EP3423605A1 - Alliage de cuivre contenant de l'étain, procédé pour sa préparation ainsi que son utilisation - Google Patents

Alliage de cuivre contenant de l'étain, procédé pour sa préparation ainsi que son utilisation

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Publication number
EP3423605A1
EP3423605A1 EP17708428.2A EP17708428A EP3423605A1 EP 3423605 A1 EP3423605 A1 EP 3423605A1 EP 17708428 A EP17708428 A EP 17708428A EP 3423605 A1 EP3423605 A1 EP 3423605A1
Authority
EP
European Patent Office
Prior art keywords
tin
alloy
optionally
copper alloy
maximum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17708428.2A
Other languages
German (de)
English (en)
Other versions
EP3423605B1 (fr
Inventor
Kai Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
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Wieland Werke AG
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Filing date
Publication date
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Publication of EP3423605A1 publication Critical patent/EP3423605A1/fr
Application granted granted Critical
Publication of EP3423605B1 publication Critical patent/EP3423605B1/fr
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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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
    • 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

  • Tin-containing copper alloy Tin-containing copper alloy, process for their preparation and their
  • the invention relates to a tin-containing copper alloy with excellent
  • Hot workability and cold workability, high resistance to abrasive wear, adhesive wear and fretting wear, and improved corrosion resistance and stress relaxation resistance according to the preamble of any one of claims 1 to 3, a method of the same
  • copper-tin alloys Due to the alloying component tin, copper-tin alloys are characterized by a high strength and hardness. Furthermore, the copper-tin alloys are considered corrosion-resistant and seawater resistant.
  • 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 and sliding surfaces in engine and vehicle construction and in general mechanical engineering. Often the copper-tin alloys for sliding bearing applications to improve the
  • Copper-tin alloys are widely used in the electronics and telecommunications industries. They often have sufficient electrical conductivity and good to very good spring properties. The Setting the spring properties requires sufficient cold workability of the materials.
  • percussion instruments made of copper-tin alloys are preferably produced on account of their special sound properties.
  • the copper-tin materials tend to be particularly strong due to their wide solidification interval
  • the element phosphorus is added to the copper-tin alloys to deoxidize the melt sufficiently. However, phosphorus extends that
  • Cooling rate the hot working of the material at 720 to 920 ° C take place.
  • the document DE 704 398 A discloses the description of a method for producing copper-tin alloy fittings comprising 6 to 14% by weight of Sn, more than 0.1% by weight of P, preferably 0.2 to 0 , 4 wt .-% P, which may be replaced by silicon, boron or beryllium included.
  • the copper-tin alloy comprises about 91.2 wt% Cu, about 8.5 wt% Sn, and about 0.3% P.
  • the moldings are homogenized at a temperature below 700 ° C. until the tin and phosphorus-enriched eutectoids are dissolved.
  • the Schwingreibverschl salt in the jargon also called fretting, is a Reibverschl composition that occurs between oscillating contact surfaces.
  • fretting is a Reibverschl 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
  • Plain bearing built a high voltage, which is further increased by the thermal strains and the dynamic shaft loads in modern engines. Due to the geometry changes of the sliding bearing due to the voltage increase micro-movements of the sliding bearing relative to the bearing receptacle are possible. The cyclic relative movements with less Vibration width at the contact surfaces between bearing and bearing support lead to vibration-wear / fretting corrosion / fretting of the Glejtlagerbaumens. The result is the initiation of cracks and ultimately the Reibdauerbruch of the plain bearing.
  • connection elements of a connection arrangement are located on different assemblies which perform relative movements relative to one another as a result of mechanical loads, a corresponding relative movement of the connection elements can occur. These relative movements lead to a Schwingreibverschl foundation and to a fretting corrosion of
  • Reibkorrosions of connectors on the material side can be improved.
  • a contact material of a silver, palladium or palladium-silver alloy containing 20 to 50% by weight of tin, indium and / or antimony is applied to a support made of bronze.
  • the silver and / or palladium content ensures corrosion resistance.
  • the oxides of tin, indium and / or antimony increase the wear resistance.
  • the Consequences of a fretting corrosion are encountered.
  • Crystallization nuclei present or is formed in the melt only a small number of nuclei, so is a coarse grained, seigerungsreiches and often dendritic solidification microstructure. It is called a copper alloy with 0.1 to 25 wt .-% calcium and 0, 1 to 15 wt .-% boron, which can be added to the grain refining of the melt of copper materials. In this way, with the addition of crystallizers, a uniform and fine-grained solidification microstructure is produced in copper alloys.
