Copper-zinc-nickel-molybdenum casting alloy, casting made therefrom and method for producing such a copper-zinc-nickel-molybdenum casting alloy

Abstract

The invention relates to a copper-zinc-nickel-molybdenum casting alloy, a casting made therefrom, and a method for producing such a casting alloy.

Description

[0001] The invention relates to a copper-zinc-nickel-molybdenum casting alloy, a casting made therefrom, and a method for producing such a copper-zinc-nickel-molybdenum casting alloy.

[0002] Copper-zinc-nickel alloys, also known as nickel silver, are known in a variety of ways from the state of the art and are used, for example, in the manufacture of precision mechanical components for bearing and gear technology as well as optics.

[0003] To improve manufacturability and machinability, such copper-zinc-nickel alloys often contain lead, which, as a toxic heavy metal, is increasingly undesirable as an alloying element.

[0004] To replace lead, the addition of sulfur has been discussed, as it can act as a chip breaker and thus facilitate machining. For example, German patent DE 10 2020 106 999 A1 addresses the fact that the addition of sulfur can improve castability in copper-tin continuous casting alloys, since the copper and zinc sulfides formed by the sulfur accumulate in otherwise typically present micropores and seal these cavities. Furthermore, it has been discussed that copper sulfide can have a positive effect on the tribological properties.

[0005] However, the addition of sulfur creates a further conflict of objectives in zinc-containing alloys, as the zinc sulfide that forms can reduce strength and, due to the higher hardness, increase tool wear during machining.

[0006] The present invention is based on the objective of providing a copper-zinc casting alloy that can be produced and cast well and economically, and which is easily machinable after casting and has good tribological properties.

[0007] This problem is solved according to the invention by a casting alloy having the features of claim 1. This is a casting alloy consisting of: - 17.0 - 30.0 wt.%, preferably 20.0 - 27.0 wt.%, zinc - 10.0 - 20.0 wt.%, preferably 12.0 - 18.0 wt.%, nickel, - 2.1 - 3.3 wt% molybdenum, - 1.4 - 2.4 wt% sulfur, - possibly up to 0.1 wt% phosphorus - Residual copper and unavoidable impurities, wherein, based on weight percent, the ratio of sulfur to molybdenum in the alloy is greater than 0.6, in particular greater than 0.65, and further in particular at least 0.66 (i.e., wherein the ratio of the mass fraction (in wt.%) of sulfur in the alloy to the mass fraction (in wt.%) of molybdenum in the alloy is greater than 0.6, in particular greater than 0.65, and further in particular at least 0.66), and where the total molybdenum and sulfur content (i.e., the sum of the mass fraction (in wt%) of molybdenum in the alloy and the mass fraction (in wt%) of sulfur in the alloy) is more than 0.15 times the zinc content (i.e., the mass fraction (in wt%) of zinc in the alloy). Therefore, the following condition applies to the mass fractions of molybdenum, sulfur, and zinc: Mass fraction of sulfur (wt%) + mass fraction of molybdenum (wt%) > 0.15 x mass fraction of zinc (wt%).

[0008] The proposed casting alloy is environmentally friendly, casts well, and exhibits good machinability and tribological properties in the cast state. It has been shown that the combination of molybdenum and sulfur can at least partially replace the properties of substituted lead while simultaneously overcoming the aforementioned conflict of objectives. Specifically, it was discovered within the scope of the invention that the combination of molybdenum and sulfur in the claimed mass fraction and mass ratio causes molybdenum disulfide (MoS₂) to precipitate during solidification, and that this precipitates onto or even encapsulates the zinc sulfide that also precipitates. It has been shown that in this way the damaging effects of the zinc sulfide can be suppressed or at least significantly reduced.Furthermore, it was found that the addition of molybdenum increases the sulfur content in the melt and can also partially suppress or at least slow down unwanted evaporation of sulfur (e.g., in the form of ZnS). Finally, it was shown that the precipitated molybdenum disulfide, in addition to its function of coating zinc sulfide, can exhibit its well-known lubricating properties as a dry lubricant, which has a positive effect on the tribological properties.

[0009] The present invention relates to a casting alloy of the claimed composition in the molten state. Furthermore, the present invention relates to a casting alloy of the claimed composition in the cast and, in particular, the cooled state. In the casting alloy, sulfur and molybdenum are present at least partially as MoS₂.

[0010] The casting alloy is in particular lead-free, i.e., lead is not actively added as an alloying element and any residual lead due to impurities is at most 0.10 wt.%, in particular at most 0.09 wt.%, in particular at most 0.08 wt.%, in particular at most 0.07 wt.%, in particular at most 0.06 wt.% and preferably at most 0.05 wt.%.

