EP3908682B1 - Pb-free cu-zn alloy - Google Patents
Pb-free cu-zn alloy Download PDFInfo
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- EP3908682B1 EP3908682B1 EP21716326.0A EP21716326A EP3908682B1 EP 3908682 B1 EP3908682 B1 EP 3908682B1 EP 21716326 A EP21716326 A EP 21716326A EP 3908682 B1 EP3908682 B1 EP 3908682B1
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- 229910001297 Zn alloy Inorganic materials 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims description 92
- 239000000956 alloy Substances 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 229910017518 Cu Zn Inorganic materials 0.000 claims description 12
- 229910017752 Cu-Zn Inorganic materials 0.000 claims description 11
- 229910017943 Cu—Zn Inorganic materials 0.000 claims description 11
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 235000012438 extruded product Nutrition 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000001050 lubricating effect Effects 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000011135 tin Substances 0.000 description 11
- 229910001369 Brass Inorganic materials 0.000 description 9
- 239000010951 brass Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 9
- 238000003825 pressing Methods 0.000 description 8
- 238000005242 forging Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- 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 Pb-free Cu-Zn alloy, particularly for making alloy products used under lubricated conditions. An alloy product made from such an alloy is also described.
- This alloy is also used to manufacture components used in hydraulics, such as distributor plates.
- This previously known alloy has the following composition (data in % by weight): Cu: 57.0-59.0%, Mn: 1.5-3.0%, Al: 1.3-2.3%, Si : 0.3 - 1.3%, remainder zinc plus unavoidable impurities.
- Admissible admixtures are tolerated (in percent by weight): Ni: max. 1.0%, Fe: max. 1.0%, Sn: max. 0.4%, Pb: 0.2 - 0.8 %.
- this previously known alloy contains Pb. This element is responsible for machinability and, due to its incorporation in tribological layers the running-in behavior as well as friction and wear in sliding applications.
- the special brass alloy CW713R is characterized by versatile application properties, such as high wear and cavitation resistance, compatibility with lubricants and sufficient mechanical properties, especially with regard to the strength and toughness of the alloy product. These also include good machinability.
- the element Pb is introduced into brass alloys to achieve the desired machinability.
- DE 10 2005 017 574 A1 describes a wear-resistant brass alloy for synchronizer rings with an optional lead content.
- the composition (in percent by weight) is 57.5 - 59% copper, 2 - 3.5% manganese, 1 - 3% aluminum, 0.9 - 1.5% silicon, 0.15 - 0.4 % iron, 0 - 1% lead, 0 - 1% nickel, 0 - 0.5% tin and balance zinc.
- WO 2014/152619 A1 discloses a brass alloy for turbochargers with the following composition, optionally containing lead (data in % by weight): 57-60% copper, 1.5-3.0% manganese, 1.3-2.3% aluminum, 0.5 - 2.0% silicon, 0 - 1% nickel, 0 - 1% iron, 0 - 0.4% tin, 0 - 0.1% lead and the balance zinc.
- JP S56-127741 A a brass alloy with the following composition (in % by weight): 54 - 66% copper, 1.0 - 5.0% manganese, 1.0 - 5.0% aluminum, 0.2 - 1.5% silicon , 0.5 - 4.0% nickel, 0.1 - 2.0% iron, 0.2 - 2.0% tin and the balance zinc.
- the object of the invention is to propose a Pb-free Cu—Zn alloy that is fundamentally suitable for an application or use for which the alloy CuZn37Mn3Al2PbSi described above for the prior art was also suitable. It would be desirable if the mechanical strength properties were even improved compared to this previously known special brass alloy, but without having to accept losses in terms of cold and hot workability and machinability.
- Unavoidable impurities in the alloy are permitted at 0.05% by weight per element, the sum of the unavoidable impurities not exceeding 0.15% by weight.
- This alloy is characterized above all by the selection of the alloying elements Ni, Fe and Sn, as well as by the claimed content of these elements in the alloy composition in relation to the other alloying elements, above all Mn, Al and Si.
- This balanced alloy composition ensures particularly good properties of the alloy product in terms of cold and hot workability, machinability, strength and wear resistance, the latter especially under lubricated conditions.
- Bi is used as a Pb substitute in other special brass alloys, but the alloy according to the invention does not use Bi.
- the previously known alloy CuZn37Mn3Al2PbSi although it has good hot workability
- the subject matter of the claimed alloy not only has particularly good hot workability, but also good cold workability. The latter was not the case with the previously known alloy.
- the strength values achievable with this alloy and the surprisingly significantly better cavitation resistance compared to comparison alloys were not foreseeable for the people involved in the development of this alloy.
- the alloy products forged from the alloy according to the invention have a 0.2% yield strength between 330 and 350 MPa, which is significantly higher than was usual with forgings of the alloy CuZn37Mn3Al2PbSi (values of 230 to 300 MPa).