  • Phosphorus succeeds in lowering the relatively high base melt temperature in terms of processing technology.
  • High-temperature materials of the systems Ni-Si-B and Ni-Cr-Si-B are especially the alloying elements boron and silicon for the strong lowering of the
  • the lowering of the base melt temperature by the addition of boron is used for copper-tin materials, which are used as build-up welding material
  • US Pat. No. 3,392,017 A discloses an alloy containing up to 0.4% by weight of Si, from 0.02 to 0.5% by weight of B, from 0.1 to 1.0% by weight of P, 4 to 25 wt .-% Sn and a remainder Cu disclosed.
  • the addition of boron and a very high content of phosphorus of greater than or equal to 0.1 wt .-% should hereby the self-fluxing properties of the hardfacing and the
  • the document DE 102 08 635 B4 describes the processes in a diffusion solder joint in which intermetallic phases are present. By diffusion soldering parts with a different coefficient of thermal expansion are to be connected to each other. With thermomechanical loading of this solder joint or during the soldering process itself, large voltages occur at the
  • particles of boron silicates or phosphorus silicates can be used due to their
  • a starting material may be used that has been prepared by conventional casting methods without the urgent need to carry out spray compacting or strip casting.
  • the copper-tin alloy should be free of gas and shrinkage pores and stress cracks and should be characterized by a uniform distribution of the Sn-rich ⁇ phase present in relation to the Sn content of the alloy.
  • the cast state of the copper-tin alloy does not necessarily have to be homogenized by means of a suitable annealing treatment in order to be able to produce sufficient hot workability.
  • the casting material should be characterized by a high strength, a high hardness and a high corrosion resistance.
  • a further processing which includes an annealing or a hot forming and / or cold working with at least one annealing, is a fine-grained structure with high strength, high hardness, high stress relaxation and corrosion resistance, high electrical conductivity and a high degree of complexity
  • the invention includes a high strength tin-containing copper alloy having excellent hot workability and cold improvability, high resistance to abrasive wear, adhesive wear and fretting wear, and improved corrosion resistance, and
  • the invention includes a high strength tin-containing copper alloy excellent in hot workability and cold workability
  • remainder copper mixed crystal consisting of tin-poor a-phase, wherein the Si-containing and B-containing phases of tin and / or the Sn rich ⁇ phase are coated;
  • the Si-containing and B-containing phases which are formed as silicon borides, nuclei for a uniform crystallization during the solidification / cooling of the melt, so that the
  • Sn-rich ⁇ -phase is distributed island-like and / or net-like uniformly in the structure
  • Si-containing and B-containing phases which are formed as boron silicates and / or Borphosphorsilikate, together with the
  • Phosphorsilikaten take over the role of a wear-protective and / or corrosion-protective coating on the semi-finished products and components of the alloy.
  • the structure Due to the uniform distribution of the Sn-rich ⁇ phase in island form and / or in net shape, the structure is free of Sn-rich segregations. Under such rich segregations are ⁇ -phase accumulations in the cast structure understood as so-called reverse block segregations and / or
  • Grain boundary segregations are formed, 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 after casting is still free of gas pores and shrinkage pores and stress cracks.
  • the alloy is in the cast state.
  • the invention includes a high strength tin-containing copper alloy having excellent hot workability and cold workability
  • the following structural constituents are present: a) up to 75% by volume of Sn-rich ⁇ -phase, b) 1 up to 20% by volume of Si-containing and B-containing phases,
  • Si-containing and B-containing phases are coated with tin and / or the Sn-rich ⁇ phase;
  • Silicon borides are formed, germs for a static and dynamic
  • the Si-containing and B-containing phases which are formed as boron silicates and / or Borphosphorsilikate, take over together with the phosphorus silicates the role of a wear-protective and / or corrosion-protective coating on the semi-finished products and components of the alloy.
  • the Sn-rich ⁇ phase is preferably at least 1% by volume.
  • the Sn-rich ⁇ -phase is uniformly distributed in the structure like an island and / or net-like and / or line-like stretched.
  • the alloy is in the processed state.
  • the invention is based on the consideration in the alloy variants that a tin-containing copper alloy in the cast state as well as in
  • Si-containing and B-containing phases which can be produced by means of the sand casting, shell molding, precision casting, full cast, die casting and chill casting process or by means of the continuous or semi-continuous continuous casting process.
  • process-technically complex and cost-intensive arching techniques is possible, but provides for the preparation of tin-containing invention
  • Copper alloy is not a mandatory requirement dar.
  • the casting formats of Tin-containing copper alloy according to the present invention can be hot-worked over the entire range of Sn content, for example, by hot rolling, extrusion or forging.
