JP6679742B2 - Tin-containing copper alloy, its manufacturing method, and its use - Google Patents

Description

  The present invention is excellent in hot workability and cold workability described in the preamble of any one of claims 1 to 3, and has high resistance to abrasive wear, adhesive wear and fretting wear, And a tin-containing copper alloy with improved corrosion resistance and stress relaxation resistance, a method for its production according to the preamble of claims 10 to 11, and a method for its use according to the preamble of claims 17 to 19. It is about.

  Due to the alloying component tin, the copper-tin alloy is excellent in high strength and hardness. Moreover, copper-tin alloys are recognized as corrosion and seawater resistant.

  This group of materials has a high resistance to abrasive wear. Moreover, copper-tin alloys exhibit good sliding properties and high fatigue limits, thus demonstrating their excellent suitability as sliding members and surfaces in engine and vehicle construction and in general machine construction. Copper-tin alloys for plain bearing applications often include lead additives to improve galling resistance and machinability.

  Copper-tin alloys are widely used in the electronics and telecommunications industries. They often have sufficient conductivity and good or very good spring properties. Sufficient cold workability of the material is a prerequisite for adjusting the spring properties.

  In the music industry, percussion instruments are advantageously manufactured from copper-tin alloys on the basis of their special acoustic properties. The manufacture of these concave disks, also called cymbals in technical terms, requires that the material has very good hot workability. In particular, two types of copper-tin alloys with 8% and 20% tin by weight are prevalent.

  In the first manufacturing step, casting, the copper-tin material is particularly prone to subsequent bubble formation and segregation after absorbing the gas due to its long solidification period. Sn-rich segregation can be removed in a very limited manner by homogenizing annealing following the casting process. The tendency of bubbles and segregation in copper-tin alloys increases with increasing Sn content.

  Elemental phosphorus is added to the copper-tin alloy to fully deoxidize the melt. However, phosphorus further extends the solidification period of the copper-tin alloy, which results in an increased tendency for bubbles and segregation in this family of materials.

  For this reason, Patent Documents 1 and 2 describe that, in addition to the spray compression method, strip casting is advantageous for the primary molding of a copper-tin alloy. In this way, by accurately adjusting the solidification rate of the melt, it is possible to manufacture a preform with a small segregation in which the δ phase containing a large amount of Sn is finely and uniformly distributed for the subsequent hot working. You can

  US Pat. No. 6,037,898 describes how pure copper-tin alloys with Sn 14 to 32 wt% and alloys containing copper and tin with Sn 10 to 32 wt% can be hot workable. Basic suggestions are given. It is proposed that the alloy be heated to a temperature of 820 to 970 ° C and then cooled at a very slow rate to 520 ° C. At this time, the period of cooling needs to be at least 5 hours. After cooling to room temperature at normal cooling rates, the material can be hot worked at 720 to 920 ° C.

  From US Pat. No. 6,037,009, Sn 6 to 14 wt.%, P greater than 0.1 wt.%, Preferably P 0.2 to 0.4 wt.%, Where P is copper-tin which may be replaced by silicon, boron or beryllium. A method of making a shaped part from an alloy is described. Preferably, the copper-tin alloy has about 91.2 wt% Cu, about 8.5 wt% Sn, and about 0.3 wt% P. According to it, before final processing by cold working or hot working, the castings are homogenized at a temperature below 700 ° C. until the tin and phosphorus enriched eutectoids are dissolved.

  The meanings of crystal nuclei forming a fine grain structure containing a large amount of Sn and having a small segregation ratio due to the hot workability of the Sn-containing copper alloy are described in Patent Documents 5 and 6. The phosphide compound is the crystal nucleus, which causes tempering of the cast structure and reduces the formation of low melting point copper-phosphorus or copper-phosphorus-tin phases to a minimum. Thereby, the hot workability is decisively improved.

  As the operating temperatures and pressures of modern engines, machines, equipment and units increase, different failure mechanisms occur in individual system components. Therefore, in addition to the type of sliding wear, it is also necessary to take into account the mechanism of oscillating frictional wear damage, especially in the material and structural design of the sliding member and the plug connector.

  Vibration friction wear, also called fretting in technical terms, is the friction wear that occurs between vibrating contact surfaces. In addition to geometrical and / or volumetric wear of the parts, further reaction with the surrounding medium results in frictional corrosion. Due to material damage, the partial strength of the wear area, in particular the fatigue limit, can be significantly reduced. Vibrational cracks leading to vibrational / friction-fatigue fractures can start from the damaged part surface. Under frictional corrosion, the fatigue limit of a part may be significantly below the fatigue limit characteristic value of the material.

  Vibratory friction wear is significantly different in its mechanism from the types of sliding wear with unidirectional movement. Particularly, the influence of corrosion due to vibration friction wear is particularly remarkable.

