 2, characterised in that the sum of the manganese proportion, the iron proportion and three times the aluminium proportion is at least 52.0% by weight.
  4. Copper/manganese/aluminium/iron wrought alloy according to any one of the preceding claims, characterised in that the manganese proportion is from 12.0 to 16.0% by weight.
  5. Copper/manganese/aluminium/iron wrought alloy according to any one of the preceding claims, characterised in that the aluminium proportion is from 11.0 to 12.0% by weight.
  6. Copper/manganese/aluminium/iron wrought alloy according to any one of the preceding claims, characterised in that the iron proportion is from 6.0 to 7.0% by weight.
  7. Copper/manganese/aluminium/iron wrought alloy according to any one of the preceding claims, characterised in that it has Mn and Fe-rich KIVprecipitations with a volume proportion of at least 20%.
  8. Copper/manganese/aluminium/iron wrought alloy according to any one of the preceding claims, characterised in that the 0.2% permanent elongation limit Rp0.2 complies depending on the elongation at break x in % with the following relationship: Rp 0.2 ≥ 920 MPa x x − 0.17
    Figure imgb0003
     wherein the elongation at break x assumes values of from 0.5 to 5.0%.
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US2715577A (en) 1951-07-24 1955-08-16 Stone & Company Charlton Ltd J Copper-base alloys
GB762235A (en) 1954-06-11 1956-11-28 Manganese Bronze And Brass Com New aluminium bronzes
FR1177060A (en) 1957-05-29 1959-04-20 Forges Chantiers Mediterranee Aluminum bronzes
FR1358505A (en) * 1963-03-04 1964-04-17 Ct Technique Des Ind Fonderie Parts intended to be used in hot conditions while being subjected to thermal shock
US5104457A (en) * 1988-02-23 1992-04-14 Country Club Golf Equipment (Proprietary) Limited Golf clubs and method of making thereof
JPH059619A (en) 1991-07-08 1993-01-19 Furukawa Electric Co Ltd:The Production of high-strength copper alloy
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DE102005035709A1 (en) 2005-07-27 2007-02-15 Technische Universität Clausthal Copper alloy with high damping capacity and process for its preparation
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