  • the Sn content of the alloy according to the invention increases, not only does the proportion of the ⁇ phase in the microstructure increase, but the shape of the arrangement of the ⁇ phase in the microstructure also changes.
  • the ⁇ -phase with up to 40 vol .-% is distributed evenly in island form uniformly in the structure.
  • the Sn content of the alloy is between 9.0 and 13.0% by weight, the island shape of the ⁇ phase, which is present in the microstructure with up to 60% by volume, changes into the network form. This ⁇ mesh is also distributed very uniformly in the structure of the alloy.
  • the ⁇ phase with up to 80 vol .-% is almost exclusively in the form of a uniform network in the structure.
  • Sn content of the alloy of 17.0 to 23.0 wt .-% is the
  • the elements boron and silicon have a special significance in the tin-containing copper alloy according to the invention.
  • the phases of the system Si-B precipitate.
  • These SiB phases can be present in the modifications SiB 3 , SiB 4 , SiB 6 and SiB n .
  • the symbol "n" in the latter modification is based on the fact that boron has a high solubility in the silicon lattice.
  • the Si-containing and B-containing phases, which are formed as silicon borides, are referred to below as hard particles
  • the alloy according to the invention has the function of crystallization nuclei during solidification and cooling. As a result, there is no longer any need to supply so-called foreign nuclei to the melt, which has a uniform shape
  • the casting state of the invention depending on the Sn content, has a very uniform microstructure with a fine distribution of the ⁇ phase in the form of uniformly and densely arranged islands and / or in the form of a uniformly dense network.
  • Accumulations of Sn-rich ⁇ -phase known as so-called reverse block segregations and / or as
  • Grain boundary segregations are formed, can not be observed in the cast structure of the invention.
  • the elements boron, silicon and phosphorus cause a reduction of the metal oxides.
  • the elements are themselves oxidized, rise to the surface of the castings and form there as boron silicates, phosphorus silicates and / or Borphosphorsilikate a protective layer that protects the castings from gas absorption.
  • a basic idea of the invention consists in the transfer of the effect of boron silicates and phosphorus silicates with regard to the matching of the different coefficients of thermal expansion of the joining partners during diffusion soldering to the processes during casting, hot forming and thermal treatment of the copper-tin materials. Due to the wide solidification interval of this
  • Alloys are between the offset-crystallizing Sn-poor and Sn-rich structural areas to large mechanical stresses that can lead to cracks and pores. Furthermore, these damage characteristics can also be applied during hot forming and high-temperature annealing of the copper-tin oxide Alloys due to the different hot forming behavior and the different thermal expansion coefficient of Sn-poor and Sn-rich microstructural constituents occur.
  • tin-containing copper alloy according to the invention causes on the one hand during the solidification of the melt by means of the action of the hard particles as
  • Crystallization nuclei a uniform structure with a fine distribution of the structural components with different Sn content.
  • Hard particles ensure that during the solidification of the melt forming boron silicates, phosphorus silicates and / or Borphosphorsilikate the necessary equalization of the thermal expansion coefficients of the Sn-poor and Sn-rich phases. In this way, the formation of pores and stress cracks between the phases with different Sn content is prevented.
  • 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.
  • the hard particles are responsible for the fact that the dynamic recrystallization takes place favorably in the hot working of the alloy according to the invention. This results in a further increase in the uniformity and the fine grain of the microstructure. As after casting, so could after hot forming of the
  • Recrystallization was manifested in the possible lowering of the necessary recrystallization temperature, which additionally facilitates the adjustment of a fine-grained microstructure of the alloy according to the invention.
  • the height of the parameter R p o, 2 is for the sliding elements and guide elements in internal combustion engines, valves, turbochargers,
  • the Sn content of the invention is in the limits between 4.0 and 23.0 Wt .-%.
  • a tin content of less than 4.0 wt .-% would result in low strength values and hardness values.
  • the running properties would be insufficient in a sliding load.
  • the resistance of the alloy to the abrasive and adhesive wear would not meet the requirements.
  • the toughness properties of the alloy according to the invention would rapidly deteriorate, causing the
  • the alloy according to the invention has a hard phase component which, due to the high hardness of the silicon borides, contributes to an improvement in the material resistance to abrasive wear.
