EP3899073B1 - Cu-zn alloy - Google Patents

Cu-zn alloy Download PDF

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Publication number
EP3899073B1
EP3899073B1 EP20711876.1A EP20711876A EP3899073B1 EP 3899073 B1 EP3899073 B1 EP 3899073B1 EP 20711876 A EP20711876 A EP 20711876A EP 3899073 B1 EP3899073 B1 EP 3899073B1
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alloy
cavitation
max
product
alloys
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German (de)
French (fr)
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EP3899073A1 (en
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Björn Reetz
Thomas Plett
Tileman MÜNCH
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Otto Fuchs KG
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Otto Fuchs KG
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    • 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
    • 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
    • C22C9/04—Alloys based on copper with zinc 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
    • C22C9/10—Alloys based on copper with silicon as the next major constituent

Definitions

  • the invention relates to the use of a Cu-Zn alloy.
  • Such alloys are also referred to as special brass alloys.
  • special brass alloys The field of application of special brass alloys is very extensive.
  • Such brass alloys are used, for example, to produce components used in oil environments, such as transmissions, including those that are used in thermally demanding environments, such as valve guides in an internal combustion engine. is known from DE 10 2014 101 346 A1 a brass alloy specially designed to meet the requirements of a component used in an oil environment. Specifically, a synchronizing ring is described as such a component in this prior art.
  • the oil environment in which the synchronizer ring is located can change depending on the oil and especially its additives, which can affect the mechanical properties and thermal load capacity.
  • the reason for this is that, depending on the additives in the oil, they have a different influence on the corrosion resistance of the synchronizing ring as an example of a special brass alloy product.
  • the material requirements for a cavitation erosion-resistant product are highly complex.
  • the brass alloy should have a certain deformability so that the material can be displaced during the cavitation attack. However, this must not break out.
  • the brass alloy must not build up too quickly on obstacles, otherwise material will protrude from the surface and can be removed in the next cavitation attack, resulting in a loss of mass leads.
  • the difference between the brass alloys described above and considered to be cavitation-resistant shows how difficult it is to find cavitation-erosion-resistant brass alloys. It is even more difficult to find such brass alloys whose cavitation erosion resistance is even better than conventional ones.
  • EP 1 777 305 A1 discloses cast copper alloys intended for use as water valves, faucets, marine propellers and the like. Some of these alloys are hot extruded. These alloys are Al-free.
  • the invention is therefore based on the object of proposing a brass alloy which, compared to the alloy CuZn16Si4-C, which is already regarded as particularly cavitation-resistant, has improved resistance to cavitation erosion and which also meets the temperature requirements placed on such a workpiece, above all without having to use a costly or complicated manufacturing process for this purpose.
  • the alloy should be suitable as a wrought alloy, so that products can also be produced from the alloy that cannot be produced with a cast alloy or cannot be produced with the desired requirements.
  • This object is achieved according to the invention by using a Cu-Zn alloy as a wrought alloy with the following composition (in percent by weight): Cu: 80 - 85, Si: 2.0 - 6.0, Al: 0.55 - 2.0, Fe: max 0.8, Ni: max. 0.5, Sn: max. 0.5, Mn: max 0.1, pb: max. 0.3, remainder Zn and unavoidable impurities for the manufacture of a cavitation-resistant product, the surface of which comes into contact with fluids flowing past when used as intended.
  • the Si content is 2.0 to 6.0% by weight. Increasing the Si content does not lead to further cavitation resistance. In one embodiment, the Si content is between 3.7 and 6.0% by weight. In a further exemplary embodiment, this is between 4.7 and 5.3% by weight. In yet another exemplary embodiment, it is provided that the Si content is between 2.0 and 2.8% by weight.
  • the aluminum content is between 0.55 and 2.0% by weight.
  • the Al content is preferably between 0.65 and 1.5% by weight. In a further embodiment, the Al content is 0.8 and 1.3% by weight. With these Al contents the best results in terms of corrosion resistance were achieved.
  • a particular advantage of this alloy is that the positive cavitation resistance properties of this alloy are set directly in a hot forming step following casting, without a subsequent special thermal treatment being required to set or produce the cavitation resistance.
  • a cavitation-resistant product can therefore be manufactured from this alloy using the usual process steps.
  • This brass alloy product is also compatible with a wide range of lubricants, has excellent mechanical properties and is temperature-resistant.
  • DE 10 2014 101 346 A1 reference is made to the same applicant, through which reference the statements in the document mentioned are also made the subject matter and disclosure content of these statements and count. Investigations have shown that the 0.2 yield strength is 240 and 260 N/mm 2 , the tensile strength is 530 and 600 N/mm 2 , the elongation at break is 16 to 22% and the Brinell hardness is 155 to 165 HBW.
  • the specimens produced as a wrought alloy have a higher density compared to cast materials.
  • CuAl10Fe5Ni5 and CuZn16Si4-C Three Cu-Zn alloys were examined for cavitation investigations, specifically the alloys CuAl10Fe5Ni5 and CuZn16Si4-C and an alloy according to the invention (example) as comparison alloys.
  • the chemical composition of the alloys examined is given below (data in % by weight): CuAl10Fe5Ni5-C CuZn16Si4-C example Cu 80.32 79.4 83.7 si 0.08 4.2 4.9 Al 9.2 0.03 1.0 feet 4.6 0.04 0.2 no 4.7 0.51 0.1 sn 0.05 0.1 0.1 Mn 1.2 0.12 - pb - 0.2 - Zn 0.5 rest rest rest rest rest
  • the alloy of the exemplary embodiment can be referred to as the CuZn10Si5Al1 alloy.
  • the two comparison alloys CuAl10Fe5Ni5-C and CuZn16Si4-C are cast alloys.
  • the alloy of the exemplary embodiment is a wrought alloy. It goes without saying that the alloy according to the invention can also be cast in order to produce castings.
  • Specimens were made from the alloys, from the comparative alloys by casting them into the desired specimen shape, while in the embodiment the specimen was made by hot working, namely extrusion.
  • the test pieces have a diameter of about 15 mm and a thickness of about 5 mm.
  • the samples were ground and polished prior to conducting the tests.
  • the specimens were then tested for cavitation erosion resistance (cavitation resistance) using the parameters defined in ASTM G32-10.
  • the samples were subjected to the ultrasonic inspection for the cavitation erosion resistance tests in distilled water at 20°C as the test medium.
  • the distance between the tip of the sonotrode and the sample is 0.5 mm.
  • the sonotrode tip was operated at a frequency of 20 kHz and an amplitude of 40 ⁇ m.
  • the mass loss determined by the cavitation impact on the samples examined is shown in the diagram figure 1 shown.
  • the two comparison alloys show a largely consistent mass loss over time.
  • the cavitation resistance of the exemplary embodiment according to the invention is again significant improved. While the loss of mass in the comparative samples is around 7 mg after a measurement time of 300 minutes, it is around 2 mg in the sample according to the invention examined, in any case below 2.5 mg. Also measured over a longer sample period of the cavitation test, the mass loss determined with the sample according to the invention remains significantly lower than that of the comparison alloys. While the mass loss in the comparison alloys is about 18-18.5 mg after a sample time of 600 minutes, this is not even 7.5 mg in the examined sample of the exemplary embodiment according to the invention. The loss of mass determined for the tested sample is about 6.5 mg and is therefore about three times lower than that of the comparison alloys currently considered to be particularly cavitation-resistant.
  • Figures 2a, 2b show raster electronic images of the comparison alloy CuAl10Fe5Nl5-C after a 90-minute cavitation exposure according to ASTM G32-10 in different scales.
  • the surface of the sample is characterized by breakouts.
  • the material eruptions caused by cavitation give the surface of the sample a crater-like appearance, as shown in Figs Figures 3a, 3b is recognizable.
  • These scanning electron micrographs show this sample tilted 45°. Scanning electron micrographs of the comparison alloy CuZn16Si4-C are very similar.
  • FIG 4 shows a scanning electron micrograph of the embodiment of the invention.
  • the ones in the photograph figure 4 marked areas A - E show those excerpts in the Figures 5a - 5e are shown in a different representation and scale.
  • a comparison with the recordings of Figures 2a, 2b makes it clear that the surface is almost unaffected by cavitation, although the sampling time of the cavitation test is twice as long was like the sample time in the comparative sample.
  • the scanning electron micrographs tilted by 45° Figure 5a - 5e clarifies this.
  • the surface of the sample remains uniform and does not show the crater-like structures of the images Figures 3a, 3b of the comparison sample.
  • the Figures 5a - 5e make it clear that only very slight cavitation phenomena can be seen over the entire surface of the sample according to the invention, at least none that correspond to those attributed to comparison alloys CuAl10Fe5Ni5-C or CuZn16Si4-C, which were previously considered to be particularly cavitation-resistant.
  • the improved cavitation resistance of the alloy according to the invention allows the use of products which, when used in cavitation-prone environments, have a significantly longer service life. The damage that otherwise occurs due to cavitation and has hitherto had to be accepted is thus drastically reduced when the claimed alloy is used to produce a cavitation-resistant product or component.
  • the electrical conductivity of this alloy is around 5 MS/m.
  • This alloy thus combines the properties of a high-strength special brass alloy and high formability with the advantages of excellent cavitation erosion resistance.
  • the positive alloy properties are also attributed to the heterogeneous texture of the grain orientations.
  • DSC analyses Differential scanning calorimetry analyzes (DSC analyses) were carried out on samples of the alloy according to the invention and thus also on the exemplary embodiment described. It was surprisingly found that contrary to the earlier assumption that cavitation-resistant alloys must have a certain pseudo-elasticity, the alloy according to the invention does not actually exhibit such pseudo-elastic material behavior, at least not to any significant extent.
  • the significantly improved resistance to cavitation in the alloy according to the invention is based on the special balance between formability and strength. This obviously has a positive effect on the cavitation resistance.
  • the cavitation energy is introduced into the material and distributed to the grains via deformation. This progresses over a long duration of the cavitation test, but without this leading to disadvantageous accumulations of material, which would be the case with previously known alloys that are considered to be cavitation-resistant, which would be removed from the surface.
  • a product manufactured with the alloy according to the invention is particularly suitable for the production of gear pumps or parts for steam and water fittings, ie parts which are exposed to increased cavitation stress on their surface. It goes without saying that other products which are exposed to cavitation on their surface by fluids flowing past can also be produced from this.