  From Patent Document 7, a description of the damage result of the vibration friction wear of the plain bearing can be seen. The process of press-fitting the plain bearing into the bearing receptacle creates high stresses in the plain bearing, which are further increased by thermal expansion and by dynamic axial loads in modern engines. The change in shape of the plain bearing due to the excessive increase in stress allows a fine movement of the plain bearing relative to the bearing receiver. Due to the small relative amplitude of the cyclic relative movements at the contact surface between the bearing and the bearing receiver, a vibrating friction wear / friction corrosion / fretting of the sliding bearing back surface occurs. As a result, cracks start and finally frictional fatigue failure of the plain bearing occurs.

  In engines and machines, electrical plug connectors are often located on the periphery where they are exposed to mechanical oscillatory motion. If the components of the connecting device are in different assemblies that move relative to each other under mechanical load, mutual movement of the connecting members may result. These mutual movements result in oscillating frictional wear and frictional corrosion in the contact area of the plug connector. Microcracks form in this contact area, which significantly reduces the fatigue limit of the plug connector material. This may result in the plug connector dropping due to fatigue failure. Further, frictional corrosion causes an increase in contact resistance.

  In order to reduce these types of damage, Patent Document 8 proposes to structurally install a strain relief device on every wire connected to the plug connector so that movement of the wire cannot reach the plug connector. are doing.

  US Pat. No. 6,037,049 contains instructions on how the frictional corrosion behavior of a plug connector can be improved from the material side. That is, for example, a support material made of bronze is coated with a contact material consisting of a silver-, palladium- or palladium-silver-alloy with a content of 20 to 50% by weight of tin, indium and / or antimony. The silver and / or palladium content ensures corrosion resistance. Oxides of tin, indium and / or antimony enhance wear resistance. Nevertheless, the consequences of frictional corrosion may occur.

  It is therefore the combination of the material properties of wear resistance, ductility and corrosion resistance that is important for good resistance to vibration friction wear / friction corrosion.

  Patent Document 10 describes a crystallization mechanism of a metal melt. If only a small number of crystal nuclei are present, or if only a small number of nuclei are formed in the melt, the result is a coarse-grained, highly segregated, often dendritic solidification structure. Mention is made of copper alloys having 0.1 to 25% by weight of calcium and 0.1 to 15% by weight of boron, which can be added for refining the melt particles of the copper material. Thus, by adding the crystallization agent, a uniform and fine-grained solidification structure is generated in the copper alloy.

  By making alloys with metalloids such as boron, silicon and phosphorus, a relatively high lowering of the base melting temperature, which is important in processing technology, is successful. Ni-Si-B and Ni-Cr-Si-B-based coating materials and high-temperature materials can significantly lower the melting temperature of nickel-based hard alloys due to the alloying element of boron and silicon, and thus, Can be used as a self-fluidizing nickel-based hard alloy.

  Reducing the base melting temperature by adding boron to make an alloy has been utilized in copper-tin materials used as overlay welding materials. Patent Document 11 discloses an alloy having Si 0.4% by weight, B 0.02 to 0.5% by weight, P 0.1 to 1.0% by weight, Sn 4 to 25% by weight, and the balance Cu. ing. By adding boron and a very high phosphorus content above 0.1% by weight, here the self-fluidity of the overlay welding alloy as well as the wettability of the substrate surface are improved and the use of additional flux is impaired. Will be needed. Here, a particularly high P content of 0.2 to 0.6% by weight is specified when the Si content of the alloy is 0.05 to 0.15% by weight. This underscores the superficial demand for the material to be self-flowing. However, this high P content greatly limits the hot workability of the alloy.

  Patent Document 12 describes a process in a diffusion soldering place where an intermetallic phase exists. Diffusion soldering is used to bond parts having different coefficients of thermal expansion together. During the thermo-mechanical loading of this soldering point, or during the soldering process itself, large stresses may occur at the interface, which may lead to cracking especially around the intermetallic phase. As a countermeasure, it has been proposed to mix particles that cancel out different expansion coefficients of the bonding materials with a solder component. That is, particles made of borosilicate or phosphosilicate can minimize thermomechanical stresses in the solder bond due to their favorable coefficient of thermal expansion. Moreover, the expansion of cracks that have already occurred is prevented by these particles.

  The publication of US Pat. No. 6,096,849 describes, among other things, the effect of the elemental boron on the conductivity of casting silicon alloys having 0.1 to 2.0% by weight boron and 4 to 14% by weight iron. In this Si-based alloy, a high melting point Si-B phase called silicon boride is precipitated.

Silicon boride, which is predominantly present in the form of SiB ₃ , SiB ₄ , SiB ₆ and / or SiB _n , determined by the boron content, is much different from silicon in its nature. These silicon borides have a metallic character and are therefore electrically conductive. They have very high heat resistance and oxidation resistance. Due to its extremely high hardness and high abrasive wear resistance, the form SiB ₆ preferably used in sintered products is used, for example, in ceramic production and processing.