  • Hard particles, the hot strength and stress relaxation resistance of components of the invention This is an important prerequisite for the use of the alloy according to the invention, in particular for sliding elements and for components, line elements, guide elements and
  • silicate phases also take on the role of a wear-protective and / or
  • the alloy of the present invention ensures a combination of the properties of wear resistance and corrosion resistance. These Property combination leads to a requirement high resistance to the mechanisms of sliding wear and a high
  • the invention is outstandingly suitable for use as a sliding element and connector, since it has a high degree of resistance to sliding wear and the Schwingreibverschl altern, the so-called fretting.
  • the effect of the hard particles as crystallization nuclei and recrystallization nuclei, as wear carriers and the effect of the silicate phases for the purpose of corrosion protection can only achieve a technically significant degree in the alloy according to the invention if the silicon content is at least 0.05% by weight and the boron Content is at least 0.005 wt .-%. On the other hand, if the Si content exceeds 2.0 wt% and / or the B content exceeds 0.6 wt%, the casting performance is deteriorated. The too high content of hard particles 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 1, 5 wt .-% and in particular from 0.5 to 1, 5 wt -% evaluated.
  • the content of 0.01 to 0.6 wt .-% is considered advantageous.
  • the content of boron has proven to be particularly advantageous from 0.1 to 0.6% by weight.
  • Element contents (in% by weight) of the elements silicon and boron of A ratio Si / B of 1 to 10 and further from 1 to 6 has proved to be particularly advantageous.
  • the precipitation of hard particles influences the viscosity of the melt of the alloy according to the invention. This circumstance also underlines why it may not be waived to add phosphorus. Phosphor causes the melt, despite the content of hard particles is sufficiently thin liquid, which is of great importance for the pourability of the invention.
  • the content of phosphorus of the alloy according to the invention is 0.001 to 0.08 wt .-%. A P content in the range of 0.001 to 0.05 wt .-% is advantageous.
  • the sum of the element contents of the elements silicon, boron and phosphorus is advantageously at least 0.5% by weight.
  • Machining area of the machine must be removed.
  • the hard particles in whose regions, depending on the Sn content of the alloy, the element tin and / or the ⁇ phase crystallized or precipitated, serve as chip breakers.
  • the tin-containing Copper alloys consist of (in% by weight):
  • tin-containing copper alloy consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • the Sn-rich ⁇ phase is uniformly arranged in island form up to 40% by volume.
  • the element tin and / or the ⁇ phase is usually crystallized in the regions of the hard particles and / or encapsulates these.
  • the castings of these embodiments have excellent hot workability at the working temperature in the range of 600 to 880 ° C.
  • the dynamic recrystallization favored by the hard particles is the structure of the embodiments according to the
  • the hard particles precipitated in the microstructure act in the thermal
  • Recrystallization nuclei By means of this further processing step, it is possible to set a structure with a particle size of up to 20 ⁇ m. The favor of the
  • Recrystallization by the hard particles allows a lowering of the recrystallization temperature, so that a microstructure can be produced with a particle size up to 10 pm.
  • values for the tensile strength R m of over 700 to 800 MPa can be achieved by over 600 to 700 MPa.
  • the toughness properties of the embodiments are at a very high level. This fact is expressed by the high values for the elongation at break A5.
  • Copper alloys consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • microstructure of these embodiments of the invention is characterized by a content of the ⁇ -phase of up to 60 vol .-%, this phase in
  • Island shape and network shape is uniformly distributed in the structure.
  • the element tin and / or the ⁇ -phase is usually crystallized in the areas of hard particles and / or encapsulates them.
  • the castings of these embodiments have excellent hot workability at the working temperature in the range of 600 to 880 ° C.
  • Hot working in air or in water and / or by an annealing after the hot forming process at the temperature of 200 to 880 ° C with a duration of 10 minutes to 6 hours can be further improved.
  • the microstructural feature of the crystallization of the element tin and / or the ⁇ -phase in the areas of the hard particles and / or the cladding of these hard particles with the element tin and / or the ⁇ -phase with respect to the casting state is more fully pronounced.
  • the hard particles precipitated in the microstructure act in the thermal
  • Recrystallization nuclei By means of this further processing step, it is possible to set a finer grain structure.
  • Recrystallization through the hard particles allows a lowering of the recrystallization temperature, so that a microstructure with a further reduced particle size can be generated.
  • the fine grain of the microstructure can be further optimized.
  • Copper alloys consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • the ⁇ phase in the cast structure of these embodiments of the invention is in the form of a uniform network of up to 80% by volume.
  • the element tin and / or the ⁇ phase is usually crystallized in the regions of the hard particles and / or encapsulates these.