Description

Die Erfindung betrifft die Verwendung einer Cu-Zn-Legierung.The invention relates to the use of a Cu-Zn alloy.

Bei vielen Anwendungsfällen einer Cu-Zn-Legierung werden neben Cu und Zn weitere Legierungselemente in diese eingebracht, um bestimmte Legierungseigenschaften erzielen zu können. Derartige Legierungen werden auch als Sondermessinglegierungen angesprochen. Das Einsatzgebiet von Sondermessinglegierungen ist sehr umfangreich. Eingesetzt werden derartige Messinglegierungen beispielsweise zum Herstellen von in Ölumgebungen, wie beispielsweise Getrieben eingesetzten Bauteilen, auch solche, die in thermisch anspruchsvoller Umgebung eingesetzt werden, wie beispielsweise als Ventilführung bei einem Verbrennungsmotor. Bekannt ist aus DE 10 2014 101 346 A1 eine Messinglegierung, die in besonderer Weise an die Anforderungen eines in einer Ölumgebung eingesetzten Bauteils, ausgelegt ist. Konkret ist in diesem Stand der Technik ein Synchronring als derartiges Bauteil beschrieben. Die Ölumgebung, in der sich der Synchronring befindet, kann sich in Abhängigkeit von dem Öl und insbesondere dessen Additiven ändern, was Einfluss auf die mechanischen Eigenschaften und die thermische Belastbarkeit haben kann. Begründet liegt dieses darin, dass in Abhängigkeit von den im Öl befindlichen Additiven diese einen unterschiedlichen Einfluss auf die Korrosionsbeständigkeit des Synchronrings als beispielhaftes Sondermessinglegierungsprodukt haben.In many applications of a Cu-Zn alloy, other alloying elements are introduced in addition to Cu and Zn in order to be able to achieve certain alloy properties. Such alloys are also referred to as special brass alloys. The field of application of special brass alloys is very extensive. Such brass alloys are used, for example, to produce components used in oil environments, such as transmissions, including those that are used in thermally demanding environments, such as valve guides in an internal combustion engine. is known from DE 10 2014 101 346 A1 a brass alloy specially designed to meet the requirements of a component used in an oil environment. Specifically, a synchronizing ring is described as such a component in this prior art. The oil environment in which the synchronizer ring is located can change depending on the oil and especially its additives, which can affect the mechanical properties and thermal load capacity. The reason for this is that, depending on the additives in the oil, they have a different influence on the corrosion resistance of the synchronizing ring as an example of a special brass alloy product.