- the tensile strength of alloy products made from the alloy according to the invention is 600 to 640 MPa. In the case of the previously known alloy CuZn37Mn3Al2PbSi, the tensile strength values are usually between 590 and 670 MPa. Slightly higher tensile strength values can also be achieved with special treatments.
- the special properties of an alloy product made from this alloy are based on the fact that the Si content is preferably not less than the Ni content. Furthermore, the Sn content of the alloy is preferably adjusted in such a way that it is at most only 50% of the Ni content or only at most 50% of the Si content. The Ni content is preferably not less than the Si content, deviations of up to 0.075% being tolerated.
- the Fe content also plays a role in interaction with the other elements. Preferably, the Fe content is less than the Ni content by about 0.05% to 0.1% by weight.
- Figures 1a, 1b show micrographs of sample 1 in the pressed state from the start of pressing ( Figure 1a along the direction of pressing; Figure 1b perpendicular to the pressing direction).
- Figures 2a, 2b show corresponding microstructure images from the pressing end.
- the samples cut from the pressed rods were thermally relaxed for three hours at 360° C.
- an ⁇ -mixed crystal phase was formed in the structure, resulting in a ⁇ -mixed crystal-dominated structure with an ⁇ -mixed crystal component of about 14%.
- the proportion of intermetallic phases is around 3%.
- Figures 3a, 3b show micrographs of sample 2 after the stress-relief annealing described above.
- the intermetallic phases are denoted by IMP.
- the hardness HBW was measured as HBW 2.5/62.5.
- the microstructure of the comparative sample CW713R in the pressed state is ⁇ -phase dominated with a proportion of ⁇ -mixed crystal phase of about 10%.
- the Pb contained in this alloy has a grain-refining effect and serves as a chip breaker.
- figure 4 shows a micrograph of sample CW713R in the pressed state and after an annealing treatment, corresponding to that of sample 2.
- the proportion of ⁇ -mixed crystal phase is about 40 - 45%.
- Pipes were also made from the alloy of Sample 2 and that of the comparative alloy (CW713R) by extrusion. Sections were cut from the tubes which were then machined by turning to compare the machinability of the two alloys. In the course of this turning, rings were created. Interestingly, the machinability of the ring made from the alloy according to sample 2 is at least as good as the machinability of the ring made from the comparison alloy. This is remarkable since the sample according to the invention (sample 2), unlike the alloy composition of the comparative sample, does not contain any Pb because the alloying element Pb in the comparative sample is held responsible for the good machinability of this alloy.
- the alloy product of the present invention can be drawn directly. Nevertheless, an intermediate anneal before drawing is preferred in order to achieve as stress-free an alloy product as possible. Furthermore, additional investigations with the alloy compositions of samples 1 and 2 for differently adjusted material states have shown that the tensile strength R m , the 0.2% yield strength, the elongation at break and the hardness HB are also opposite for directly drawn specimens or specimens drawn after an intermediate annealing step Semi-finished product made from the comparison alloy CW713R is significantly increased. The same was the case for both variants of the samples for a material condition after a final stress-relief annealing. This was found in forgings made from the alloy as well as in extruded semi-finished products that were drawn (stretched) after pressing. In both cases, subsequent annealing can be helpful in relieving stresses contained in the respective workpiece.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Forging (AREA)
- Sliding-Contact Bearings (AREA)
- Mechanical Operated Clutches (AREA)
Description
Die Erfindung betrifft eine Pb-freie Cu-Zn-Legierung, insbesondere zum Herstellen von unter geschmierten Bedingungen eingesetzten Legierungsprodukten. Beschrieben ist des Weiteren ein aus einer solchen Legierung hergestelltes Legierungsprodukt.The invention relates to a Pb-free Cu-Zn alloy, particularly for making alloy products used under lubricated conditions. An alloy product made from such an alloy is also described.
