EP3485048A1 - Alliage cuivre-nickel-étain, procédé de préparation et utilisation de celui-ci - Google Patents

Alliage cuivre-nickel-étain, procédé de préparation et utilisation de celui-ci

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Publication number
EP3485048A1
EP3485048A1 EP17736566.5A EP17736566A EP3485048A1 EP 3485048 A1 EP3485048 A1 EP 3485048A1 EP 17736566 A EP17736566 A EP 17736566A EP 3485048 A1 EP3485048 A1 EP 3485048A1
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EP
European Patent Office
Prior art keywords
copper
nickel
alloy
phases
volume
Prior art date
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EP17736566.5A
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German (de)
English (en)
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EP3485048B1 (fr
Inventor
Kai Weber
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Wieland Werke AG
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Wieland Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt 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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the invention relates to a copper-nickel-tin alloy with excellent castability, hot workability and cold workability, high resistance to abrasive wear, adhesive wear and fretting wear and improved corrosion resistance and
  • the binary copper-tin alloys are of great importance in mechanical engineering and vehicle construction and in a wide range of electronics and electrical engineering.
  • This material group has a high resistance to abrasive wear.
  • the copper-tin alloys ensure good sliding properties and a high fatigue strength, resulting in their excellent suitability for sliding elements in engine construction and vehicle construction and in general mechanical engineering.
  • the copper-nickel-tin alloys have improved mechanical properties, such as hardness, compared to the binary copper-tin materials. Tensile strength and yield strength. The increase of the mechanical characteristics is achieved by the hardenability of the Cu-Ni-Sn alloys.
  • the precipitation processes are essential for adjusting the properties of this group of materials.
  • DE 0833954 T1 proposes a spinodal Cu-Ni-Sn continuous casting alloy with 8 to 16 wt.% Ni, 5 to 8 wt.% Sn and optionally up to 0.3 wt. % Mn, up to 0.3 wt.% B, up to 0.3 wt.% Zr, up to 0.3 wt.% Fe, up to 0.3 wt.% Nb and up to 0 , 3 wt .-% Mg without kneading to produce.
  • the alloy After aging, the alloy must be rapidly cooled by means of water quenching in order to obtain a spinodally segregated structure without discontinuous precipitations.
  • Copper alloys with the conventional method of ingot casting with subsequent hot forming and cold forming with intermediate annealing are not or only with poor efficiency to produce, because the
  • These copper alloys also include the copper-nickel-tin materials. To ensure cold forming of the cast state of such alloys, therefore, a thin strip casting process with precise control of
  • the Schwingreibverschl composition in technical language called Fretting, is a Reibverschl yield that occurs between oscillating contact surfaces.
  • Fretting is a Reibverschl corrosion that occurs between oscillating contact surfaces.
  • the reaction with the surrounding medium leads to fretting corrosion.
  • Material damage can significantly lower the local strength in the wear zone, in particular the fatigue strength. From the damaged component surface can go out Schwinganrisse, the
  • Vibratory friction / Friction corrosion / Fretting is therefore a combination of material properties wear resistance, ductility and
  • Nickel silicides and nickel phosphides are said to provide high strength and good stress relaxation resistance of the alloy.
  • Contract welding is applied to the base body and 77 to 92 wt .-% Cu, 8 to 18 wt .-% Sn, 1 to 5 wt .-% Ni, 0.5 to 3 wt .-% Si and 0.25 to 1 Wt .-% contains Fe.
  • the wear-resisting agents used here are the silicides and phosphides of the alloying elements nickel and iron.
  • Copper alloy with up to 0.4 wt .-% Si, 1 to 10 wt .-% Ni, 0.02 to 0.5 wt .-% B, 0.1 to 1 wt .-% P and 4 to 25 wt .-% Sn known.
  • This alloy can be used in the form of cast iron as welding filler metal on suitable metallic
  • the alloy has improved ductility over the prior art and is machinable. Except for build-up welding, this Cu-Sn-Ni-Si-P-B alloy is for
  • Deposition can be used by spraying.
  • the addition of phosphorus, silicon and boron is said to be the self-fluxing properties of
  • the teaching disclosed in this document prescribes a particularly high P content of from 0.2 to 0.6% by weight in the case of a mandatory Si content of the alloy of from 0.05 to 0.15% by weight. This underlines the superficial demand for the self-flowing properties of the material. With this high P content, the hot workability of the alloy will be poor and the spinodal demixability of the structure will be insufficient.
  • US 4 818 307 A has the size of a
  • complex silicide formations / boride formations of the elements nickel and iron reaching a size of 5 to 100 pm increase the wear resistance of a copper alloy containing 5 to 30 wt% Ni, 1 to 5 wt% Si, 0 , 5 to 3 wt .-% B and 4 to 30 wt .-% Fe considerably.
  • the element tin is not included in this material. This material is by means of build-up welding on a suitable substrate as
  • Sn and / or zinc in particular increases the resistance of the material to adhesive wear. This material is also applied by deposition welding on a suitable substrate as a wear protection layer.
  • the copper alloy according to the documents US Pat. No. 4,818,307 A and US Pat. No. 5,004,581 A will have only a very limited cold workability due to the required size of the silicide formations / boride formations of the elements nickel and iron of 5 to 100 .mu.m.
  • This copper base alloy contains 0.1 to 10 wt% Ni, 0.1 to 10 wt% Sn, 0.05 to 5 wt% Si, 0.01 to 5 wt .-% Fe and 0.0001 to 1 wt .-% boron.
  • This material has a content of disperse distributed intermetallic phases of the system Ni-Si. The properties of the alloy are also explained in embodiments which have no Fe content.