Neben einer Beständigkeit gegen Korrosion und wie im Falle der DE 10 2014 101 346 A1 auch gegenüber unterschiedlichen Ölumgebungen ist in aller Regel gefordert, dass ein solches Sondermessinglegierungsprodukt auch bestimmte mechanische Festigkeitswerte aufweist. Bei anderen Anwendungen wird anstelle oder auch zusätzlich eine Entzinkungsbeständigkeit gefordert. Auch spielt die Möglichkeit einer spanenden Bearbeitung eines solchen Messinglegierungsproduktes oftmals eine entscheidende Rolle.In addition to a resistance to corrosion and as in the case of DE 10 2014 101 346 A1 Also in relation to different oil environments, it is generally required that such a special brass alloy product also has certain mechanical strength values. In other applications, resistance to dezincification is required instead or in addition. The possibility of machining such a brass alloy product often also plays a decisive role.

Derartige Messinglegierungsprodukte werden allerdings auch in Umgebungen eingesetzt, in denen eine Kavitationsbeständigkeit gefordert wird. Kavitation tritt an solchen Messinglegierungsteilen ein, an deren Oberfläche Fluide vorbeiströmen, wie beispielsweise bei Schiffsschrauben, Pumpen, wie etwa Kreiselpumpen oder Zahlradpumpen oder dergleichen ein. Die Kavitation an der Oberfläche macht sich in Form von kurzzeitigen, sehr starken Druckstößen bemerkbar, die zu einer sogenannten Kavitationserosion (Kavitationsfraß) führen. Eine dauerhafte Beanspruchung durch Kavitation führt dazu, dass aus der Oberfläche Partikel herausbrechen, was zu einer Beschädigung und damit zu einer Schwächung oder sogar zu einer vollständigen Zerstörung des Bauteils führen kann. Aus diesem Grunde werden Bauteile, die möglichst kavitationsbeständig sein sollen, aus ganz speziellen Messinglegierungen hergestellt. Die derzeit als besonders kavitationsbeständig angesehene Cu-Zn-Legierung ist die Legierung CuZn16Si4-C. Hierbei handelt es sich um eine Gusslegierung. Eine vergleichbare Kavitationsbeständigkeit (Kavitationserosionsresistenz) bieten nur Aluminiumbronzen (CuAl10Ni5Fe5). Die Kavitationsbeständigkeit der CuZn16Si4-C-Legierung ist in "Entwicklung einer kavitationserosionsresistenten pseudoelastischen CuZnSi-Legierung", veröffentlicht in der Zeitschrift METALL, 72. Jahrgang, Ausgabe 11/2018, beschrieben.However, such brass alloy products are also used in environments where resistance to cavitation is required. Cavitation occurs on those brass alloy parts where fluids flow past the surface, such as in marine propellers, pumps such as centrifugal or gear pumps, or the like. The cavitation on the surface is noticeable in the form of short-term, very strong pressure surges, which lead to what is known as cavitation erosion (cavitation corrosion). Permanent stress from cavitation causes particles to break out of the surface, which can lead to damage and thus to weakening or even complete destruction of the component. For this reason, components that should be as cavitation-resistant as possible are made from very special brass alloys. The Cu-Zn alloy currently considered to be particularly cavitation-resistant is the CuZn16Si4-C alloy. This is a cast alloy. Only aluminum bronzes (CuAl10Ni5Fe5) offer comparable cavitation resistance (cavitation erosion resistance). The cavitation resistance of the CuZn16Si4-C alloy is described in "Development of a cavitation-erosion-resistant pseudoelastic CuZnSi alloy", published in the journal METALL, Volume 72, Issue 11/2018.

Um die Kavitationserosionsbeständigkeit von Silizium-Messinglegierungen weiter zu verbessern, wird gemäß dieser Veröffentlichung versucht, eine bei Raumtemperatur pseudoelastische, feinkörnige Legierung bereit zu stellen. Eine besonders gute Kavitationserosionsresistenz konnte mit der Legierung CuZn35Si1 nachgewiesen werden. Allerdings genügt diese Legierung bzw. das daraus hergestellte Produkt nicht den üblicherweise an ein solches Produkt gestellten Temperaturanforderungen.According to this publication, in order to further improve the cavitation erosion resistance of silicon-brass alloys, an attempt is made to provide a fine-grained alloy that is pseudo-elastic at room temperature. A particularly good resistance to cavitation erosion could be demonstrated with the alloy CuZn35Si1. However, this alloy or the product made from it does not meet the temperature requirements usually placed on such a product.

Die Werkstoffanforderungen an ein kavitationserosionsbeständiges Produkt sind hochkomplex. Einerseits soll die Messinglegierung eine gewisse Verformbarkeit aufweisen, damit bei dem Kavitationsangriff das Material verschoben werden kann. Allerdings darf dieses nicht herausbrechen. Andererseits darf sich die Messinglegierung nicht zu schnell an Hindernissen aufbauen, weil sonst Material von der Oberfläche hervorsteht und beim nächsten Kavitationsangriff entfernt werden kann, was zu einem Masseverlust führt. Die Unterschiedlichkeit der vorbeschriebenen und als kavitationsbeständig angesehenen Messinglegierungen zeigt, wie schwierig das Auffinden von kavitationserosionsbeständigen Messinglegierungen ist. Noch schwieriger ist es, solche Messinglegierungen aufzufinden, deren Kavitationserosionsbeständigkeit gegenüber herkömmlichen sogar noch verbessert ist.The material requirements for a cavitation erosion-resistant product are highly complex. On the one hand, the brass alloy should have a certain deformability so that the material can be displaced during the cavitation attack. However, this must not break out. On the other hand, the brass alloy must not build up too quickly on obstacles, otherwise material will protrude from the surface and can be removed in the next cavitation attack, resulting in a loss of mass leads. The difference between the brass alloys described above and considered to be cavitation-resistant shows how difficult it is to find cavitation-erosion-resistant brass alloys. It is even more difficult to find such brass alloys whose cavitation erosion resistance is even better than conventional ones.