Das im Werkstoff-Datenblatt (Stand 2005) des Deutschen Kupferinstituts beschriebene Sondermessing CuZn37Mn3Al2PbSi (CW713R) ist eine seit vielen Jahren in großem Umfange eingesetzte Legierung, die sich durch einen hohen Verschleißwiderstand und eine gute Warmumformbarkeit auszeichnet. Dieser Werkstoff weist hohe Festigkeitswerte und eine mittlere Spanbarkeit auf und hat eine gute Korrosionsbeständigkeit. Aus diesem Grunde wird diese Legierung für Konstruktionsteile im Maschinenbau, für Synchronringe und Ventilführungsrohre im Automobilbau sowie für eine Reihe von Gleitlagerelementen und Warmpressteilen eingesetzt. Dieses bedeutet, dass aus dieser Legierung hergestellte Legierungsprodukte unter geschmierten Bedingungen eingesetzt werden. Mögliche Anwendung betreffen das permanente Eintauchen in Öl oder die Zuführung von Schmierstoff durch dafür vorgesehene Kanal- und Nutsysteme. Synchronringe befinden sich in einer Ölumgebung. Gleiches kann für Gleitlagerelemente gelten, die jedoch auch nur ölgeschmiert sein können. Eingesetzt wird diese Legierung auch zum Herstellen von Bauteilen, die in der Hydraulik verwendet werden, wie beispielsweise Verteilerplatten. Diese vorbekannte Legierung weist folgende Zusammensetzung auf (Angaben in Gew.-%): Cu: 57,0 - 59,0 %, Mn: 1,5 - 3,0 %, Al: 1,3 - 2,3 %, Si: 0,3 - 1,3 %, Rest Zink nebst unvermeidbaren Verunreinigungen. Als zulässige Beimengungen werden geduldet (Angaben in Gew.-%): Ni: max. 1,0 %, Fe: max. 1,0 %, Sn: max. 0,4 %, Pb: 0,2 - 0,8 %.The special brass CuZn37Mn3Al2PbSi (CW713R) described in the material data sheet (status 2005) of the German Copper Institute is an alloy that has been used extensively for many years and is characterized by high wear resistance and good hot workability. This material has high strength values and average machinability and has good corrosion resistance. For this reason, this alloy is used for structural parts in mechanical engineering, for synchronizer rings and valve guide tubes in automobile construction, as well as for a range of plain bearing elements and hot-pressed parts. This means that alloy products made from this alloy are used under lubricated conditions. Possible applications relate to permanent immersion in oil or the supply of lubricant through channel and groove systems provided for this purpose. Synchronizer rings are in an oil environment. The same can apply to plain bearing elements, which can also only be lubricated with oil. This alloy is also used to manufacture components used in hydraulics, such as distributor plates. This previously known alloy has the following composition (data in % by weight): Cu: 57.0-59.0%, Mn: 1.5-3.0%, Al: 1.3-2.3%, Si : 0.3 - 1.3%, remainder zinc plus unavoidable impurities. Admissible admixtures are tolerated (in percent by weight): Ni: max. 1.0%, Fe: max. 1.0%, Sn: max. 0.4%, Pb: 0.2 - 0.8 %.
Wie sich aus der bereits eingangs wiedergegebenen Werkstoffbezeichnung ergibt, enthält diese vorbekannte Legierung Pb. Dieses Element ist für die Zerspanbarkeit verantwortlich und beeinflusst aufgrund dessen Einbaus in tribologische Schichten das Einlaufverhalten sowie Reibung und Verschleiß bei Gleitanwendungen.As can be seen from the material description given above, this previously known alloy contains Pb. This element is responsible for machinability and, due to its incorporation in tribological layers the running-in behavior as well as friction and wear in sliding applications.
Die Sondermessinglegierung CW713R zeichnet sich durch vielseitige Anwendungseigenschaften aus, wie beispielsweise einen hohen Verschleiß- und Kavitationswiderstand, eine Schmierstoffverträglichkeit und hinreichend mechanische Eigenschaften, insbesondere im Hinblick auf die Festigkeit und Zähigkeit des Legierungsprodukts. Zu diesen zählt auch eine gute Zerspanbarkeit. Das Element Pb wird zum Erzielen der gewünschten Zerspanbarkeit in Messinglegierungen eingebracht.The special brass alloy CW713R is characterized by versatile application properties, such as high wear and cavitation resistance, compatibility with lubricants and sufficient mechanical properties, especially with regard to the strength and toughness of the alloy product. These also include good machinability. The element Pb is introduced into brass alloys to achieve the desired machinability.
Aus gesundheitlichen Aspekten sowie aufgrund von Umweltgesichtspunkten ist man in jüngerer Zeit bemüht, Messinglegierungen bleifrei auszulegen. Dabei ist man bemüht, wenn möglich, nicht auf die durch das Element Pb in der Legierung bewirkten Eigenschaften verzichten zu müssen.For health reasons and because of environmental aspects, efforts have recently been made to design brass alloys without lead. Whenever possible, efforts are made not to have to do without the properties brought about by the element Pb in the alloy.
Für Gleitanwendungen nennt
Ausgehend von diesem diskutierten Stand der Technik liegt der Erfindung die Aufgabe zugrunde, eine Pb-freie Cu-Zn-Legierung vorzuschlagen, die sich grundsätzlich für einen Einsatzzweck bzw. eine Verwendung eignet, für die auch die vorstehend zum Stand der Technik beschriebene Legierung CuZn37Mn3Al2PbSi geeignet war. Dabei wäre es wünschenswert, wenn die mechanischen Festigkeitseigenschaften gegenüber dieser vorbekannten Sondermessinglegierung sogar noch verbessert wären, ohne jedoch Einbußen hinsichtlich der Kalt- und Warmumformbarkeit und der Zerspanbarkeit hinnehmen zu müssen.Proceeding from this discussed prior art, the object of the invention is to propose a Pb-free Cu—Zn alloy that is fundamentally suitable for an application or use for which the alloy CuZn37Mn3Al2PbSi described above for the prior art was also suitable. It would be desirable if the mechanical strength properties were even improved compared to this previously known special brass alloy, but without having to accept losses in terms of cold and hot workability and machinability.