  • From the patent US 5 028 282 A is the disclosure of a copper alloy with 6 to 25 wt .-% Ni, 4 to 9 wt .-% Sn and other additives with a
  • alloying elements Zn, Mn, Mg, P and B are added to deoxidize the melt of the alloy.
  • the elements Ti, Cr, Zr, Fe and Co have a grain-refining and strength-increasing function
  • Phosphorus succeeds in lowering the relatively high base melt temperature in terms of processing technology. Therefore, the use of this takes place Alloy additives in particular in the field of wear-resistant coating materials and high-temperature materials, which include, for example, the alloys of systems Ni-Si-B and Ni-Cr-Si-B. In these
  • the alloying elements boron and silicon are responsible for the strong lowering of the melting temperature of nickel base age alloys
  • Nickel base age alloys becomes possible.
  • thermomechanical loading of this solder joint or during the soldering process itself large voltages occur at the interfaces, which can lead to cracks, especially in the vicinity of the intermetallic phases.
  • a mixing of the solder components with particles is proposed, the one
  • SiB 3 , SiB 4 , SiB 6 and / or SiB n silicon borides which are usually determined in the boron content, differ in their properties
  • Surface coating consists of a relatively ductile matrix of the metals iron, cobalt and nickel with embedded silicides and borides as hard particles (Knotek, O. Lugscheider, E., Reimann, H .: A contribution to the
  • Ni-Cr-Si Ni-Cr-B, Ni-B-Si and Ni-Cr-B-Si.
  • the Ni-B-Si alloys also contain the borides Ni 3 B and the Ni-Si borides / Ni silicoborides Ni 6 Si 2 B.
  • a certain degree of inertia is also reported silicidation in the presence of the element boron. Further investigations of the alloy system Ni-B-Si led to the detection of the refractory Ni-Si-borides Ni 6 Si 2 B and Ni 4i29 Si 2 Bi i43 (Lugscheider, E .;
  • Ni-Si borides exist in a relatively large homogeneity region towards boron and silicon.
  • the element zinc is added to the copper-nickel-tin alloys to lower the metal price. Functionally, the alloying element zinc causes the stronger formation of Sn-rich or Ni-Sn-rich phases from the melt. In addition, zinc enhances the formation of the alloying element zinc.
  • Precipitants in the spinodal Cu-Ni-Sn alloys are also added to the copper-nickel-tin alloys to improve runflat properties and to improve machinability.
  • the invention has for its object to provide a high-strength copper-nickel-tin alloy, over the entire range of nickel content and tin content of 2 to 10 wt .-% each an excellent
  • the copper-nickel-tin alloy after casting should be free of gas pores and shrinkage pores and stress cracks and by a structure with
  • intermetallic phases should already be present in the microstructure of the copper-nickel-tin alloy after casting. This is important so that the alloy already has a high strength, a high hardness and a sufficient wear resistance in the cast state.
  • the cast state of the copper-nickel-tin alloy should not first be homogenized by means of a suitable annealing treatment to a
  • the processing properties of the copper-nickel-tin alloy on the one hand, the goal is that their cold workability does not significantly deteriorate in spite of the content of intermetallic phases with respect to the conventional Cu-Ni-Sn alloys. On the other hand, for the alloy should
  • Cooling speed after removal of the materials is considered necessary to rapidly cool the materials by means of water quenching after the spinodal removal, in order to obtain a spinodally segregated structure without discontinuous precipitations. Since, however, dangerous residual stresses can form as a result of this cooling method after the removal, the invention is based on the further object of preventing the formation of discontinuous precipitates during the entire production process, including the aging, on the alloy side.
  • a further processing which comprises at least one annealing or at least one hot forming and / or cold forming together with at least one annealing, is a fine-grained, hard particle-containing structure with high strength, high heat resistance, high hardness, high stress relaxation resistance and corrosion resistance, sufficient electrical conductivity and a high Level of resistance to the mechanisms of Sliding wear and the Schwingreibverschl devises set.
  • the invention is with respect to a copper-nickel-tin alloy by the
  • the invention includes a high strength copper-nickel-tin alloy having excellent castability, hot workability and cold workability, high resistance to abrasive wear, adhesive wear and tear
  • the invention includes a high-strength copper-nickel-tin alloy, with excellent castability, hot workability and
  • Corrosion resistance and stress relaxation resistance consisting of
  • Molar formula Cu p Ni r Sn s can be given and a ratio (p + r) / s of the element contents in atomic% of 10 to 15 and have a3) a balance of copper mixed crystal;
  • Silicon borides are formed, the Ni-Si borides, Ni borides, Ni phosphides, Mg phosphides, Ni silicides, Mg silicides and the Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases which are present individually and / or as addition compounds and / or mixed compounds, nuclei for a uniform crystallization during the solidification / cooling of the melt, so that the first phase constituents and / or the second phase constituents island-like and / or reticulate uniformly are distributed in the structure;
  • the Si-containing and B-containing phases which are formed as boron silicates and / or Borphosphorsilikate, together with the phosphorus silicates and Mg oxides take the role of a wear-protective and corrosion-protective coating on the semifinished products and components of the alloy.
  • the first phase components and / or the second Contain phase components with at least 1% by volume in the cast structure of the alloy.
  • the structure Due to the uniform distribution of the first phase components and / or the second phase components in island form and / or in network form, the structure is free of segregations. Among such segregations are accumulations of the first phase components and / or the second phase components in the
  • Understood cast structure which are designed as grain boundary segregations, which cause damage to the structure in the form of cracks in thermal and / or mechanical stress of the casting, which can lead to breakage.
  • the structure is still free of water after casting
  • the alloy is in the cast state.