  • the castings of these embodiments also exhibit excellent hot workability at the working temperature in the range of 600 to 880 ° C. Especially in this content range for the alloying element tin of 13.0 to 17.0 wt .-%, the conventional copper-tin alloys are very difficult without the occurrence of hot cracks and warm breaks
  • the hard particles precipitated in the microstructure act in the thermal
  • Recrystallization nuclei By means of this further processing step, it is possible to set a microstructure with a grain size of up to 30 ⁇ m.
  • the favoring of the recrystallization mechanisms by the hard particles allows a lowering of the recrystallization temperature so that a structure with a grain size of up to 15 m can be produced.
  • the net-like arrangement of the ⁇ phase in the microstructure is retained.
  • Recrystallization temperature it is even possible to adjust the size of the crystallites in the material structure to less than 5 pm.
  • Copper alloys consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • the tin-containing copper alloy may consist of (in% by weight):
  • a very dense network of the ⁇ -phase which is uniformly arranged in the structure with up to 98% by volume, is a feature of these embodiments of the invention.
  • the element tin and / or the ⁇ phase is usually crystallized in the regions of the hard particles and / or encapsulates these.
  • the castings of these embodiments also exhibit excellent hot workability at the working temperature in the range of 600 to 880 ° C.
  • 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 hard particles cause a higher temperature stability of the microstructure of the copper alloy according to the invention.
  • the element zinc can be added to the tin-containing copper alloy according to the invention with a content of 0.1 to 2.0 wt .-%. It has been found that the alloying element zinc, depending on the Sn content of the alloy, increases the proportion of Sn-rich phases in the invention, whereby strength and hardness increase. However, no evidence was found that adding zinc has a positive effect on the uniformity of the microstructure as well as on further reducing the content of pores and cracks in the microstructure. Obviously, the relative influence of the combined alloy content on boron, silicon and phosphorus predominates. Under 0.1% by weight of Zn, a strength and hardness increasing effect could not be observed. At Zn contents above 2.0 wt%, the toughness properties of the alloy were lowered to a lower level. In addition, the deteriorated
  • the invention may be added to a zinc content in the range of 0.5 to 1, 5 wt .-%.
  • a zinc content in the range of 0.5 to 1, 5 wt .-%.
  • the addition of the alloying elements iron and magnesium can be done individually or in combination.
  • the alloy according to the invention may contain from 0.01 to 0.6% by weight of iron.
  • in the Microstructures are thus up to 10 vol .-% Fe borides, Fe phosphides and Fe silicides and / or Fe-rich particles before. Furthermore, it comes in the structure for the formation of addition compounds and / or mixed compounds of the Fe-containing phases and the Si-containing and B-containing phases.
  • the element of magnesium of 15 0.01 to 0.5 wt .-% may be added to the alloy according to the invention.
  • up to 15% by volume of Mg borides, Mg phosphides and Cu-Mg phases and Cu-Sn-Mg phases are present in the microstructure. Furthermore, it comes in the structure for the training of
  • the tin-containing copper alloy may have low levels of lead. Just acceptable and lying above the impurity limit are lead contents up to 0.25 wt .-%. In a particularly preferred
  • the tin-containing copper alloy is free of lead, except for any unavoidable impurities.
  • the extensive freedom of the structure of gas pores and shrinkage pores, voids, Seigerungen and cracks is considered in the cast state.
  • the alloy composition according to the invention in particular the formation of an open porosity can be suppressed during the reflow process, whereby the
  • Compressive strength of the sliding layer is increased.
  • an aspect of the invention includes a method for
  • an aspect of the invention includes a method of making tapes, sheets, plates, bolts, round wires, tread wires, round bars, section bars, hollow bars, tubes and profiles from a present invention tin-containing copper alloy by means of the chill casting process or the continuous or semi-continuous continuous casting process.
  • ⁇ -phase which is already uniformly and finely distributed in the cast structure of the alloy according to the invention with a corresponding Sn content, assumes an essential function for the service properties of the alloy.
  • the further processing of the casting state the implementation of at least one hot working in the temperature range of 600 to 880 ° C include.
  • the cooling of the semi-finished products and components can be carried out after the hot deformation of calmed or accelerated air or water.
  • Temperature range from 200 to 880 ° C with the duration of 10 minutes to 6
  • One aspect of the invention relates to an advantageous process for further processing the cast state or the hot worked state or the annealed cast state or the annealed hot worked state which comprises the
  • Implementation of at least one cold forming comprises.
  • At least one annealing treatment of the cold-worked state of the invention may be performed in the temperature range of 200 to 880 ° C for a period of 10 minutes to 6 hours.
  • flash annealing may be performed in the temperature range of 200 to 650 ° C for 0.5 to 6 hours.