[0011] Preferably, the ratio of sulfur to molybdenum in the alloy is at most 2.5, more preferably at most 1.5, further preferably at most 1.0, and further preferably at most 0.8.

[0012] In particular, the ratio of sulfur to molybdenum in the alloy is between 0.6 and 2.5, preferably between 0.65 and 2.0, more preferably between 0.65 and 1.5, and even more preferably between 0.65 and 1.0. A ratio of sulfur to molybdenum in the alloy between 0.66 and 0.8 is particularly preferred.

[0013] It proves advantageous if the casting alloy contains 2.3 - 3.0 wt.%, in particular 2.6 - 2.8 wt.%, molybdenum.

[0014] Furthermore, it proves advantageous if the casting alloy contains 1.5 - 2.2 wt.%, in particular 1.7 - 2.1 wt.%, sulfur.

[0015] A higher molybdenum / sulfur content contributes to improved tribological properties.

[0016] The zinc content and the nickel content are preferably selected such that the total proportion of zinc and nickel (i.e. the sum of the mass fraction (in wt.%) of zinc in the alloy and the mass fraction (in wt.%) of nickel in the alloy) does not exceed 48.5 wt.%.

[0017] In an advantageous embodiment, the casting alloy can contain 20.0–27.0 wt.%, in particular 20.5–26.5 wt.%, and further in particular 21.0–26.0 wt.%, zinc and 10.5–13.5 wt.%, in particular 11.0–13.0 wt.% nickel. It can then be advantageous if the casting alloy contains 2.3–3.0 wt.% molybdenum and 1.5–2.2 wt.% sulfur.

[0018] In an alternative advantageous embodiment, the casting alloy can contain 17.0–24.0 wt.%, in particular 17.5–23.5 wt.%, and further in particular 18.0–23.0 wt.%, zinc and 16.0–20.0 wt.%, in particular 16.5–19.5 wt.%, and further in particular 17.0–19.0 ​​wt.% nickel. It can then be advantageous if the casting alloy contains 2.1–2.8 wt.% molybdenum and 1.4–2.1 wt.% sulfur.

[0019] In a further alternative advantageous embodiment, the casting alloy can contain 24.0–30.0 wt.%, in particular 24.5–29.5 wt.% zinc and 16.0–20.0 wt.%, in particular 16.5–19.5 wt.% nickel. It can then be advantageous if the casting alloy contains 2.6–3.3 wt.% molybdenum and 1.7–2.4 wt.% sulfur.

[0020] Furthermore, it can prove advantageous if the casting alloy contains 0.01–0.1 wt.%, particularly 0.01–0.05 wt.%, phosphorus. Phosphorus can contribute to the deoxidation of the melt. However, in combination with molybdenum disulfide, excessively high proportions can lead to degeneration of the sulfur phase and the formation of phosphorus-rich intermetallic phases, which, due to their hardness, can impair formability and increase brittleness. Therefore, the phosphorus content should be limited.

[0021] Furthermore, it is advantageous if the proportion of unavoidable impurities is less than 0.5 wt.%, in particular less than 0.2 wt.%, and in particular less than 0.1 wt.%, and in total not more than 0.8 wt.%, and in particular not more than 0.5 wt.%. The impurities may optionally include: up to 0.05 wt.% tin, up to 0.2 wt.% silicon, up to 0.2 wt.% aluminum, up to 0.04 wt.% manganese, up to 0.5 wt.% iron, up to 0.001 wt.% magnesium, up to 0.09 wt.% lead, and up to 0.05 wt.% carbon.

[0022] The invention also relates to a casting, in particular a continuous casting, especially in continuous or tube form, made from one of the casting alloys described above. The casting is produced in particular by casting, especially continuous casting, a casting alloy described above to form a casting blank and optionally by machining the casting blank.

[0023] The casting consists in particular of - 17.0 - 30.0 wt.%, preferably 20.0 - 27.0 wt.%, zinc - 10.0 - 20.0 wt.%, preferably 12.0 - 18.0 wt.%, nickel, - 2.1 - 3.3 wt% molybdenum, - 1.4 - 2.4 wt% sulfur, - possibly up to 0.1 wt% phosphorus - Residual copper and unavoidable impurities, wherein, based on weight percent, the ratio of sulfur to molybdenum in the alloy is greater than 0.6, in particular greater than 0.65, and further in particular at least 0.66, where the total molybdenum and sulfur content (i.e., the sum of the mass fraction (in wt%) of molybdenum in the alloy and the mass fraction (in wt%) of sulfur in the alloy) is more than 0.15 times the zinc content (i.e., the mass fraction (in wt%) of zinc in the alloy). Therefore, the following condition applies to the mass fractions of molybdenum, sulfur, and zinc: Mass fraction of sulfur (wt%) + mass fraction of molybdenum (wt%) > 0.15 x mass fraction of zinc (wt%).