  • the invention includes a high-strength copper-nickel-tin alloy, with excellent castability, hot workability and
  • Corrosion resistance and stress relaxation resistance consisting of
  • Ni-Si borides with 2 to 35% by volume as Si-containing and B-containing phases
  • B2 are contained in the structure with up to 80% by volume as continuous precipitations of the system (Cu, Ni) -Sn,
  • Ni phosphides with 2 to 35% by volume as Ni phosphides, Mg phosphides, Ni silicides, Mg silicides and as Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases contained in the structure, which are present individually and / or as addition compounds and / or mixed compounds of
  • Precipitations of the system (Cu, Ni) -Sn are sheathed and a size of have less than 3 ⁇ ;
  • Si-containing and B-containing phases which are called silicon borides
  • Addition compounds and / or mixed compounds are present, nuclei for a static and dynamic recrystallization of the microstructure during the
  • the Si-containing and B-containing phases which are formed as boron silicates and / or Borphosphorsilikate, together with the phosphorus silicates and Mg oxides take the role of a wear-protective and corrosion-protective coating on the semifinished products and components of the alloy.
  • Segregations are understood as meaning accumulations of the first phase constituents and / or of the second phase constituents in the microstructure, which are formed as grain boundary segregations, which cause damage to the microstructure in the form of cracks, which can lead to breakage, especially under dynamic loading of the components.
  • the structure of the alloy is free of gas pores, shrinkage pores and stress cracks after further processing. It should be emphasized as an essential feature of the invention that the structure of the further processed state is free of discontinuous precipitates of the system (Cu, Ni) -Sn.
  • the alloy is in the processed state in front.
  • the invention is based on the consideration that a copper-nickel-tin alloy with Si-containing and B-containing phases and with phases of the systems Ni-Si-B, Ni-B, Ni-P, Mg-P, Ni-Si, Mg-Si and with other Mg-containing phases is provided. These phases significantly improve the copper-nickel-tin alloy with Si-containing and B-containing phases and with phases of the systems Ni-Si-B, Ni-B, Ni-P, Mg-P, Ni-Si, Mg-Si and with other Mg-containing phases is provided. These phases significantly improve the
  • the copper-nickel-tin alloy according to the invention can be produced by means of the sand casting method, shell molding method, precision casting method, full casting method, die casting method, lost foam method and chill casting method or with the aid of the continuous or semi-continuous
  • Cast formats of the copper-nickel-tin alloy according to the invention can in particular over the entire range of Sn content and Ni content directly without the mandatory implementation of a
  • Homogenmaschinesglühung be hot-formed, for example, by hot rolling, extrusion or forging. Furthermore, it is noteworthy that after chill casting or continuous casting of the formats from
  • the metallic matrix of the structure of the copper-nickel-tin alloy according to the invention consists in the cast state with increasing Sn content of the alloy, depending on the casting process, from increasing proportions of tin
  • tin-enriched phases which are evenly distributed in the copper mixed crystal ( ⁇ -phase).
  • These tin-enriched phases of the metallic matrix may be divided into first phase components and second phase components.
  • the first phase constituents can be given by the empirical formula Cu h Ni k Sn m and have a ratio (h + k) / m of the element contents in atomic% of 2 to 6.
  • the second phase components can be used with the molecular formula
  • Cu p Ni r Sn s are given and have a ratio (p + r) / s of
  • the alloy according to the invention is characterized by Si-containing and B-containing phases which can be subdivided into two groups.
  • the first group concerns the Si-containing and B-containing phases, which as
  • Silicon borides are formed and can be present in the modifications SiB 3 , SiB 4 , SiB 6 and SiB n .
  • the "n" in the compound SiB n denotes the high solubility of the element boron in the silicon lattice.
  • the second group of Si-containing and B-containing phases relates to the silicatic compounds of boron silicates and / or Borphosphorsilikate.
  • the microstructure content of the Si-containing and B-containing phases which as silicon borides and as
  • Borosilicate and / or Borphosphorsilikate are formed, a minimum of 0.01 and a maximum of 10% by volume.
  • the uniformly distributed arrangement of the first phase constituents and / or second phase constituents in the microstructure of the alloy according to the invention results in particular from the effect of the Si-containing and B-containing phases, which are formed as silicon borides, and the Ni-Si borides with the
  • the Ni phosphides, Mg phosphides, Ni silicides, Mg silicides and the Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg- containing phases preferably on the already existing primary nuclei of silicon borides, Ni-Si borides and Ni borides, which are present individually and / or as addition compounds and / or mixed compounds, as secondary nuclei.
  • the Ni-Si borides and the Ni borides are each contained in the structure with 1 to 15% by volume.
  • the Ni phosphides and Ni silicides are present in a proportion of 1 to 5% by volume each.
  • the Mg phosphides take one Proportion of the structure of 0.1 to 5% by volume.
  • the Mg silicides and the Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases are each present in the microstructure 0.1 to 5% by volume.
  • the Si-containing and B-containing phases which as
  • nuclei These phases are referred to below as nuclei.
  • Phase components and / or the second phase components of the metallic matrix preferably in the regions of the crystallization nuclei, whereby the crystallization nuclei of tin and / or the first phase components and / or the second phase components are coated.
  • first-grade hard particles These crystallization nuclei encased in tin and / or the first phase constituents and / or the second phase constituents are referred to below as first-grade hard particles.
  • the hard particles of the first class have a size of less than 80 ⁇ m in the cast state of the alloy according to the invention.
  • the size of the hard particles of the first class is less than 50 pm.
  • the island-like arrangement of the first phase constituents and / or of the second phase constituents changes into a network-like arrangement in the microstructure.