EP 1 777 305 A1 offenbart Kupfergusslegierungen, die für die Verwendung als Wasserventile, Wasserhähne, Schiffspropeller und dergleichen verwendet werden. Diese Legierungen werden zum Teil heiß extrudiert. Diese Legierungen sind Al-frei. EP 1 777 305 A1 discloses cast copper alloys intended for use as water valves, faucets, marine propellers and the like. Some of these alloys are hot extruded. These alloys are Al-free.

Ausgehend von diesem diskutierten Stand der Technik liegt der Erfindung daher die Aufgabe zu Grunde, eine Messinglegierung vorzuschlagen, die gegenüber der bereits als besonders kavitationsbeständig angesehenen Legierung CuZn16Si4-C eine verbesserte Kavitationserosionsbeständigkeit aufweist und die zudem den an ein solches Werkstück gestellten Temperaturanforderungen genügt, vor allem ohne dass zu diesem Zweck ein aufwendiges bzw. kompliziertes Herstellungsverfahren bemüht werden müsste. Zudem soll sich die Legierung als Knetlegierung eignen, damit aus der Legierung auch Produkte hergestellt werden können, die mit einer Gusslegierung nicht oder nicht mit den gewünschten Anforderungen hergestellt werden können.Proceeding from this discussed state of the art, the invention is therefore based on the object of proposing a brass alloy which, compared to the alloy CuZn16Si4-C, which is already regarded as particularly cavitation-resistant, has improved resistance to cavitation erosion and which also meets the temperature requirements placed on such a workpiece, above all without having to use a costly or complicated manufacturing process for this purpose. In addition, the alloy should be suitable as a wrought alloy, so that products can also be produced from the alloy that cannot be produced with a cast alloy or cannot be produced with the desired requirements.

Gelöst wird diese Aufgabe erfindungsgemäß durch die Verwendung einer Cu-Zn-Legierung als Knetlegierung mit folgender Zusammensetzung (Angaben in Gew.-%): Cu: 80 - 85, Si: 2,0 - 6,0, Al: 0,55 - 2,0, Fe: max. 0,8, Ni: max. 0,5, Sn: max. 0,5, Mn: max. 0,1, Pb: max. 0,3, Rest Zn sowie unvermeidbare Verunreinigungen
zum Herstellen eines kavitationsbeständigen Produktes, dessen Oberfläche bei bestimmungsgemäßer Anwendung in Kontakt zu vorbeiströmenden Fluiden gelangt.This object is achieved according to the invention by using a Cu-Zn alloy as a wrought alloy with the following composition (in percent by weight): Cu: 80 - 85, Si: 2.0 - 6.0, Al: 0.55 - 2.0, Fe: max 0.8, Ni: max. 0.5, Sn: max. 0.5, Mn: max 0.1, pb: max. 0.3, remainder Zn and unavoidable impurities
for the manufacture of a cavitation-resistant product, the surface of which comes into contact with fluids flowing past when used as intended.

Vor dem Hintergrund der Erkenntnisse aus dem Stand der Technik war es für die am Zustandekommen der Erfindung beteiligten Personen überaus überraschend, dass die prinzipiell aus DE 10 2014 101 346 A1 vorbekannte Legierung innerhalb der beanspruchten Gehalte der Legierungselemente eine sogar gegenüber der CuZn16Si4-C deutlich verbesserte Kavitationsbeständigkeit aufweist. Unerwartet war dieses Ergebnis deswegen, da die Entwicklung ausgehend von CuZn16Si4-C zum Bereitstellen kavitationsbeständiger Legierungen den Cu-Anteil signifikant reduziert und dementsprechend den Zn-Anteil signifikant angehoben hat, wie das Beispiel CuZn35Si1 als Weiterentwicklung der CuZn16Si4-C-Legierung deutlich macht. Die erfindungsgemäße kavitationsbeständige Legierung verfügt demgegenüber über einen gegenüber CuZn16Si4-C höheren Cu-Gehalt und setzt auf das Element Aluminium als Legierungsbestandteil. Aluminium wirkt bekanntermaßen in einer Cu-Zn-Legierung festigkeitssteigernd. Daher war nicht zu erwarten, dass diese Legierung die für erforderlich gehaltenen pseudoelastischen Eigenschaften aufweist, durch die diese besondere Kavitationsbeständigkeit dieser Legierung begründet ist. Hingegen liegt in Bezug auf die Legierung CuZn16Si4-C, die einen Ni-Gehalt von bis zu 1,0 Gew.-% aufweisen kann, der zugelassene Ni-Gehalt bei der erfindungsgemäßen Legierung zum Herstellen des kavitationsbeständigen Produktes nur bei 0,5 Gew.-%.Against the background of the findings from the prior art, it was extremely surprising for the people involved in the creation of the invention that the principle from DE 10 2014 101 346 A1 previously known alloy within the claimed contents of the alloying elements even has a significantly improved cavitation resistance compared to CuZn16Si4-C. This result was unexpected because the development based on CuZn16Si4-C to provide cavitation-resistant alloys significantly reduced the Cu content and accordingly significantly increased the Zn content, as the example of CuZn35Si1 as a further development of the CuZn16Si4-C alloy makes clear. In contrast, the cavitation-resistant alloy according to the invention has a higher Cu content than CuZn16Si4-C and relies on the element aluminum as an alloy component. Aluminum is known to increase strength in a Cu-Zn alloy. It was therefore not to be expected that this alloy would have the pseudo-elastic properties that were considered necessary and which are the reason for this special cavitation resistance of this alloy. On the other hand, with regard to the CuZn16Si4-C alloy, which can have a Ni content of up to 1.0% by weight, the permitted Ni content in the alloy according to the invention for producing the cavitation-resistant product is only 0.5% by weight. -%.