Gelöst wird diese Aufgabe durch eine Pb-freie Cu-Zn-Legierung mit folgender Zusammensetzung (Angaben in Gew.-%):
- Cu: 57 - 59%,
- Mn: 1,7 - 2,7 %,
- Al: 1,3 - 2,2 %,
- Si: 0,4 - 1,0 %,
- Ni: 0,4 - 0,85 %,
- Fe: 0,3 - 0,7 %,
- Sn: 0,15 - 0,4 %,
- Rest Zn nebst unvermeidbaren Verunreinigungen mit 0,05 Gew.-% je Element, wobei die Summe der unvermeidbaren Verunreinigungen 0,15 Gew.-% nicht überschreitet.
- Cu: 57 - 59%,
- Mn: 1.7 - 2.7%,
- Al: 1.3 - 2.2%,
- Si: 0.4 - 1.0%,
- Ni: 0.4 - 0.85%,
- Fe: 0.3 - 0.7%,
- Sn: 0.15 - 0.4%,
- Balance Zn plus unavoidable impurities with 0.05% by weight per element, the sum of the unavoidable impurities not exceeding 0.15% by weight.
Unvermeidbare Verunreinigungen in der Legierung sind zugelassen mit 0,05 Gew.-% je Element, wobei die Summe der unvermeidbaren Verunreinigungen 0,15 Gew.-% nicht überschreitet.Unavoidable impurities in the alloy are permitted at 0.05% by weight per element, the sum of the unavoidable impurities not exceeding 0.15% by weight.
Diese Legierung zeichnet sich vor allem durch die Auswahl der Legierungselemente Ni, Fe und Sn aus, ebenso wie durch die beanspruchten Gehalte dieser Elemente an der Legierungszusammensetzung im Verhältnis zu den weiteren Legierungselementen vor allem Mn, Al und Si. Diese ausgewogene Legierungszusammensetzung gewährleistet besonders gute Eigenschaften des Legierungsproduktes in Bezug auf eine Kalt- und Warmumformbarkeit, die Zerspanbarkeit, die Festigkeit und den Verschleißwiderstand, letzterer vor allem unter geschmierten Bedingungen. Dieses Ergebnis ist überraschend, da als Pb-Ersatz in anderen Sondermessinglegierungen Bi eingesetzt wird, die erfindungsgemäße Legierung jedoch Bi nicht verwendet. Während auch die vorbekannte Legierung CuZn37Mn3Al2PbSi zwar eine gute Warmumformbarkeit aufweist, ist beim Gegenstand der beanspruchten Legierung nicht nur eine besonders gute Warmumformbarkeit gegeben, sondern auch eine gute Kaltumformbarkeit. Letzteres war bei der vorbekannten Legierung nicht der Fall. Von Interesse bei dieser Legierung ist, dass sich diese eignet, um Schmiedestücke herzustellen. Werden die Schmiedestücke einem anschließenden Entspannungsglühen unterworfen, wobei dieses in einem Temperaturbereich zwischen 300° C und 450° C durchgeführt wird, kann durch diese Maßnahme der Anteil an eingelagerten α-Mischkristallen auf 10 - 15 % erhöht werden. Um die gewünschten Eigenschaften zu erreichen, ist ein Glühen in einem Temperaturbereich bereits von 350 bis 380° C in vielen Fällen bereits ausreichend. Dieser erhöhte Anteil an α-Mischkristallen begründet die verbesserte Kaltumformbarkeit. Ohne einen solchen Glühschritt enthält das Legierungsgefüge einen Anteil von α-Mischkristallen von weniger als 3 - 5 %. Dieselben Vorteile eines Entspannungsglühens stellen sich auch bei stranggepressten Produkten ein, wobei ebenfalls ein Gefüge mit α-Mischkristallanteil von 10 - 15 % durch die genannte thermische Behandlung erzielt werden kann.This alloy is characterized above all by the selection of the alloying elements Ni, Fe and Sn, as well as by the claimed content of these elements in the alloy composition in relation to the other alloying elements, above all Mn, Al and Si. This balanced alloy composition ensures particularly good properties of the alloy product in terms of cold and hot workability, machinability, strength and wear resistance, the latter especially under lubricated conditions. This result is surprising since Bi is used as a Pb substitute in other special brass alloys, but the alloy according to the invention does not use Bi. While the previously known alloy CuZn37Mn3Al2PbSi although it has good hot workability, the subject matter of the claimed alloy not only has particularly good hot workability, but also good cold workability. The latter was not the case with the previously known alloy. Of interest with this alloy is that it is suitable for making forgings. If the forgings are then subjected to stress-relief annealing, which is carried out in a temperature range between 300° C. and 450° C., this measure can increase the proportion of embedded α-solid solution to 10-15%. In order to achieve the desired properties, annealing in a temperature range of 350 to 380°C is sufficient in many cases. This increased proportion of α-mixed crystals is the reason for the improved cold workability. Without such an annealing step, the alloy structure contains less than 3-5% α-mixed crystals. The same advantages of stress-relief annealing also apply to extruded products, whereby a structure with an α-mixed crystal content of 10 - 15% can also be achieved through the thermal treatment mentioned.