  • the first phase components account for up to 30% by volume.
  • the second phase constituents assume a proportion of up to 20% by volume.
  • the first phase constituents and / or the second phase constituents are contained in the structure of the casting state of the alloy with at least 1% by volume.
  • the conventional copper-nickel-tin alloys have a relatively large solidification interval. This large solidification interval increases the risk of gas absorption during casting and, as a result, uneven, coarse, usually dendritic crystallization of the melt. The consequences are often gas pores and coarse Sn-rich segregations, at the phase boundary often shrinkage pores and stress cracks occur. In addition, with this material group, the Sn-rich segregations preferably occur at the grain boundaries.
  • the elements boron, silicon and phosphorus assume a deoxidizing function in the melt of the invention.
  • By adding boron and silicon it is possible to lower the content of phosphorus without lowering the intensity of deoxidation of the melt.
  • By means of this measure it is possible to suppress the adverse effects of a sufficient amount Deoxidation of the melt by means of a phosphorus additive.
  • a high P content would additionally expand the already very large solidification interval of the copper-nickel-tin alloy, resulting in an increase in the
  • Solidification interval of the alloy according to the invention As a result, the cast state of the invention has a very uniform microstructure with a fine distribution of the individual phase components. Thus occur in the
  • alloy according to the invention in particular at the grain boundaries, no tin-enriched segregations.
  • the elements boron, silicon and phosphorus cause a reduction of the metal oxides.
  • the elements are themselves oxidized, rising mostly to the surface of the castings and form there as boron silicates and / or Borphosphorsilikate and as phosphorus silicates a protective layer that protects the castings against gas absorption. Exceptionally smooth surfaces of the castings from the
  • a basic idea of the invention consists in the transfer of the effect of boron silicates, boron phosphorsilicates and phosphorus silicates with respect to the
  • Copper-nickel-tin alloy according to the invention causes on the one hand during the solidification of the melt by means of the action of the crystallization nuclei a structure with a uniform island-shaped and / or reticular distribution of the first phase constituents and / or the second phase constituents of the metallic matrix.
  • the Si-containing and B-containing phases which form during the solidification of the melt and which are in the form of borosilicates and / or borophosphorus silicates together with the phosphorus silicates ensure the necessary matching of the thermal expansion coefficients of the first phase components and / or the second Phase components and the copper mixed crystal of the metallic matrix. In this way, the formation of pores as well
  • the alloy content of the copper-nickel-tin alloy according to the invention further causes a significant change in the grain structure in the cast state.
  • a substructure with a grain size of the subgrains of less than 30 ⁇ m is formed in the primary cast structure.
  • the alloy according to the invention may be subjected to further processing by annealing or by hot working and / or cold working together with at least one annealing.
  • One possibility of further processing of the copper-nickel-tin alloy according to the invention consists of the castings by means of at least one
  • the alloy according to the invention already has a high strength in the cast state.
  • the castings thus have a lower cold workability, which makes economic processing difficult. For this reason, the implementation of a
  • Cooling speed can be used.
  • the use of accelerated air cooling has also proven to be practicable to a sufficient degree to increase the hardness and increase the strength of the precipitation processes and segregation processes in the structure during the process To lower homogenization annealing of the invention.
  • the outstanding effect of the nucleation nuclei for the recrystallization of the microstructure of the invention can be seen in the microstructure which can be adjusted after cold working by means of annealing in the temperature range from 170 to 880 ° C. and an annealing time of between 10 minutes and 6 hours.
  • the extraordinarily fine structure of the recrystallized alloy allows further cold forming steps with a degree of deformation ⁇ of mostly over 70%. In this way, high-strength states of the alloy can be produced.
  • Tensile strength R m , the yield strength R p0 , 2 and the hardness are set.
  • the height of the parameter R p o, 2 is for the sliding elements
  • R p0 , 2 is a prerequisite for the necessary spring characteristics of connectors in electronics and electrical engineering.
  • Kaltumformgraden of less than 20% the structure of the invention free of discontinuous precipitates of the system (Cu, Ni) -Sn remains.
  • Hot forming of the alloy according to the invention in the temperature range of 600 to 880 ° C favorably takes place. This results in a further increase in the uniformity and the fine grain of the microstructure.
  • the cooling of the semi-finished products and components can be carried out after the hot deformation of calmed or accelerated air or water.
  • the surface of the hot-formed parts and the structure, as after casting, were free from cracks and pores even after hot working.
  • Further processing of the as-cast or hot-worked state or annealed cast state or annealed hot-worked state comprising performing at least one cold working.
  • At least one annealing treatment of the cold-worked state of the invention may be carried out in the temperature range of 170 to 880 ° C for 10 minutes to 6 hours, alternatively with quenched or accelerated air or water cooling.
  • flash annealing may be performed in the temperature range of 170 to 550 ° C for 0.5 to 8 hours.
  • At least one annealing precipitates of the system (Cu, Ni) -Sn are formed preferentially in the areas of the crystallization nuclei, whereby the
  • Crystallization nuclei are encased in these precipitates.
  • Crystallization nuclei are referred to below as hard particles of second class.
  • the size of the second-class hard particles decreases in comparison to the size of the hard particles first class off.
  • there is a progressive comminution of hard particles of the second class since these can not support the change in shape of the metallic base material surrounding them as the hardest constituents of the alloy.
  • resulting hard particles second class and / or the resulting segments of the hard particles second class have a size of less than 40 ⁇ to even less than 5 ⁇ depending on the degree of cold work.
  • Ni content and the Sn content of the invention are each within the limits of 2.0 to 10.0 wt%.
  • a Ni content and / or an Sn content of less than 2.0% by weight would result in too low strength values and hardness values.