Der Si-Gehalt beträgt 2,0 bis 6,0 Gew.-%. Eine Erhöhung des Si-Gehaltes führt nicht zu einer weiteren Kavitationsbeständigkeit. In einem Ausführungsbespiel ist vorgesehen, den Si-Gehalt zwischen 3,7 und 6,0 Gew.-% vorzusehen. In einem weiteren Ausführungsbeispiel liegt dieser zwischen 4,7 und 5,3 Gew.-%. In noch einem weiteren Ausführungsbeispiel ist vorgesehen, dass der Si-Gehalt zwischen 2,0 und 2,8 Gew.-% beträgt.The Si content is 2.0 to 6.0% by weight. Increasing the Si content does not lead to further cavitation resistance. In one embodiment, the Si content is between 3.7 and 6.0% by weight. In a further exemplary embodiment, this is between 4.7 and 5.3% by weight. In yet another exemplary embodiment, it is provided that the Si content is between 2.0 and 2.8% by weight.

Der Aluminiumgehalt beträgt zwischen 0,55 und 2,0 Gew.-%. Vorzugsweise liegt der Al-Gehalt zwischen 0,65 und 1,5 Gew.-%. In einem weiteren Ausführungsbeispiel beträgt der Al-Gehalt 0,8 und 1,3 Gew.-%. Mit diesen Al-Gehalten wurden die besten Ergebnisse bezüglich der Korrosionsbeständigkeit erzielt.The aluminum content is between 0.55 and 2.0% by weight. The Al content is preferably between 0.65 and 1.5% by weight. In a further embodiment, the Al content is 0.8 and 1.3% by weight. With these Al contents the best results in terms of corrosion resistance were achieved.

Die aus DE 10 2014 101 346 A1 vorbekannte Legierung eignet sich als Knetlegierung. Insofern war auch bezüglich dieser Eigenschaft nicht zu erwarten, dass sich vor dem Hintergrund, dass herkömmlich maßgeblich nur Gusslegierungen zum Herstellen von kavitationsbeständigen Produkten oder Bauteilen eingesetzt worden sind. Dadurch ist die Produktvielfalt, die mit der erfindungsgemäßen Legierung hergestellt werden kann, auch bezüglich der möglichen Gefügeeigenschaften deutlich verbessert.From DE 10 2014 101 346 A1 previously known alloy is suitable as a wrought alloy. In this respect, it was also not to be expected with regard to this property that, against the background that conventionally only cast alloys were used to manufacture cavitation-resistant products or components. As a result, the variety of products that can be produced with the alloy according to the invention is also significantly improved with regard to the possible structural properties.

Von besonderem Vorteil bei dieser Legierung ist, dass sich die positiven Eigenschaften der Kavitationsbeständigkeit dieser Legierung unmittelbar in einem dem Gießen nachfolgenden Warmumformschritt einstellen, ohne dass eine nachgeschaltete besondere thermische Behandlung zum Einstellen bzw. Herstellen der Kavitationsbeständigkeit erforderlich wäre. Daher kann aus dieser Legierung ein kavitationsbeständiges Produkt mit den an sich üblichen Prozessschritten hergestellt werden.A particular advantage of this alloy is that the positive cavitation resistance properties of this alloy are set directly in a hot forming step following casting, without a subsequent special thermal treatment being required to set or produce the cavitation resistance. A cavitation-resistant product can therefore be manufactured from this alloy using the usual process steps.

Dieses Messinglegierungsprodukt ist zudem breitbandig schmierstoffverträglich, hat hervorragende mechanische Eigenschaften und ist temperaturbeständig. Auf die diesbezüglichen Ausführungen in DE 10 2014 101 346 A1 derselben Anmelderin wird Bezug genommen, durch welche Bezugnahme die Ausführungen in dem genannten Dokument gleichfalls zum Gegenstand und Offenbarungsgehalt dieser Ausführungen gemacht werden und zählen. Untersuchungen haben gezeigt, dass die 0,2-Dehngrenze 240 und 260 N/mm2, die Zugfestigkeit 530 und 600 N/mm2, die Bruchdehnung 16 bis 22 % und die Brinellhärte 155 bis 165 HBW beträgt. Zudem weisen die als Knetlegierung hergestellten Probenstücke eine höhere Dichte auf im Vergleich zu Gusswerkstoffen.This brass alloy product is also compatible with a wide range of lubricants, has excellent mechanical properties and is temperature-resistant. On the relevant statements in DE 10 2014 101 346 A1 reference is made to the same applicant, through which reference the statements in the document mentioned are also made the subject matter and disclosure content of these statements and count. Investigations have shown that the 0.2 yield strength is 240 and 260 N/mm 2 , the tensile strength is 530 and 600 N/mm 2 , the elongation at break is 16 to 22% and the Brinell hardness is 155 to 165 HBW. In addition, the specimens produced as a wrought alloy have a higher density compared to cast materials.

Nachfolgend ist die Erfindung unter Bezugnahme auf die beiliegenden Figuren anhand eines Ausführungsbeispiels beschrieben. Es zeigen:

Fig. 1:
ein Masseverlustdiagramm, in dem der Masseverlust einer erfindungsgemäßen Probe sowie von zwei Vergleichsproben aus herkömmlichen Legierungen gegenüber der Zeit der Untersuchung aufgetragen sind,
Fig. 2a, 2b:
rasterelektronenmikroskopische Aufnahmen einer Aluminiumbronze nach einer 90-minütigen Kavitationsbeaufschlagung,
Fig. 3a, 3b:
rasterelektronenmikroskopische Aufnahmen einer Aluminiumbronze nach einer 90-minütigen Kavitationsbeaufschlagung, jedoch um 45° gekippt,
Fig. 4:
eine rasterelektronenmikroskopische Aufnahme der erfindungsgemäßen Legierung nach 180 Minuten Kavitationsbeaufschlagung und
Fig. 5a - 5e:
eine rasterelektronenmikroskopische Aufnahme der erfindungsgemäßen Legierung nach 180 Minuten Kavitationsbeaufschlagung, jedoch um 45° gekippt.
The invention is described below with reference to the enclosed figures using an exemplary embodiment. Show it:
Figure 1:
a mass loss diagram in which the mass loss of a sample according to the invention and two comparative samples made of conventional alloys are plotted against the time of the test,
Figures 2a, 2b:
Scanning electron micrographs of an aluminum bronze after 90 minutes of cavitation exposure,
Figures 3a, 3b:
Scanning electron micrographs of an aluminum bronze after 90 minutes of cavitation exposure, but tilted by 45°,
Figure 4:
a scanning electron micrograph of the alloy according to the invention after 180 minutes of cavitation and
Figures 5a - 5e:
a scanning electron micrograph of the alloy according to the invention after 180 minutes of cavitation, but tilted by 45 °.