Nicht vorhersehbar für die an der Entwicklung dieser Legierung beteiligten Personen waren die mit dieser Legierung erzielbaren Festigkeitswerte und die gegenüber Vergleichslegierungen überraschend deutlich bessere Kavitationsbeständigkeit. Die aus der erfindungsgemäßen Legierung durch Schmieden hergestellten Legierungsprodukte weisen eine 0,2 %-Dehngrenze zwischen 330 und 350 MPa auf, was deutlich mehr ist als mit Schmiedestücken der Legierung CuZn37Mn3Al2PbSi üblich war (Werte von 230 bis 300 MPa). Die Zugfestigkeit von aus der erfindungsgemäßen Legierung hergestellten Legierungsprodukten beträgt 600 bis 640 MPa. Bei der vorbekannten Legierung CuZn37Mn3Al2PbSi liegen die Zugfestigkeitswerte üblicherweise zwischen 590 bis 670 MPa. Mit besonderen Behandlungen können auch etwas höhere Zugfestigkeitswerte erzielt werden.The strength values achievable with this alloy and the surprisingly significantly better cavitation resistance compared to comparison alloys were not foreseeable for the people involved in the development of this alloy. The alloy products forged from the alloy according to the invention have a 0.2% yield strength between 330 and 350 MPa, which is significantly higher than was usual with forgings of the alloy CuZn37Mn3Al2PbSi (values of 230 to 300 MPa). The tensile strength of alloy products made from the alloy according to the invention is 600 to 640 MPa. In the case of the previously known alloy CuZn37Mn3Al2PbSi, the tensile strength values are usually between 590 and 670 MPa. Slightly higher tensile strength values can also be achieved with special treatments.
Untersuchungen haben gezeigt, dass das Zusammenspiel der Elemente Ni, Fe und Sn untereinander, aber auch mit Mn, Al und Si und im Zusammenhang mit einer Ausbildung von intermetallischen Phasen zu besonders guten Ergebnissen führt, wenn der Mn-Gehalt auf 1,9 - 2,6 %, der Al-Gehalt auf 1,4 - 2,1 %, der Ni-Gehalt von 0,45 - 0,75 % und der Fe-Gehalt von 0,3 - 0,6 % kontrolliert wird. Als besonders geeignet hat sich für die gewünschten Zwecke mit einer besonderen Ausprägung aus guter Kalt- und Warmumformbarkeit, Zerspanbarkeit, Festigkeit und Verschleißwiderstand ergeben, wenn die Legierungszusammensetzung wie folgt gewählt ist (Angaben in Gew.-%):
- Cu: 57,5 - 58,5 %,
- Mn: 2,0 - 2,5 %,
- Al: 1,5-2,0 %,
- Si: 0,50 - 0,70 %,
- Ni: 0,50 - 0,70 %,
- Fe: 0,5 - 0,55 %,
- Sn: 0,20 - 0,35 %.
- Cu: 57.5 - 58.5%,
- Mn: 2.0 - 2.5%,
- Al: 1.5-2.0%,
- Si: 0.50 - 0.70%,
- Ni: 0.50 - 0.70%,
- Fe: 0.5 - 0.55%,
- Sn: 0.20 - 0.35%.
Die besonderen Eigenschaften eines aus dieser Legierung hergestellten Legierungsproduktes liegen darin begründet, dass vorzugsweise der Si-Gehalt nicht kleiner als der Ni-Gehalt ist. Ferner ist der Sn-Gehalt der Legierung vorzugsweise so abgestimmt, dass dieser maximal nur 50 % des Ni-Gehaltes bzw. nur maximal 50 % des Si-Gehaltes beträgt. Vorzugsweise ist der Ni-Gehalt nicht kleiner als der Si-Gehalt, wobei Abweichungen von bis zu 0,075 % toleriert werden. Auch der Fe-Gehalt spielt im Zusammenspiel mit den anderen Elementen eine Rolle. Vorzugsweise ist der Fe-Gehalt um etwa 0,05 % bis 0,1 Gew.-% geringer als der Ni-Gehalt.The special properties of an alloy product made from this alloy are based on the fact that the Si content is preferably not less than the Ni content. Furthermore, the Sn content of the alloy is preferably adjusted in such a way that it is at most only 50% of the Ni content or only at most 50% of the Si content. The Ni content is preferably not less than the Si content, deviations of up to 0.075% being tolerated. The Fe content also plays a role in interaction with the other elements. Preferably, the Fe content is less than the Ni content by about 0.05% to 0.1% by weight.