  • the running properties of the alloy would be at
  • the toughness properties of the alloy according to the invention would deteriorate rapidly, whereby the dynamic load capacity of the components is reduced from the material.
  • the content of nickel and tin in the range from 3.0 to 9.0 wt .-% proves to be advantageous.
  • the range of 4.0 to 8.0 wt% is particularly preferable for the content of the elements nickel and tin.
  • Copper materials are known to increase the degree of spinodal segregation of the microstructure as the Ni / Sn ratio of the element contents increases in weight percent of the elements nickel and tin. This is valid for a Ni content and an Sn content from about 2% by weight. Gets with decreasing Ni / Sn ratio the mechanism of precipitation formation of the system (Cu, Ni) -Sn a higher weight, resulting in a reduction of the spinodal segregated
  • Part of the structure leads.
  • One consequence is, in particular, a more pronounced formation of discontinuous precipitates of the system (Cu, Ni) -Sn with decreasing Ni / Sn ratio.
  • the element magnesium is alloyed with the inventive alloy with 0.01 to 0.8 wt .-%. Magnesium contributes to increasing the proportion of
  • the Mg-containing hard particles in the structure cause an increase in the strength, hardness and wear resistance of the alloy. If the Mg content is below 0.01% by weight, these are
  • Mg phosphides and Mg silicides are contained in the structure of the invention.
  • Mg borides due to the relatively low melting temperature of the element magnesium, no clearly analyzable content of Mg borides could be determined in the alloy according to the invention. Nevertheless, it is considered possible that, under certain process conditions during the production and further processing of the invention, Mg borides can form as further Mg-containing phases. These Mg borides can be present in the modifications MgB 2 and / or MgBi 2 in a proportion of 0.1 to 5% by volume in the microstructure as hard particles of first and second class.
  • Cu-containing and Mg-containing phases are also present in the microstructure of the alloy according to the invention as further Mg-containing phases.
  • these phases can be partially or completely replaced by Cu-containing and Sn-containing and Mg-containing phases.
  • Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases are present in the microstructure of the copper-nickel-tin alloy according to the invention.
  • the effect of the crystallization nuclei as recrystallization nuclei and the effect of the silicate-based phases for the purpose of wear protection and corrosion protection can only achieve a technically significant degree in the alloy according to the invention if the silicon content is at least 0.01% by weight and the boron Content is at least 0.002 wt .-%. exceeds on the other hand, the Si content of 1, 5 wt .-% and / or the B content of 0.45 wt .-%, this leads to a deterioration of the casting behavior. The too high content of crystallization nuclei would make the melt significantly thicker. In addition, reduced toughness properties of the alloy according to the invention would result.
  • the range for the Si content within the limits of 0.05 to 0.9 wt .-% is evaluated.
  • the content of silicon from 0.1 to 0.6% by weight has proven particularly advantageous.
  • the content of 0.01 to 0.4 wt .-% is considered advantageous.
  • the content of boron has proven particularly advantageous from 0.02 to 0.3% by weight.
  • Borphosphorsilikate are formed, has a lower limit of
  • the minimum ratio Si / B of the element contents of the elements silicon and boron in wt.% Of 0.8 is advantageous.
  • the minimum ratio Si / B of the element contents of the elements silicon and boron in wt.% Of 1 is preferred.
  • Hard particles of first class During a thermal or thermomechanical further processing of the casting state, at least partial dissolution of the casting occurs
  • silicidic components of the hard particles of first class This increases the Si content of the metallic matrix. If this exceeds an upper one
  • the maximum ratio Si / B of the elemental contents of the elements silicon and boron in wt .-% of the alloy according to the invention at 8.
  • the size of forming during a thermal or thermomechanical processing of the cast state of the alloy silicides Lower to less than 3 pm. Furthermore, this limits the content of silicides.
  • the limitation of the ratio Si / B of the element contents of the elements silicon and boron in% by weight to the maximum value of 6 has proven particularly advantageous.
  • the content of phosphorus of the alloy according to the invention is 0.004 to 0.3 wt .-%.
  • the P content no longer contributes to ensuring sufficient castability of the invention. If the phosphorus content of the alloy assumes values above 0.3% by weight, on the one hand an excessively high Ni content is bound in the form of phosphides, whereby the spinodal separability of the microstructure is reduced. On the other hand, would be at a P-content above 0.3 wt .-% worsen the hot workability of the invention significantly. For this reason, a P content of 0.01 to 0.3 wt .-% has proved to be particularly advantageous. Preferred is a P content in the range of 0.02 to 0.2 wt%.
  • the alloying element phosphorus is of very great importance for another reason. Together with the required maximum
  • Ratio Si / B of the elemental contents of the elements silicon and boron in wt.% Of 8 is attributable to the phosphorus content of the alloy, that after further processing of the invention, Ni phosphides, Mg phosphides, Ni silicides, Mg silicides as well as Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases which individually and / or as
  • Adjuvant compounds and / or mixed compounds are present and are coated by precipitates of the system (Cu, Ni) -Sn, with a size of not more than 3 pm and with a content of 2 up to 35% by volume in the microstructure.
  • Ni phosphides, Mg phosphides, Ni silicides, Mg silicides and Cu-containing and Mg-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases which are used individually and / or as addition compounds and / or or mixed compounds, are coated by precipitates of the system (Cu, Ni) -Sn and have a maximum size of 3 pm, are referred to as hard particles of the third class.
  • these hard particles of the third class supplement the hard particles of the second class in their function as wear carriers. So they increase the strength and Hardness of the metallic matrix and thus improve the resistance of the alloy to abrasive wear.