  • the matrix of the uniform structure of the invention consists of ductile a-phase with, depending on the Sn content of the alloy, of ⁇ -phase fractions. Due to its high strength and hardness, the ⁇ phase leads to the high resistance of the alloy to abrasive wear. In addition, due to its high Sn content, which results in its tendency to form a tribo layer, the ⁇ phase increases the resistance of the material to the adhesive
  • the hard particles are embedded in the metallic matrix. In further embodiments of the invention are still in the metallic
  • Base mass precipitated Fe and / or Mg-containing phases added.
  • the alloy according to the invention Due to the uniform and fine-grained structure with extensive freedom from pores, freedom from cracks and freedom from segregation and the content of hard particles, the alloy according to the invention already has a high degree of strength, hardness, ductility, complex wear resistance and as-cast condition
  • the alloy according to the invention has a wide range of uses already in the cast state.
  • Treatment temperatures for tempered steels (hardening 820 to 860 ° C, tempering 540 to 660 ° C, DIN EN 10083-1) in the heat treatment range of
  • bearing composite shells or composite bearing bushes can be produced by roll cladding, inductive or conductive roll cladding or by laser cladding. Walzplattieren be produced.
  • Sliding elements and guide elements in internal combustion engines, valves, turbochargers, transmissions, exhaust aftertreatment systems, lever systems, brake systems and components can already be found in the casting formats in strip form, sheet form, plate form, bolt form, wire form, rod form, tubular form or profile shape
  • Joint systems, hydraulic units or in machinery and equipment of general engineering can be produced.
  • semi-finished products and components with complicated geometry and increased mechanical properties can be used for these applications
  • the invention is suitable for the metal objects in constructions for the rearing of marine organisms (aquaculture).
  • Another aspect of the invention includes use of the tin-containing copper alloy for propellers, blades,
  • Ship propellers and hubs for shipbuilding for housings of water pumps, oil pumps and fuel pumps, for guide wheels, impellers and impellers for pumps and water turbines, for gears, worm wheels, helical gears, as well as for pressure nuts and spindle nuts, as well as for pipes, gaskets and seals Connecting bolts in the maritime and chemical industry.
  • the material is of great importance. Especially, the material is of great importance.
  • Basins so-called cymbals, of high quality are made of tin-containing copper alloys by means of hot forming and at least one annealing before they are usually brought by means of a bell or a bowl in the final shape. The basins are then annealed again before their final machining takes place.
  • the production of the different variants of the pools for example ride cymbals, hi-hat, crash cymbals, China cymbals, splash cymbals and effect cymbals, thus requires a particularly advantageous hot workability of the material, which is ensured by the alloy according to the invention.
  • different microstructural fractions for the ⁇ -phase and for the 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.
  • Tab. 1 shows the chemical composition of alloy variants 1 and 2. These materials are characterized by an Sn content of about 7 wt .-%, a P content of 0.015 wt .-% and by a different
  • the structure of embodiments 1 and 2 is characterized by a very uniform, mostly island-shaped distribution of a relatively small proportion of the ⁇ -phase (about 15 to 20% by volume) and the hard particles.
  • the texture of the cast state of Alloy 1 is shown in Fig. 1 (200x magnification). It can be seen that the Sn-rich ⁇ -phase 1 is uniformly arranged like an island in the copper mixed crystal 3 consisting of the low-tin ⁇ -phase.
  • the hard particles 2 can be seen, which are coated with tin and / or the Sn rich ⁇ phase.
  • Alloy variant 3 can be seen. This material contains about 15 wt .-% Sn and 0.024 wt .-% P, the other elements Si (0.77 wt .-%) and boron (0.20 wt .-%).
  • the invention is inter alia characterized in that the microstructure casting state with increasing Sn content of the alloy, depending on the casting / cooling process, consists of increasing proportions of ⁇ -phase.
  • the Arrangement of this Sn-rich ⁇ -phase goes from a finely distributed island shape with increasing Sn content of the alloy in a dense network form.
  • Cast structure of alloy grade 3 is the ⁇ phase with a significantly higher content (up to about 70 vol .-%). This structure is shown in Fig. 3 in 200-fold and from Fig. 4 in 500-fold magnification.
  • the reference numeral 1 in Fig. 4 the net-like structure arranged in the Sn-rich ⁇ phase is characterized. Furthermore, the hard particles 2, which are sheathed by tin and / or the Sn-rich ⁇ phase, can be recognized. Labeled by the reference numeral 3 is the
  • Microstructure component of copper mixed crystal is Microstructure component of copper mixed crystal.