Die vorstehend beschriebenen besonderen Eigenschaften eines aus dieser Legierung hergestellten Legierungsproduktes ergeben sich sowohl bei Schmiedeprodukten als auch bei stranggepressten Produkten.The special properties described above of an alloy product made from this alloy arise both in the case of forged products and in the case of extruded products.
Etliche Legierungen aus der erfindungsgemäßen Legierung wurden gegossen, anschließend stranggepresst und Teile davon einem nachgeschalteten Schmiedeschritt unterworfen. Parallel wurde eine Vergleichsprobe des Werkstoffes CW713R in derselben Weise hergestellt. Nachstehend sind beispielhaft zwei erfindungsgemäße Proben bezüglich ihrer Legierungszusammensetzung - die Proben 1 und 2 - und die Zusammensetzung einer Vergleichsprobe (CW713R) wiedergegeben:
Nach dem Guss (Stranguss) wurden Blöcke gesägt und anschließend aus den Blöcken Stangen mit einem Durchmesser von 50 mm und einer Länge von 20 m gepresst. Die Strangpresstemperatur der untersuchten Probenreihe lag zwischen 685° C und 710° C. Die Strangpresstemperatur der beschriebenen Proben betrug etwa 700° C. Das sich einstellende Gefüge ist über die gepresste Stange sehr homogen, und zwar sowohl in Längsrichtung als auch in Querrichtung der gepressten Stange über ihre gesamte Länge hinweg. Einzig zu beobachten ist, dass die Korngröße vom Pressanfang zum Pressende hin etwas abnimmt, wie dieses üblicherweise beim Strangpressen zu beobachten ist. Das Gefüge besteht so gut wie ausschließlich aus β-Phase mit eingelagerten intermetallischen Verbindungen (Mischsiliziden, die in Pressrichtung eingeregelt sind). Der Anteil der intermetallischen Verbindungen liegt bei etwa 3 - 4 %.After casting (continuous casting), blocks were sawn and then bars with a diameter of 50 mm and a length of 20 m were pressed from the blocks. The extrusion temperature of the examined series of samples was between 685°C and 710°C. The extrusion temperature of the described samples was around 700°C. The resulting structure is very homogeneous over the pressed bar, both in the longitudinal direction and in the transverse direction of the pressed bar over its entire length. The only thing that can be observed is that the grain size decreases somewhat from the start of pressing to the end of pressing, as is usually observed in extrusion. The structure consists almost exclusively of β-phase with intercalated intermetallic compounds (mixed silicides, which are adjusted in the pressing direction). The proportion of intermetallic compounds is around 3 - 4%.
Die vorgenannten Gefügeparameter und die Festigkeitswerte dieser Proben sind in nachstehender Tabelle wiedergegeben:
Mit IMP sind die intermetallischen Phasen bezeichnet. Die Härte HBW wurde als HBW 2,5/62,5 gemessen.The intermetallic phases are denoted by IMP. The hardness HBW was measured as HBW 2.5/62.5.
Das Gefüge der Vergleichsprobe CW713R im Presszustand ist β-Phasendominiert mit einem Anteil an α-Mischkristallphase von etwa 10 %. Das in dieser Legierung enthaltene Pb wirkt kornfeinend und dient als Spanbrecher.
Aus den gepressten Stangen wurden in einem nachfolgenden Schritt zum Herstellen von Verteilerplatten Stutzen als Schmiedevorprodukte abgetrennt und diese warm geschmiedet. Geschmiedet wurden die Schmiedestücke bei der Probenreihe bei Temperaturen zwischen 635° C und 670° C. Die Probe 2 und die Vergleichsprobe sind bei etwa 650° C geschmiedet worden. Das sich einstellende Mikrogefüge eines solchermaßen geschmiedeten Vorproduktes für eine Verteilerplatte für eine hydraulische Anwendung ist in
Diese Abbildungen verdeutlichen das über den Durchmesser des geschmiedeten Halbzeuges sehr homogene Gefüge. Dieses besteht so gut wie ausschließlich aus β-Phase mit eingelagerten intermetallischen Phasen von gut 3 %.These images illustrate the very homogeneous structure across the diameter of the forged semi-finished product. This consists almost exclusively of β-phase with incorporated intermetallic phases of a good 3%.