  • the third-class hard particles increase the resistance of the alloy to the adhesive wear.
  • these hard particles of third class cause a significant increase in the heat resistance and the
  • the alloy according to the invention has the character of a precipitation hardenable material.
  • the invention corresponds to a precipitation hardenable and spinodal
  • the sum of the element contents of the elements silicon, boron and phosphorus is advantageously at least 0.25 wt .-%.
  • alloy according to the invention may contain the following choice elements:
  • the element cobalt can be added to the copper-nickel-tin alloy according to the invention with a content of up to 2.0 wt .-%.
  • the alloying element cobalt may be added to assist in the formation of the
  • Crystallization nuclei and the hard particles of the first, second and third class of Alloy participate. Thereby, the Ni content bound in the hard particles can be reduced. In this way it can be achieved that the Ni content, effective in the metallic matrix for the spinodal
  • Segregation of the structure is available increases.
  • Advantagely 0.1 to 2.0 wt .-% Co it is thus possible to significantly increase the strength and hardness of the invention.
  • the element zinc can be added to the copper-nickel-tin alloy according to the invention with a content of 0.01 to 2.5 wt .-%. It turned out that the alloying element zinc as a function of the Sn content of the alloy, the proportion of the first phase components and / or second
  • Phase components in the metallic matrix of the invention increases, thereby increasing strength and hardness.
  • responsible for this are the interactions between the Ni content and the Zn content.
  • a decrease in the size of the hard particles of the first and second class was found, which thus formed more finely distributed in the structure.
  • Phases, Cu-containing and Mg-containing and Zn-containing phases and / or Cu-containing and Sn-containing and Mg-containing phases and Cu-containing and Sn-containing and Mg-containing and Zn-containing phases may be included.
  • the invention can be added to a zinc content in the range of 0.05 to 2.0 wt .-%.
  • a content of zinc in the range of 0.1 to 1, 0 wt .-%.
  • the copper-nickel-tin alloy according to the invention may have low, above the impurity limit Bleianteile up to 0.25 wt .-%.
  • the copper-nickel-tin alloy is free of lead, with the exception of any unavoidable impurities, thus meeting current environmental standards
  • Si-containing and B-containing phases which are formed as boron silicates and / or Borphosphorsilikate, and of phosphorus silicates not only leads to a significant reduction in the content of pores and cracks in the structure of the alloy according to the invention.
  • These silicate-based phases also play the role of one together with the Mg oxides
  • the alloying element tin contributes in particular to the formation of a so-called tribo layer between the sliding partners. Especially under mixed friction conditions, this mechanism is significant when the emergency running characteristics of a
  • the tribo layer leads to the reduction of the purely metallic contact surface between the sliding partners, whereby a welding or seizing of the elements is prevented.
  • the alloy of the present invention ensures a combination of the properties of wear resistance and corrosion resistance. This combination of properties leads to a demand high resistance to the mechanisms of sliding wear and a high
  • the heat resistance and stress relaxation resistance are among the other essential properties of an alloy suitable for molding
  • the alloy according to the invention already has a cast state high level of strength, hardness, ductility, complex wear resistance and corrosion resistance. Through this combination of properties, sliding elements and guide elements can already be produced from the casting formats.
  • the casting state of the invention can also be used for the manufacture of valve housings and housings of water pumps, oil pumps and fuel pumps.
  • the invention is suitable for the metal objects in constructions for the rearing of marine organisms (aquaculture). Furthermore, from the invention, pipes, gaskets and
  • the material is of great importance.
  • cymbals of high quality have hitherto been made of tin-containing copper alloys by means of hot forming and at least one annealing, before they are usually brought into the final shape by means of a bell or a shell. Then the tanks are annealed again before the final machining is completed.
  • the production of the different variants of the tanks eg Ride tank, hi-hat, crash tank, China tank, Splash basin and effect basin
  • the material eg Ride tank, hi-hat, crash tank, China tank, Splash basin and effect basin
  • composition of the invention different microstructural proportions of the phases of the metallic matrix and the different hard particles can be adjusted in a very wide range. In this way it is already possible on the alloy side, to act on the sound of the pelvis.
  • the invention can be used to be applied to a composite partner by means of a joining process.
  • bearing composite shells or composite bearing bushes can be produced by roll cladding, inductive or conductive roll cladding or by laser roll cladding, also with the optional performance of at least one anneal in the temperature range of 170 to 880 ° C.
  • high-performance composite sliding elements such as bearing composite shells or composite bearings can also be used as a three-layer system, with a bearing back made of steel, the actual bearing from the
  • alloy according to the invention and the running layer are made of tin or of the Sn-rich coating.
  • This multilayer system has a particularly advantageous effect on the adaptability and running ability of the plain bearing and improves the embedding ability of foreign particles and abrasive particles, and it does not damage even by thermal or thermomechanical stress of the sliding bearing by a repeal of the composite layer system due to pore formation and cracking in the border region individual layers comes.
  • the great potential of the copper-nickel-tin materials in particular with regard to strength, spring properties and stress relaxation resistance, can also be used for the field of application of tinned components, line elements, guide elements and connecting elements in electronics and electrical engineering by using the alloy according to the invention.
  • the damage mechanism of pore formation and cracking in the boundary region between the alloy according to the invention and the tinning is reduced even at elevated temperatures, whereby an increase in the electrical contact resistance of the components or even a replacement of tinning is counteracted.
  • the different hard particles serve as chip breakers.
  • the resulting short shavings chips and / or random chips facilitate the machinability, which is why the semi-finished products and components from the cast state and the further processed state of the alloy according to the invention have a better machinability.