  • One aspect of the invention relates to a method for producing strips, sheets, plates, bolts, wires, rods, tubes and profiles from the tin-containing copper alloy according to the invention with the aid of
  • the alloy according to the invention can also be further processed
  • the further processing of the cast state can advantageously comprise carrying out at least one hot working in the temperature range from 600 to 880 ° C.
  • the forging processes are suitable to produce near-net shape components with partly complicated geometry.
  • a further advantageous possibility of further processing the cast state or the hot-formed state or the annealed cast state or the annealed hot-formed state comprises performing at least one cold forming.
  • At least one annealing treatment can be carried out in one
  • Temperature range from 200 to 880 ° C with the duration of 10 minutes to 6
  • a further processing can be selected, which comprises at least one cold working or the combination of at least one hot working and at least one cold forming in conjunction with at least one annealing in a temperature range of 200 to 880 ° C with the duration of 10 minutes to 6 hours and a recrystallized structure of the alloy according to the invention leads.
  • the fine-grained structure of the alloy set in this manner ensures a combination of high strength, high hardness and good toughness properties.
  • to lower the residual stresses of the components a
  • Relaxation annealing in the temperature range from 200 to 650 ° C for a period of 0.5 to 6 hours.
  • the hot-rolled plates could be cold-rolled cold with a cold forming ⁇ of about 70%.
  • the cold-rolled strips were annealed at the temperature of 280 ° C for a period of 2 hours.
  • the characteristic values of the thus relaxed bands are shown in Tab. 6.
  • the bands of both alloys have exceptionally good results
  • Corrosion resistance compared to the alloy 2 found.
  • the values for R m and R p0 , 2 of the strips of alloy 1 are at a significantly higher level.
  • a higher Si content was bound in the hard particles in the structure of the alloy 2.
  • Even the results of the production 1 indicate that with a variation of the chemical composition of the invention, the properties can be adapted exactly to the respective fields of application.
  • the strips of alloy variants 1 and 2 were annealed after the first cold rolling at 680 ° C for 3 hours. Subsequently, the cold rolling of the strips was carried out with a cold forming ⁇ of about 60%. At the end of production, the strips were thermally relaxed at different temperatures between 280 and 400 ° C. The characteristic values of the resulting material states are listed in Tab.
  • Embodiment 1 the higher strength values, whereas the
  • Embodiment 2 characterized by higher values for the electrical conductivity and for the elongation at break A5. Furthermore, from Tab. 7 to
  • Deformation features include why no value for the grain size
  • the temperature of the annealing was reduced to 450 ° C. after the first cold forming. After the three-hour annealing at this temperature, the cold rolling of the strips with the cold forming ⁇ of about 30%. The final two-hour
  • Fig. 2 Final state of the band of the embodiment 1 is shown in Fig. 2. Visible is the fine-grained microstructure with the hard particles 2, which are embedded in the copper mixed crystal 3. The hard particles are coated with tin and / or the Sn-rich ⁇ -phase 1. The results indicate a fully recrystallized microstructure with extremely high strength and hardness values. Nevertheless, the high values for the elongation at break A5 indicate the excellent ductility of the material states. Even after the production 3, the strength values of the states of the alloy 1 are above that of the alloy 2. In contrast, the states of the
  • Table 8 Structural characteristics and mechanical characteristics of the bands of the
  • Table 10 Grain size and hardness of the cold-rolled (after manufacturing step 4 in Tab. 8) and subsequently annealed strips from the exemplary embodiment 3
  • the belt 3-B was subjected to further processing with several cold rolling / annealing cycles.
  • the characteristic values of the end states relaxed at different temperatures are listed in Tab.
  • Embodiment 3 of the invention With each cycle consisting of a cold rolling step and an annealing treatment, the structure of Embodiment 3 of the invention is progressively stretched in a line.
  • the brittle character of the alloy increases, which is expressed by the very low values for the elongation at break A11, 3.