[0024] In the cast alloy, particularly in the casting, a portion of the sulfur and molybdenum is present as molybdenum disulfide (MoS2), especially in the form of, preferably spherical, MoS2 precipitates. Preferably, the molybdenum sulfide is finely dispersed within the microstructure.

[0025] In particular, in the cast alloy, especially in the casting, some of the sulfur and zinc is present as zinc sulfide (ZnS).

[0026] Preferably, the cast alloy, and in particular the casting, has a base matrix consisting primarily of copper and zinc, in which ZnS-rich phases, particularly in the form of ZnS precipitates, are present, to which a MoS2-rich phase, particularly in the form of MoS2 precipitates, is attached. In particular, the zinc sulfide is at least partially enclosed by MoS2, preferably spherically or at least with a rounded outer contour.

[0027] The invention also relates to a method for producing a casting alloy described above. The method comprises the following steps: - Providing, in particular layers, of the alloying elements in a melting furnace, in particular an induction melting furnace, wherein the alloying elements are added at room temperature (the furnace itself, however, may have a higher temperature.); - Generating a melt from the alloy components in the melting furnace to form the alloy, especially at temperatures between 1080°C - 1250°C.

[0028] It was discovered according to the invention that a homogeneous melt can be produced by providing, and in particular layering, the alloying elements at room temperature (i.e., the alloying elements are not preheated or added in a molten state). After the melt has been produced, it can be cast and then cooled.

[0029] The alloying elements can be provided in pure form or as an alloy or compound. In particular, sulfur can be added partially in the form of molybdenum disulfide (MoS₂), which improves the solubility of sulfur and molybdenum in the melt. The molybdenum disulfide is especially dissolved in the melt.

[0030] Furthermore, it has proven advantageous to cover the alloy components with a covering agent, particularly before and during the melting process, to protect the melt from environmental influences, especially oxidation. The covering agent can be, in particular, charcoal.

[0031] Furthermore, it can prove advantageous – as an alternative or in addition to covering the melt with the covering agent – ​​if the melt is produced under a protective gas atmosphere or under negative pressure.

[0032] The invention also relates to a method for producing a casting from a casting alloy as described above. The method comprises the following steps: - Generating a melt from the alloy components in a melting furnace, in particular an induction melting furnace, further in particular as described above; - Pouring the molten metal; - Cooling (and thus solidifying) of the melt, particularly to obtain a casting blank. The casting blank can form the final casting. The casting blank can also be further processed to obtain the final casting. Therefore, the process can optionally include processing the casting blank, in particular forming, heat treatment, and / or machining of the casting blank.

[0033] The casting of the molten metal can be carried out in various ways. For example, casting the molten metal can involve one of the following processes: casting into a lost or permanent mold, sand casting, die casting, centrifugal casting, continuous casting, pressure die casting, investment casting, or composite casting by centrifugal injection. Continuous casting of the molten metal has proven to be particularly advantageous. Therefore, the casting alloy described above is also, in particular, a continuously cast alloy.

[0034] In particular, the alloy or casting exhibits a dendritic microstructure after casting. This microstructure can be modified for specific applications through subsequent forming and / or heat treatments (e.g., rolling and recrystallization).

[0035] The invention also relates to the use of a casting alloy described above for the manufacture of precision mechanical components for bearing and gear technology as well as optics, in particular for the manufacture of keys, tableware, plain bearings, nuts, screws, worm gears, linear guide elements, hinges, springs, and / or eyeglass components.

[0036] The following table summarizes advantageous compositions of the proposed casting alloy (values ​​in wt.%). Nr. Zn It’s With S Verunreininguen Rest I 21,0-26,0 11,0-13,0 2,3-3,0 1,5-2,2 < 0,8 Cu FAN 18,0-23,0 17,0-19,0 2,1-2,8 1,4-2,1 < 0,8 Cu III 24,5-29,5 17,0-19,0 2,6-3,3 1,7-2,4 < 0,8 Cu

[0037] The Figs.Figure 1 shows a simplified schematic representation of typical microstructures of a cast alloy. The microstructures were extracted from a micrograph taken under a light microscope.