In einem nachfolgenden Schritt wurden Proben dieser Art geglüht, und zwar für drei Stunden bei 360° C. Im Zuge dieses Glühprozesses bildete sich ein Anteil an α-Phase von etwa 12 %. Der Anteil an intermetallischen Phasen erhöhte sich auf etwa 3,7 %. Das Gefüge des geglühten Halbzeuges zum Herstellen einer Verteilerplatte für hydraulische Anwendungen ist in
In der nachstehenden Tabelle sind die Gefügeparameter und die mechanischen Festigkeitswerte zu diesen Proben wiedergegeben:
Wird die geschmiedete Vergleichsprobe (CW713R) einem Glühprozess unterzogen, wie vorstehend beschrieben, erhöht sich der Anteil an α-Phase deutlich, und zwar auf bis zu etwa 40 %.When the comparative forged sample (CW713R) is subjected to an annealing process as described above, the proportion of α-phase increases significantly, up to about 40%.
Aus der Legierung gemäß Probe 2 und derjenigen der Vergleichslegierung (CW713R) wurden zudem Rohre durch Strangpressen hergestellt. Von den Rohren wurden Abschnitte abgetrennt, die anschließend zum Vergleichen der Zerspanbarkeit der beiden Legierungen zerspanend durch Drehen bearbeitet wurden. Im Zuge dieser Drehbearbeitung wurden Ringe erstellt. Die Zerspanbarkeit des aus der Legierung gemäß Probe 2 hergestellten Ringes ist interessanterweise mindestens so gut wie die Zerspanbarkeit des Ringes, hergestellt aus der Vergleichslegierung. Dieses ist bemerkenswert, da die erfindungsgemäße Probe (Probe 2) im Unterschied zu der Legierungszusammensetzung der Vergleichsprobe kein Pb enthält, und zwar deswegen, da das Legierungselement Pb bei der Vergleichsprobe für die gute Zerspanbarkeit dieser Legierung verantwortlich gemacht wird.Pipes were also made from the alloy of Sample 2 and that of the comparative alloy (CW713R) by extrusion. Sections were cut from the tubes which were then machined by turning to compare the machinability of the two alloys. In the course of this turning, rings were created. Interestingly, the machinability of the ring made from the alloy according to sample 2 is at least as good as the machinability of the ring made from the comparison alloy. This is remarkable since the sample according to the invention (sample 2), unlike the alloy composition of the comparative sample, does not contain any Pb because the alloying element Pb in the comparative sample is held responsible for the good machinability of this alloy.
Das erfindungsgemäße Legierungsprodukt kann direkt gezogen werden. Dennoch wird ein Zwischenglühen vor dem Ziehen bevorzugt, um ein möglichst spannungsfreies Legierungsprodukt zu erzielen. Ferner haben zusätzliche Untersuchungen mit den Legierungszusammensetzungen der Proben 1 und 2 für unterschiedlich eingestellte Werkstoffzustände ergeben, dass die Zugfestigkeit Rm, die 0,2%-Dehngrenze, die Bruchdehnung und die Härte HB auch für direkt gezogene oder für nach einem Zwischenglühschritt gezogene Probestücke gegenüber Halbzeug aus der Vergleichslegierung CW713R deutlich gesteigert ist. Entsprechendes ergab sich bei beiden Varianten der Proben für einen Werkstoffzustand nach einem abschließenden Entspannungsglühen. Festgestellt wurde dieses an aus der Legierung hergestellten Schmiedestücken ebenso wie an stranggepressten Halbzeugen, die nach dem Pressen gezogen (gereckt) worden sind. In beiden Fällen kann ein anschließendes Glühen zum Abbau von in dem jeweiligen Werkstück enthaltenen Spannungen hilfreich sein.The alloy product of the present invention can be drawn directly. Nevertheless, an intermediate anneal before drawing is preferred in order to achieve as stress-free an alloy product as possible. Furthermore, additional investigations with the alloy compositions of samples 1 and 2 for differently adjusted material states have shown that the tensile strength R m , the 0.2% yield strength, the elongation at break and the hardness HB are also opposite for directly drawn specimens or specimens drawn after an intermediate annealing step Semi-finished product made from the comparison alloy CW713R is significantly increased. The same was the case for both variants of the samples for a material condition after a final stress-relief annealing. This was found in forgings made from the alloy as well as in extruded semi-finished products that were drawn (stretched) after pressing. In both cases, subsequent annealing can be helpful in relieving stresses contained in the respective workpiece.