Für Kavitationsuntersuchungen wurden drei Cu-Zn-Legierungen untersucht, und zwar als Vergleichslegierungen die Legierungen CuAl10Fe5Ni5 und CuZn16Si4-C und eine erfindungsgemäße Legierung (Ausführungsbeispiel). Die chemische Zusammensetzung der untersuchten Legierungen ist nachfolgend wiedergegeben (Angaben in Gew.-%): CuAl10Fe5Ni5-C CuZn16Si4-C Ausführungsbeispiel Cu 80,32 79,4 83,7 Si 0,08 4,2 4,9 Al 9,2 0,03 1,0 Fe 4,6 0,04 0,2 Ni 4,7 0,51 0,1 Sn 0,05 0,1 0,1 Mn 1,2 0,12 - Pb - 0,2 - Zn 0,5 Rest Rest Three Cu-Zn alloys were examined for cavitation investigations, specifically the alloys CuAl10Fe5Ni5 and CuZn16Si4-C and an alloy according to the invention (example) as comparison alloys. The chemical composition of the alloys examined is given below (data in % by weight): CuAl10Fe5Ni5-C CuZn16Si4-C example Cu 80.32 79.4 83.7 si 0.08 4.2 4.9 Al 9.2 0.03 1.0 feet 4.6 0.04 0.2 no 4.7 0.51 0.1 sn 0.05 0.1 0.1 Mn 1.2 0.12 - pb - 0.2 - Zn 0.5 rest rest

Die Legierung des Ausführungsbeispiels kann als Legierung CuZn10Si5Al1 angesprochen werden.The alloy of the exemplary embodiment can be referred to as the CuZn10Si5Al1 alloy.

Bei den beiden Vergleichslegierungen CuAl10Fe5Ni5-C und CuZn16Si4-C handelt es sich um Gusslegierungen. Die Legierung des Ausführungsbeispiels ist hingegen eine Knetlegierung. Es versteht sich, dass die erfindungsgemäße Legierung auch gegossen werden kann, um Gussstücke herzustellen.The two comparison alloys CuAl10Fe5Ni5-C and CuZn16Si4-C are cast alloys. The alloy of the exemplary embodiment, on the other hand, is a wrought alloy. It goes without saying that the alloy according to the invention can also be cast in order to produce castings.

Aus den Legierungen wurden Probenstücke gefertigt, und zwar aus den Vergleichslegierungen durch Gießen derselben in die gewünschte Probenform, während bei dem Ausführungsbeispiel die Probe durch Warmumformen, und zwar Strangpressen hergestellt worden ist. Die Probenstücke haben einen Durchmesser von etwa 15 mm und eine Dicke von etwa 5 mm. Die Proben wurden vor dem Durchführen der Versuche geschliffen und poliert. Die Probenstücke wurden anschließend auf ihre Kavitationserosionsresistenz (Kavitationsbeständigkeit) mit den in ASTM G32-10 definierten Parametern untersucht. Die Proben wurden für die Kavitationserosionsresistenzuntersuchungen in destilliertem Wasser bei 20°C als Prüfmedium der Ultraschalluntersuchung unterzogen. Der Abstand der Sonotrodenspitze zur Probe beträgt 0,5 mm. Die Sonotrodenspitze wurde mit einer Frequenz von 20 kHz und einer Amplitude von 40 µm betrieben. Der durch die Kavitationsbeaufschlagung bei den untersuchten Proben festgestellte Masseverlust ist in dem Diagramm der Figur 1 gezeigt.Specimens were made from the alloys, from the comparative alloys by casting them into the desired specimen shape, while in the embodiment the specimen was made by hot working, namely extrusion. The test pieces have a diameter of about 15 mm and a thickness of about 5 mm. The samples were ground and polished prior to conducting the tests. The specimens were then tested for cavitation erosion resistance (cavitation resistance) using the parameters defined in ASTM G32-10. The samples were subjected to the ultrasonic inspection for the cavitation erosion resistance tests in distilled water at 20°C as the test medium. The distance between the tip of the sonotrode and the sample is 0.5 mm. The sonotrode tip was operated at a frequency of 20 kHz and an amplitude of 40 µm. The mass loss determined by the cavitation impact on the samples examined is shown in the diagram figure 1 shown.

Die beiden Vergleichslegierungen zeigen einen weitgehend übereinstimmenden Masseverlust über die Zeit.The two comparison alloys show a largely consistent mass loss over time.

Während die beiden Vergleichslegierungen bereits eine als besonders gut angesehene Kavitationsbeständigkeit aufweisen, ist die Kavitationsbeständigkeit des erfindungsgemäßen Ausführungsbeispiels nochmals signifikant verbessert. Während der Masseverlust bei den Vergleichsproben nach einer Messzeit von 300 Minuten bei etwa 7 mg liegt, liegt dieser bei der untersuchten erfindungsgemäßen Probe bei etwa 2 mg, jedenfalls unterhalb von 2,5 mg. Auch über eine längere Probenzeit der Kavitationsprüfung gemessen, bleibt der bei der erfindungsgemäßen Probe festgestellte Masseverlust deutlich geringer als derjenige der Vergleichslegierungen. Während bei den Vergleichslegierungen nach einer Probenzeit von 600 Minuten der Masseverlust etwa 18 - 18,5 mg beträgt, beträgt dieser bei der untersuchten Probe des erfindungsgemäßen Ausführungsbeispiels noch nicht einmal 7,5 mg. Der festgestellte Masseverlust beträgt bei der untersuchten Probe etwa 6,5 mg und ist damit etwa dreimal geringer als derjenige der derzeitig als besonders kavitationsbeständig angesehenen Vergleichslegierungen.While the two comparison alloys already have a cavitation resistance that is regarded as particularly good, the cavitation resistance of the exemplary embodiment according to the invention is again significant improved. While the loss of mass in the comparative samples is around 7 mg after a measurement time of 300 minutes, it is around 2 mg in the sample according to the invention examined, in any case below 2.5 mg. Also measured over a longer sample period of the cavitation test, the mass loss determined with the sample according to the invention remains significantly lower than that of the comparison alloys. While the mass loss in the comparison alloys is about 18-18.5 mg after a sample time of 600 minutes, this is not even 7.5 mg in the examined sample of the exemplary embodiment according to the invention. The loss of mass determined for the tested sample is about 6.5 mg and is therefore about three times lower than that of the comparison alloys currently considered to be particularly cavitation-resistant.