  • Embodiment A is characterized by a Ni content of 6.06 wt%, an Sn content of 5.63 wt%, a Mg content of 0.26 wt%, an Si content of 0 , 29 wt .-%, a B content of 0.1 1 wt .-%, a P content of 0.12 wt .-% and characterized by a balance copper.
  • the reference material R a conventional copper-nickel-tin-phosphorus alloy, has a Ni content of 5.78 wt.%, An Sn content of 5.75 wt.%, A P content of 0.032 wt .-% and a residue of copper.
  • the structure of the continuous casting plates of the reference material R has gas and shrinkage pores as well as Sn-rich segregations, especially at the grain boundaries.
  • the reference material R has the continuous casting of the embodiment A due to the action of the crystallization nuclei a uniformly solidified, pore-free and segregation-free structure.
  • the metallic base material of the casting state of the exemplary embodiment A consists of a copper mixed crystal with, based on the overall structure, about 10 to 15% by volume of inscribed first phase constituents, which can be given the empirical formula Cu h Ni k Sn m and a ratio (h + k) / m of the element contents in atomic% of 2 to 6 have.
  • Immersed island components in the form of an insulator which can be given the empirical formula Cu p Ni r Sn s and have a ratio (p + r) / s of elemental contents in atomic% of 10 to 15.
  • the compounds CuNi 3 Sn 8 and CuNi 4 Sn 7 were detected with a ratio (p + r) / s of 1 1, 5 and 13.3.
  • the first and second phase components of the metallic matrix are predominantly crystallized in the region of the crystallization nuclei and encase them.
  • Embodiment A gave indications of the compound SiB 6 as a representative of the Si-containing and B-containing phases, Ni 6 Si 2 B as a representative of the Ni-Si borides, on Ni 3 B as a representative of the Ni borides, on Ni 3 P as a representative of Ni phosphides, on Mg 3 P 2 as a representative of Mg phosphides, on Ni 2 Si as a representative of Ni silicides, on Mg 2 Si as a representative of Mg silicides and on Cu 4 SnMg as a representative of Cu -containing and Sn-containing and Mg-containing phases, which individually and / or as
  • Addition compounds and / or mixed compounds are present in the microstructure.
  • these hard particles are of tin and / or the first
  • Phase components and / or second phase components of the metallic Encased in the basic material Phase components and / or second phase components of the metallic Encased in the basic material.
  • Cast structure of the embodiment A of the invention has a grain size of less than 10 pm.
  • Embodiment A of the hard particles precipitated according to the invention the hardness HB of the casting state with 143 is significantly higher than the hardness of 94 HB of the continuous casting of R (Table 2).
  • Tab. 2 Also shown in Tab. 2 are the hardness values which were determined on the continuous casting of alloys A and R at a storage time of 3 hours at 400 ° C. The hardness increase from 94 to 145 HB falls at the
  • Reference material R is the largest.
  • the hardening is due in particular to a thermally activated segregation of the Sn-rich phase in the microstructure.
  • the tin-enriched phase components are distinguished in the structure of the embodiment A much finer in the hard particles. For this reason, the hardness increases from 143 to 151 HB not so pronounced.
  • An object of the invention is to maintain the good
  • Kaltumformgrad made. Due to the high hardness of the cast state of the embodiment A, this was annealed at the temperature of 740 ° C with the duration of 2 hours and then accelerated accelerated in water. As a result, the properties of the cast state of A and R were approximated with respect to strength and hardness.
  • the temperature sensitivity of the reference material R with regard to the formation of the Sn-rich segregations was also evident in the annealing between the two cold forming steps (No. 4 in Tab. 3). For this reason, the annealing temperature of 740 ° C used for the intermediate annealing of the cold rolled plate of alloy A had to be lowered to 690 ° C for R.
  • recrystallization of the microstructure of alloy A takes place from the temperature of about 400 ° C. This recrystallization leads to a decrease in strength and hardness, so that the effect of the precipitation hardening and the spinodal segregation can not fully take effect.
  • the hard particles of the second class are contained after aging at 450 ° C. (denoted by 3 in FIG. 3). Furthermore, further phases have been eliminated in the structure of the further processed alloy A. These include those designated in Fig. 3 with 4
  • Hard particles of the third class of less than 3 pm characteristic It is for the further processed embodiment A of the invention after aging at 450 ° C even less than 1 pm (in Fig. 4 denoted by 5).
  • Table 4 Grain size, electrical conductivity and mechanical characteristics of the cold-rolled and aged strips of alloys A and R after passing through production program 1 (Table 3)
  • This production program 2 pursued the goal of processing the continuous casting plates of materials A and R into strips by means of cold forming and annealing, identical parameters being used for the cold forming degrees and the annealing temperatures (Table 5). Due to the high hardness of the cast state of the embodiment A, this in turn was annealed before the first cold rolling step at the temperature of 740 ° C for a period of 2 hours and subsequently accelerated in water accelerated. As a result, as in the production program 1, the alignment of the properties of the cast state of A and R with respect to strength and hardness was carried out.
  • the bands of embodiment A After the last cold rolling step to the final thickness of 3.0 mm, the bands of embodiment A have the highest strength values and hardness values (Table 6). Due to the three-hour aging at 400 ° C falls due to the spinodal
  • the structure of the outsourced states of the alloy R is very uneven with a particle size of between 5 and 30 ⁇ .
  • the structure of the outsourced states of the reference material R is characterized by discontinuous precipitates of the system (Cu, Ni) -Sn (denoted 1 in FIG. 1 and FIG. 2).
  • the structure of the processed state of the Reference material R are further Ni-phosphides included (in Fig. 1 and Fig. 2 denoted by 2).