Des Weiteren wurden Kavitationsuntersuchungen mit der geschmiedeten und geglühten Probe 2 unternommen. Hierzu wurden Oberflächen von aus der Probe 2 gewonnenen Testkörpern zunächst mit einer Körnung von 1000 Mesh geschliffen und an diesen dann ein Kavitationstest gemäß ASTM G32 in destilliertem Wasser durchgeführt. Dabei hat sich gezeigt, dass der hoch eingeschätzte Kavitationswiderstand der Vergleichslegierung CW713R nochmals deutlich gesteigert werden konnte. Diese Verringerung der Kavitationsneigung in Wasser deutet darauf hin, dass Legierungsprodukte mit der erfindungsgemäßen Zusammensetzung auch bei einer hohen dynamischen Belastung in einer Schmierstoffumgebung, wie sie beispielsweise in Zylinderbuchsen von Axialkolbenpumpen auftritt, eine verbesserte Standfestigkeit aufweisen. Derartige Zylinderbuchsen sind aus stranggepressten und anschließend kaltgezogenen (gereckten) Halbzeugen hergestellt. Daher sind Zylinderbuchsen für derartige Anwendungen für die Herstellung aus erfindungsgemäßen Legierung besonders geeignet.Furthermore, cavitation investigations were undertaken with the forged and annealed sample 2. For this purpose, surfaces of test specimens obtained from sample 2 were first ground with a grain size of 1000 mesh and a cavitation test was then carried out on them in accordance with ASTM G32 in distilled water. It has been shown that the highly estimated cavitation resistance of the comparison alloy CW713R could be significantly increased again. This reduction in the cavitation tendency in water indicates that alloy products with the composition according to the invention have improved durability even under high dynamic loading in a lubricant environment, such as occurs, for example, in cylinder liners of axial piston pumps. Such cylinder liners are made from extruded and then cold-drawn (stretched) semi-finished products. Cylinder liners for such applications are therefore particularly suitable for production from the alloy according to the invention.
Claims (14)
- Pb-free Cu-Zn alloy for producing alloy products used under lubric conditions with the following composition (values in % by weight):Cu: 57-59 %Mn: 1.7 - 2.7 %Al: 1.3 - 2.2 %Si: 0.4 - 1.0 %Ni: 0.4 - 0.85 %Fe: 0.3 - 0.7 %Sn: 0.15 - 0.4 %the remainder being Zn as well as unavoidable impurities with 0.05 % by weight per element, wherein the sum total of the unavoidable impurities does not exceed 0.15 % by weight.
- Pb-free Cu-Zn alloy according to claim 1, characterised by:Mn: 1.9 - 2.6 %Al: 1.4 - 2.1 %Ni: 0.45 - 0.75 %Fe: 0.3 - 0.6 %
- Pb-free Cu-Zn alloy according to claim 2, characterised by:Cu: 57.5 - 58.5 %Mn: 2.0 - 2.5 %Al: 1.5 - 2.0 %Si: 0.50 - 0.70 %Ni: 0.50 - 0.70 %Fe: 0.35 - 0.55 %Sn: 0.20 - 0.35 %
- Pb-free Cu-Zn alloy according to any one of claims 1 to 3, characterised in that the Si content is not smaller than the Ni content.
- Pb-free Cu-Zn alloy according to any one of claims 1 to 4, characterised in that the Sn content amounts to a maximum of 50% of the Ni content and a maximum of 50% of the Si content.
- Pb-free Cu-Zn alloy according to any one of claims 1 to 5, characterised in that the Fe content is less by 0.05% to 0.1% than that of the Ni content.
- Lubricating product, produced from a Pb-free Cu-Zn alloy according to any one of claims 1 to 6, characterised in that the lubricating product produced from the alloy comprises a β structure and an embedded α-mixed crystal proportion of less than 5% and a proportion of intermetallic phases of 2.5 - 4.5 %.
- Extruded product, produced from a Pb-free Cu-Zn alloy according to any one of claims 1 to 6, characterised in that the extruded product produced from the alloy comprises a β structure and an embedded α-mixed crystal proportion of less than 5% and a proportion of intermetallic phases of 2.5 - 4.5 %.
- Alloy product according to any one of claims 7 or 8, characterised in that the alloy product is thermically stress-relieved by an annealing process, and, by means of this process the proportion of the α-mixed crystals is raised to 10 - 30%, in particular to 10 - 15%, and a proportion of intermetallic phases of 3 - 5% is formed.
- Alloy product according to any one of claims 7 to 9, characterised in that the hardness of the alloy product amounts to 160 - 190 HBW 2.5/62.5, in particular 170 - 185 HBW 2.5/62.5.
- Alloy product according to any one of claims 7 to 10, characterised in that the alloy product exhibits a 0.2% elongation limit of between 300 and 400 MPa, in particular between 300 and 350 MPa, and a tensile strength of 600 - 700 MPa, in particular of 600 - 640 MPa.
- Alloy product according to claim 7 and 11, characterised in that the alloy product exhibits an elongation after fracture of between 10 - 30%, in particular 13 - 20%.
- Alloy product according to claim 8 and 11, characterised in that the alloy product exhibits an elongation after fracture of between 10 - 16%.
- Alloy product according to any one of claims 7 to 13, characterised in that the electrical conductivity of the alloy product amounts to between 9 and 11 MS/m, in particular between 9.3 and 10.0 MS/m.
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