Dieses Ergebnis war nicht zu erwarten. Insbesondere war nicht zu erwarten, dass die erfindungsgemäße Legierung hinsichtlich ihrer Kavitationsbeständigkeit nochmals signifikant besser ist als die derzeitig als besonders kavitationsbeständig angesehenen.This result was not to be expected. In particular, it was not to be expected that the alloy according to the invention would again be significantly better in terms of its cavitation resistance than those currently considered to be particularly cavitation-resistant.

Die Wirkung der Kavitation kann anhand der Figuren 2 bis 5 verdeutlicht werden. Figuren 2a, 2b zeigen rasterelektronische Aufnahmen der Vergleichslegierung CuAl10Fe5Nl5-C nach einer 90-minütigen Kavitationsbeaufschlagung gemäß ASTM G32-10 in unterschiedlichen Maßstäben. Die Oberfläche der Probe ist durch Ausbrechungen gekennzeichnet. Die durch Kavitation bedingten Materialausbrüche verleihen der Oberfläche der Probe ein kraterartiges Aussehen, wie dieses in den Figuren 3a, 3b erkennbar ist. Diese rasterelektronenmikroskopischen Aufnahmen zeigen diese Probe bei einer Kippung um 45°. Rasterelektronenmikroskopische Aufnahmen der Vergleichslegierung CuZn16Si4-C sind ganz ähnlich.The effect of cavitation can be based on the Figures 2 to 5 be clarified. Figures 2a, 2b show raster electronic images of the comparison alloy CuAl10Fe5Nl5-C after a 90-minute cavitation exposure according to ASTM G32-10 in different scales. The surface of the sample is characterized by breakouts. The material eruptions caused by cavitation give the surface of the sample a crater-like appearance, as shown in Figs Figures 3a, 3b is recognizable. These scanning electron micrographs show this sample tilted 45°. Scanning electron micrographs of the comparison alloy CuZn16Si4-C are very similar.

Figur 4 zeigt eine rasterelektronenmikroskopische Aufnahme des erfindungsgemäßen Ausführungsbeispiels. Die in der Fotografie der Figur 4 kenntlich gemachten Bereiche A - E zeigen diejenigen Ausschnitte, die in den Figuren 5a - 5e in einer anderen Darstellung und einem anderen Maßstab gezeigt sind. Ein Vergleich mit den Aufnahmen der Figuren 2a, 2b macht deutlich, dass die Oberfläche so gut wie nicht durch Kavitation beeinflusst ist, obwohl die Probenzeit der Kavitationsprüfung doppelt so lang war wie die Probenzeit bei der Vergleichsprobe. Die um 45° gekippte rasterelektronenmikroskopische Aufnahmen der Figur 5a - 5e verdeutlicht dieses. Die Oberfläche der Probe bleibt einheitlich und weist nicht die kraterförmigen Strukturen der Aufnahmen der Figuren 3a, 3b der Vergleichsprobe auf. figure 4 shows a scanning electron micrograph of the embodiment of the invention. The ones in the photograph figure 4 marked areas A - E show those excerpts in the Figures 5a - 5e are shown in a different representation and scale. A comparison with the recordings of Figures 2a, 2b makes it clear that the surface is almost unaffected by cavitation, although the sampling time of the cavitation test is twice as long was like the sample time in the comparative sample. The scanning electron micrographs tilted by 45° Figure 5a - 5e clarifies this. The surface of the sample remains uniform and does not show the crater-like structures of the images Figures 3a, 3b of the comparison sample.

Die Figuren 5a - 5e verdeutlichen, dass über die gesamte Oberfläche der erfindungsgemäßen Probe nur sehr geringe Kavitationserscheinungen zu erkennen sind, jedenfalls keine, die derjenigen entsprechen, wie diese bislang als besonders kavitationsbeständig angesehen Vergleichslegierungen CuAl10Fe5Ni5-C bzw. CuZn16Si4-C zugeschrieben werden. Die verbesserte Kavitationsbeständigkeit der erfindungsgemäßen Legierung erlaubt den Einsatz von Produkten, die, wenn in kavitationsgefährdeten Umgebungen eingesetzt, eine signifikant längere Standzeit bzw. Lebensdauer haben. Die ansonsten durch Kavitation eintretende und bislang notwendigerweise in Kauf zu nehmenden Schäden werden somit bei einer Verwendung der beanspruchten Legierung zum Herstellen eines kavitationsbeständigen Produktes oder Bauteils drastisch reduziert.the Figures 5a - 5e make it clear that only very slight cavitation phenomena can be seen over the entire surface of the sample according to the invention, at least none that correspond to those attributed to comparison alloys CuAl10Fe5Ni5-C or CuZn16Si4-C, which were previously considered to be particularly cavitation-resistant. The improved cavitation resistance of the alloy according to the invention allows the use of products which, when used in cavitation-prone environments, have a significantly longer service life. The damage that otherwise occurs due to cavitation and has hitherto had to be accepted is thus drastically reduced when the claimed alloy is used to produce a cavitation-resistant product or component.

Die Legierung gemäß Ausführungsbeispiel - CuZn10Si5Al1 - weist als mechanische Kennwerte eine 0,2-Dehngrenze von 250 N/mm2, eine Zugfestigkeit von 530 bis 600 N/mm2, eine Bruchdehnung von 18 bis 21 % und eine Brinellhärte von 160 HBW auf. Die elektrische Leitfähigkeit dieser Legierung liegt bei etwa 5 MS/m.The alloy according to the exemplary embodiment—CuZn10Si5Al1—has a 0.2 yield strength of 250 N/mm 2 , a tensile strength of 530 to 600 N/mm 2 , an elongation at break of 18 to 21% and a Brinell hardness of 160 HBW as mechanical characteristics. The electrical conductivity of this alloy is around 5 MS/m.