  • the size of the hard particles of the third class is even less than 1 ⁇ m after aging at 450 ° C. (denoted by 5 in FIG. 6).
  • the next step involved testing the hot workability of the continuous castings of alloys A and R.
  • the hot rolling of the cast plates was carried out at a temperature of 720 ° C (Table 7). For the others
  • Embodiment A of the invention could be hot rolled without damage and made after several cold rolling and annealing processes to the final thickness of 3.0 mm.
  • Sintered belts (Table 8) largely correspond to those of the belts that were produced without hot forming with the production program 2 (Table 6). Also comparable is the structure of the bands from the
  • Embodiment A of the alloy according to the invention which were manufactured without and with a hot-forming step.
  • FIGS. 7 and 8 again show the hard particles of the second class designated 3.
  • Precipitations of the system (Cu, Ni) -Sn and the hard particles of the third class are made of the system (Cu, Ni) -Sn and the hard particles of the third class.
  • the hard particles of the third class even assume a size of less than 1 pm (denoted by 5 in FIG. 8).
  • Tab. 9 lists the process steps used in production program 4. The production took place with one cycle
  • the low cold forming of the first cold rolling step of ⁇ 16% was not sufficient to eliminate together with the subsequent annealing at 690 ° C, the dendritic and coarse-grained structure of the reference material R.
  • the assignment of the grain boundaries of the alloy R reinforced with Sn-rich segregations was not sufficient to eliminate together with the subsequent annealing at 690 ° C, the dendritic and coarse-grained structure of the reference material R.
  • the crack-free and uniform structure of the bands of embodiment A is characterized by the arrangement of hard particles of the second and third class.
  • the hard particles of the third class also have a size of less than 1 ⁇ even after this production program 4.
  • the resulting properties of the strips after the last cold rolling and after aging are shown in Table 10. Due to the high density of Cracks it was not possible to remove damage-free tensile specimens from the tapes of the material R. Thus, only the metallographic examination and the hardness measurement on these bands could be made.
  • the embodiment A has a high degree of outsourcing capability, which manifests itself through an interaction of the mechanisms of precipitation hardening and the spinodal segregation of the structure.
  • the characteristic values R m and R p0 , 2 increase from 522 to 620 and from 460 to 547 MPa due to aging at 400 ° C.
  • Table 10 Grain size, electrical conductivity and mechanical characteristics of the cold-rolled and aged strips of alloys A and R after passing through production program 4 (Table 9)
  • Precipitation hardening and the degree of spinodal segregation of the microstructure of the invention can be adapted to the required material properties In this way it is possible, in particular the strength, hardness, ductility and to align the electrical conductivity of the alloy according to the invention specifically to the intended application.

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Abstract

L'invention concerne un alliage cuivre-nickel-étain haute résistance, présentant d'excellentes aptitudes au moulage, au formage à chaud et au formage à froid, une résistance élevée à l'usure par abrasion, à l'usure par adhérence, et à l'usure de contact, ainsi qu'une résistance améliorée à la corrosion et à la relaxation des contraintes, composé de (en % en poids) : 2,0 à 10,0 % de Ni, 2,0 à 10,0 % de Sn, 0,01 à 0,8 % de Mg, 0,01 à 1,5 % de Si, 0,002 à 0,45 % de B, 0,004 à 0,3 % de P, auxquels peuvent s'ajouter en option jusqu'à 2,0 % max. de Co, en option jusqu'à 2,5 % max. de Zn, et en option jusqu'à 0,25% max. de Pb, le reste se composant de cuivre et d'impuretés inévitables, caractérisé en ce que le rapport Si/B des teneurs en % en poids en éléments silicium et bore est au minimum de 0,4 et au maximum de 8 ; en ce que l'alliage cuivre-nickel-étain comporte des phases contenant du Si et des phases contenant du B, ainsi que des phases des systèmes Ni-Si-B, Ni-B, Ni-P, Mg-P, Ni-Si, Mg-Si et des phases additionnelles contenant du Mg, qui améliorent notablement les caractéristiques de traitement et d'utilisation de l'alliage. L'invention concerne en outre une variante moulée et une variante ayant subi des traitements additionnels dudit alliage cuivre-nickel-étain haute résistance, un procédé de préparation de cet alliage, ainsi que son utilisation.
EP17736566.5A 2016-07-18 2017-06-27 Alliage cuivre-nickel-étain, procédé de préparation et utilisation de celui-ci Active EP3485048B1 (fr)

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DE102016008745.5A DE102016008745B4 (de) 2016-07-18 2016-07-18 Kupfer-Nickel-Zinn-Legierung, Verfahren zu deren Herstellung sowie deren Verwendung
PCT/EP2017/000755 WO2018014990A1 (fr) 2016-07-18 2017-06-27 Alliage cuivre-nickel-étain, procédé de préparation et utilisation de celui-ci

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CN111020282B (zh) * 2019-12-09 2021-03-16 苏州天兼新材料科技有限公司 一种电力设备用铜基合金材料
DE102020004652B3 (de) * 2020-07-31 2021-12-16 Wieland-Werke Aktiengesellschaft Verfahren zur Herstellung eines Gleitelements
JP2024056397A (ja) * 2022-10-11 2024-04-23 大同メタル工業株式会社 摺動部材およびその製造方法
CN115627379B (zh) * 2022-10-31 2023-12-26 宁波金田铜业(集团)股份有限公司 一种铜合金棒材及其制备方法

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WO2018014990A1 (fr) 2018-01-25
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US20200208240A9 (en) 2020-07-02
DE102016008745B4 (de) 2019-09-12
US11035025B2 (en) 2021-06-15
US20190153564A1 (en) 2019-05-23

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