[0038] As in Figs. As shown schematically in Figure 1, the cast alloy has a base matrix 10 consisting primarily of copper and zinc. ZnS-rich phases 12, particularly in the form of ZnS precipitates, are present in the base matrix 10 (in Figs.(1 shown hatched). A MoS2-rich phase 14 is deposited on the ZnS-rich phases 12, preferably completely enclosing the ZnS phase 12. As mentioned above, this reduces the damaging effects of the ZnS. Furthermore, pure MoS2-rich phases 14, preferably spherical or nodular, can be present in the base matrix 10. These MoS2-rich phases 14 can serve as a dry lubricant and thus improve the tribological properties of the casting alloy or a casting produced therefrom. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] DE 10 2020 106 999 A1

[0004]

Claims

[1] Copper-zinc-nickel-molybdenum casting alloy, consisting of: 17.0 - 30.0 wt.%, in particular 20.0 - 27.0 wt.%, zinc 10.0 - 20.0 wt.%, in particular 12.0 - 18.0 wt.%, nickel, 2.1 - 3.3 wt% molybdenum, 1.4 - 2.4 wt% sulfur, optionally up to 0.1 wt% phosphorus, Residual copper and unavoidable impurities, wherein, based on weight percent, the ratio of sulfur to molybdenum in the alloy is greater than 0.6, and where the total proportion of molybdenum and sulfur is more than 0.15 times the proportion of zinc. [2] Copper-zinc-nickel-molybdenum casting alloy according to claim 1, wherein the ratio of sulfur to molybdenum in the alloy is at most 2.5, in particular at most 2.0, further in particular at most 1.5, further in particular at most 1.0, further in particular at most 0.

8. [3] Copper-zinc-nickel-molybdenum casting alloy according to claim 1 or 2, wherein the alloy contains 2.3 - 3.0 wt.%, in particular 2.6 - 2.8 wt.%, molybdenum. [4] Copper-zinc-nickel-molybdenum casting alloy according to any of the preceding claims, wherein the alloy contains 1.5 - 2.2 wt.%, in particular 1.7 - 2.1 wt.%, sulfur. [5] Copper-zinc-nickel-molybdenum casting alloy according to any of the preceding claims, wherein the total proportion of zinc and nickel does not exceed 48.5 wt.%. [6] Copper-zinc-nickel-molybdenum casting alloy according to any one of the preceding claims, wherein the alloy 20.0 - 27.0 wt.%, in particular 20.5 - 26.5 wt.%, further in particular 21.0 - 26.0 wt.%, zinc and Contains 10.5 - 13.5 wt.%, in particular 11.0 - 13.0 wt.% nickel. [7] Copper-zinc-nickel-molybdenum casting alloy according to any one of claims 1 to 5, wherein the alloy 17.0 - 24.0 wt.%, in particular 17.5 - 23.5 wt.%, further in particular 18.0 - 23.0 wt.%, zinc and Contains 16.0 - 20.0 wt.%, in particular 16.5 - 19.5 wt.%, and further in particular 17.0 - 19.0 wt.%, nickel. [8] Copper-zinc-nickel-molybdenum casting alloy according to any one of claims 1 to 5, wherein the alloy 24.0 - 30.0 wt.%, in particular 24.5 - 29.5 wt.% zinc and Contains 16.0 - 20.0 wt.%, in particular 16.5 - 19.5 wt.% nickel. [9] Copper-zinc-nickel-molybdenum casting alloy according to any of the preceding claims, wherein the alloy contains 0.01 - 0.1 wt.%, in particular 0.01 - 0.05 wt.%, phosphorus. [10] Copper-zinc-nickel-molybdenum casting alloy according to any of the preceding claims, wherein the proportion of unavoidable impurities is less than 0.5 wt.%, in particular less than 0.2 wt.%, further in particular less than 0.1 wt.% and in total not more than 0.8 wt.%, in particular not more than 0.5 wt.%. [11] Casting, in particular continuous casting, especially in continuous or tube form, produced by casting a copper-zinc-molybdenum casting alloy according to one of the preceding claims. [12] Casting according to the previous claim, wherein part of the sulfur is present as MoS2. [13] Casting according to the previous claim, wherein part of the sulfur is present as zinc sulfide, wherein a MoS2-rich phase is attached to the zinc sulfide, in particular the zinc sulfide is at least partially enclosed by MoS2. [14] Method for producing a copper-zinc-nickel-molybdenum casting alloy according to any one of claims 1 to 10, comprising: - Layers of alloying elements in a melting furnace, in particular an induction melting furnace, wherein the alloying elements are added at room temperature; - Creating a melt from the alloy components in the melting furnace.

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