Diese Legierung vereint somit die Eigenschaften einer hochfesten Sondermessinglegierung und hohem Umformvermögen mit den Vorteilen einer hervorragenden Kavitationserosionsbeständigkeit.This alloy thus combines the properties of a high-strength special brass alloy and high formability with the advantages of excellent cavitation erosion resistance.

Die positiven Legierungseigenschaften vor allem hinsichtlich der Kavitationsbeständigkeit werden auch der heterogenen Textur der Kornorientierungen zugeschrieben.The positive alloy properties, especially with regard to cavitation resistance, are also attributed to the heterogeneous texture of the grain orientations.

Differential Scanning Calorimetry-Analysen (DSC-Analysen) wurden an Proben der erfindungsgemäßen Legierung und so auch an dem beschriebenen Ausführungsbeispiel durchgeführt. Überraschend stellte man fest, dass entgegen der früheren Annahme, kavitationsbeständige Legierungen müssten eine gewisse Pseudoelastizität aufweisen, tatsächlich die erfindungsgemäße Legierung ein solches pseudoelastisches Materialverhalten nicht, jedenfalls nicht nennenswert zeigt. Die signifikant verbesserte Kavitationsbeständigkeit wird bei der erfindungsgemäßen Legierung auf der besonderen Ausgewogenheit von Umformvermögen und Festigkeit begründet. Dieses wirkt sich ganz offenbar positiv auf den Kavitationswiderstand aus. Die Kavitationsenergie wird bei der erfindungsgemäßen Legierung in den Werkstoff eingetragen und über Verformung auf die Körner verteilt. Diese schreitet über eine auch lange Dauer der Kavitationsprüfung fort, jedoch ohne dass dieses zu nachteiligen Materialaufhäufungen, was bei vorbekannten Legierungen, die als kavitationsbeständig gelten, der Falls ist, führen würde, die von der Oberfläche abgetragen würden.Differential scanning calorimetry analyzes (DSC analyses) were carried out on samples of the alloy according to the invention and thus also on the exemplary embodiment described. It was surprisingly found that contrary to the earlier assumption that cavitation-resistant alloys must have a certain pseudo-elasticity, the alloy according to the invention does not actually exhibit such pseudo-elastic material behavior, at least not to any significant extent. The significantly improved resistance to cavitation in the alloy according to the invention is based on the special balance between formability and strength. This obviously has a positive effect on the cavitation resistance. In the case of the alloy according to the invention, the cavitation energy is introduced into the material and distributed to the grains via deformation. This progresses over a long duration of the cavitation test, but without this leading to disadvantageous accumulations of material, which would be the case with previously known alloys that are considered to be cavitation-resistant, which would be removed from the surface.

Ein mit der erfindungsgemäßen Legierung hergestelltes Produkt eignet sich vor dem Hintergrund seiner vorstehend beschriebenen Eigenschaften vor allem zum Herstellen von Zahnradpumpen oder Dampf- und Wasserarmaturenteilen, mithin Teilen, die einer erhöhten Kavitationsbeanspruchung an ihrer Oberfläche ausgesetzt sind. Selbstverständlich lassen sich auch andere an ihrer Oberfläche einer Kavitation durch vorbeiströmende Fluide ausgesetzte Produkte hieraus herstellen.Against the background of the properties described above, a product manufactured with the alloy according to the invention is particularly suitable for the production of gear pumps or parts for steam and water fittings, ie parts which are exposed to increased cavitation stress on their surface. It goes without saying that other products which are exposed to cavitation on their surface by fluids flowing past can also be produced from this.

Claims (7)

  1. Use of a Cu-Zn wrought alloy of the following composition (stated as wt. %): Cu: 80-85, Si: 2.0-6.0, Al: 0.55-2.0, Fe: max. 0.8, Ni: max. 0.5, Sn: max. 0.5, Mn: max. 0.1, Pb: max. 0.3,
    remainder Zn and unavoidable impurities
    as a product with increased cavitation resistance on the surface.
  2. Use of a Cu-Zn wrought alloy according to claim 1, characterised in that the alloy exhibits the following composition (stated as wt. %) Cu: 83-85, Si: 4.7-5.3, Al: 0.9-1.1, Fe: max. 0.3, Ni: max. 0.2, Sn: max. 0.3, Mn: max. 0.05, Pb: max. 0.1.
  3. Use of a Cu-Zn wrought alloy according to claim 1, characterised in that the alloy is hot-worked after a first casting.
  4. Use of a Cu-Zn wrought alloy according to any one of claims 1 to 3, characterised in that, for the manufacture of the product, the alloy is cast by extrusion pressing.
  5. Use of a Cu-Zn wrought alloy according to claim 4, characterised in that, after the hot-working step, no further thermal treatment is carried out on the product.
  6. Special brass alloy product, manufactured with the use of a Cu-Zn wrought alloy according to any one of claims 1 to 5, characterised in that the cavitation resistance of the product is characterised by the fact that, with a cavitation resistance test in accordance with ASTM G32-10 in distilled water at 20 °C as the test medium, with a spacing interval from the sonotrode tip to the sample of 0.5 mm, a frequency of 20 kHz, and an amplitude of 40 µm, with a test duration of 300 minutes, a loss of mass of 2.5 - 3.0 mg is not exceeded, and, in particular with a test duration of 500 minutes, a loss of mass of 7 - 8 mg is not exceeded.
  7. Special brass alloy product according to claim 6, characterised in that this exhibits an 0.2 elongation limit of between 450 and 260 N/mm2, in particular some 250 N/mm2, a tensile strength of between 530 and 600 N/mm2, an elongation after fracture of between 18 and 21%, and a Brinell hardness of 150 to 170 HBW, in particular some 160 HBW.
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DE202019101597.7U DE202019101597U1 (en) 2019-03-20 2019-03-20 Cu-Zn alloy
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JPH09143598A (en) * 1995-11-22 1997-06-03 Chuetsu Gokin Chuko Kk Brass alloy material for heating device
JP2002285264A (en) * 2001-03-27 2002-10-03 Ykk Corp Copper alloy for slide fastener
JP3964930B2 (en) * 2004-08-10 2007-08-22 三宝伸銅工業株式会社 Copper-base alloy castings with refined crystal grains
ES2297598T5 (en) * 2005-12-14 2016-06-03 Gebr. Kemper Gmbh + Co. Kg Metallwerke Use of a low migration copper alloy and parts of this alloy
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