  • Table 11 Structural characteristics and mechanical characteristics of the bands from the
  • the alloy according to the invention has a Sn content of 4 to 23% Sn over the entire range
  • Hard particles encased in tin and / or the Sn-rich ⁇ phase are copper mixed crystal consisting of low-tin a-phase

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Continuous Casting (AREA)
  • Polishing Bodies And Polishing Tools (AREA)

Abstract

L'invention concerne un alliage de cuivre contenant de l'étain très solide à l'état coulé présentant une remarquable aptitude au façonnage à chaud et à froid, une résistance élevée contre l'usure abrasive, contre l'usure adhésive et l'usure par frottement ainsi qu'une résistance améliorée à la corrosion et à la relaxation des contraintes, constitué par (en % en poids) : 4,0 à 23,0 % de Sn, 0,05 à 2,0 % de Si, 0,005 à 0,6 % de B, 0,001 à 0,08 % de P, éventuellement encore jusqu'à maximum 2,0 % de Zn, éventuellement encore jusqu'à maximum 0,6 % de Fe, éventuellement encore jusqu'à maximum 0,5 % de Mg, éventuellement encore jusqu'à maximum 0,25 % de Pb, le reste étant du cuivre et des impuretés inévitables, caractérisé en ce que le rapport Si/B des teneurs élémentaires des éléments silicium et bore est situé entre 0,3 et 10. En outre, l'invention concerne une variante de coulée et une variante perfectionnée de l'alliage de cuivre contenant de l'étain, un procédé de préparation ainsi que l'utilisation de l'alliage.
EP17708428.2A 2016-03-03 2017-02-10 Alliage de cuivre contenant de l'étain, procédé pour sa préparation ainsi que son utilisation Active EP3423605B1 (fr)

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DE102016002618.9A DE102016002618A1 (de) 2016-03-03 2016-03-03 Zinnhaltige Kupferlegierung, Verfahren zu deren Herstellung sowie deren Verwendung
PCT/EP2017/000190 WO2017148569A1 (fr) 2016-03-03 2017-02-10 Alliage de cuivre contenant de l'étain, procédé pour sa préparation ainsi que son utilisation

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CN109903882A (zh) * 2019-03-28 2019-06-18 江苏华威铜业有限公司 一种高耐腐蚀性铜母线及其制备工艺
CN111411259A (zh) * 2020-02-25 2020-07-14 华亿轴承科技（江苏）有限公司 一种无油轴承材料的制备方法
CN111549253B (zh) * 2020-07-03 2021-06-18 江西省科学院应用物理研究所 一种稀土铜铁合金及制备方法和应用

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DE581507C (de) 1928-03-10 1933-07-28 Bruno Sachs Verfahren zum Warmpressbarmachen von Kupfer und Zinn enthaltenden Legierungen
DE704398C (de) 1935-04-06 1941-03-29 Caro Werk Ges M B H Verfahren zur Herstellung von Formstuecken aus Bronze (Kupfer-Zinn-Legierungen)
US2128955A (en) 1937-11-26 1938-09-06 American Brass Co Hot workable phosphor bronze
AT165091B (fr) * 1946-02-08
US3392017A (en) 1965-04-15 1968-07-09 Eutectic Welding Alloys Welding consumable products
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DE2536166A1 (de) 1975-08-13 1977-03-03 Olin Corp Kupferlegierung
DE3627282A1 (de) 1986-08-12 1988-02-18 Sueddeutsche Kalkstickstoff Legierung zur kornfeinung von kupferwerkstoffen
JPS6345342A (ja) * 1986-08-13 1988-02-26 Furukawa Electric Co Ltd:The 高力伝導性銅合金
DE3932536C1 (en) 1989-09-29 1990-08-09 W.C. Heraeus Gmbh, 6450 Hanau, De Wear resistant contact material - in which is applied to support comprising copper alloy and non-noble metal contg. silver, palladium or palladium-silver alloy
DE4126079C2 (de) 1991-08-07 1995-10-12 Wieland Werke Ag Bandgießverfahren für ausscheidungsbildende und/oder spannungsempfindliche und/oder seigerungsanfällige Kupferlegierungen
DE19756815C2 (de) 1997-12-19 2003-01-09 Wieland Werke Ag Kupfer-Knetlegierung, Verfahren zur Herstellung eines Halbzeuges daraus und deren Verwendung
DE10208635B4 (de) 2002-02-28 2010-09-16 Infineon Technologies Ag Diffusionslotstelle, Verbund aus zwei über eine Diffusionslotstelle verbundenen Teilen und Verfahren zur Herstellung der Diffusionslotstelle
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AT511196B1 (de) 2011-06-14 2012-10-15 Miba Gleitlager Gmbh Mehrschichtlagerschale

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WO2017148569A1 (fr) 2017-09-08
CN108713063A (zh) 2018-10-26
MX2018010584A (es) 2018-11-09
KR20180121890A (ko) 2018-11-09
US20200181738A9 (en) 2020-06-11
US20190062875A1 (en) 2019-02-28
CN108713063B (zh) 2020-05-19
DE102016002618A1 (de) 2017-09-07
US11028463B2 (en) 2021-06-08
JP6679741B2 (ja) 2020-04-15
EP3423605B1 (fr) 2021-06-30

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