German Patent No. 4126079 German Patent No. 19756815 German Patent Application Publication No. 581507 German Patent Application Publication No. 704398 US Pat. No. 2,128,955 German Patent Application Publication No. 2536166 German Patent Application Publication No. 102012105089 DE 102007010266 German Patent No. 3932536 German Patent Application Publication No. 36272882 U.S. Pat. No. 3,392,017 German Patent No. 10208635 German Patent No. 244010

  The present invention is based on the problem of producing a copper-tin alloy having excellent hot workability over the entire tin content range.

  For hot working, precursors produced using conventional casting methods can be used without absolutely necessitating the performance of spray compression or strip casting.

  This copper-tin alloy must be characterized by a structure having no blowholes, shrinkage cavities and stress cracks, and having a uniformly distributed δ phase containing a large amount of Sn existing depending on the Sn content of the alloy. In order to obtain sufficient hot workability, it is not always necessary to first homogenize the cast state of the copper-tin alloy using an appropriate annealing treatment. Already casting materials have to be excellent in high strength, high hardness and high corrosion resistance. High strength, high hardness, high stress relaxation and corrosion resistance, high electrical conductivity and high composite wear resistance due to annealing or further processing including hot working and / or cold working with at least one annealing A fine-grained structure having is prepared.

  The present invention relates to a copper-tin alloy according to any one of claims 1 to 3, a manufacturing method according to any of claims 10 to 11, and a usage according to any one of claims 17 to 17. It is described by features up to 19. Other dependent claims relate to preferred embodiments of the invention.

The present invention comprises the following components (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
-Comprising high strength tin-containing copper alloys having an elemental silicon and boron elemental content ratio Si / B of between 0.3 and 10.

Further, the present invention provides the following ingredients (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
-The elemental silicon and boron elemental content ratio Si / B is between 0.3 and 10;
-After casting, the following structural components in the alloy:
a) δ phase containing a large amount of Sn 1 to 98% by volume,
b) Al-containing and B-containing phases, Si-containing and B-containing phases and / or addition compounds and / or mixed compounds consisting of both phases 1 to 20% by volume,
c) The balance copper solid solution consisting of an α phase containing less tin (wherein the Al-containing and B-containing phases, the Si-containing and B-containing phases and / or the addition compounds and / or mixed compounds consisting of both phases are tin and / or Or it is covered by the δ phase containing a large amount of Sn)
Exists;
-The aforementioned Al-containing and B-containing phases, Si-containing and B-containing phases formed during casting as aluminum boride and silicon boride and / or as addition compounds and / or mixed compounds of aluminum boride and silicon boride. And / or addition compounds and / or mixed compounds consisting of both phases nucleate for uniform crystallization during solidification / cooling of the melt, whereby the Sn-rich δ phase is island-shaped and / Or evenly distributed in the tissue in a mesh-like;
-A borosilicate and / or borophosphosilicate and / or aluminum oxide-a borosilicate and / or an aluminum oxide-borophosphosilicate, said Al-containing and B-containing phase, Si-containing and B-containing phase and / or both The addition compounds and / or mixed compounds of the phases (1), (2) and (3) together with the phosphosilicate and the aluminum oxide serve as antiwear and / or anticorrosion coatings on semi-finished products and parts of said alloys. And a high strength tin-containing copper alloy.

By uniformly distributing the Sn-rich δ phase in an island shape and / or a net shape, the structure has no Sn-rich segregation. It is understood that such a segregation rich in Sn is a deposit of the δ phase in the cast structure which is formed as so-called reverse block segregation and / or grain boundary segregation, and these are thermal deposits of the cast member. When and / or mechanically loaded, it may cause tissue damage in the form of cracks, which may lead to fracture. Here again, there are no blowholes and shrinkage cavities and stress cracks in the structure after casting.
In this form, the alloy is present in the cast state.

Further, the present invention provides the following ingredients (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
-The elemental silicon and boron elemental content ratio Si / B is between 0.3 and 10;
-After further processing of the alloy by at least one annealing, or by at least one hot working and / or cold working together with at least one annealing, the following structural constituents in the alloy:
a) δ phase containing a large amount of Sn up to 75% by volume,
b) Al-containing and B-containing phases, Si-containing and B-containing phases and / or addition compounds and / or mixed compounds consisting of both phases 1 to 25% by volume,
c) The balance copper solid solution consisting of an α phase containing less tin (wherein the Al-containing and B-containing phases, the Si-containing and B-containing phases and / or the addition compounds and / or mixed compounds consisting of both phases are tin and / or Or it is covered by the δ phase containing a large amount of Sn)
Exists;
-Said contained Al- and B-containing phases, Si-containing and B-containing, formed as aluminum boride and silicon boride and / or as addition compounds and / or mixed compounds of aluminum boride and silicon boride Phases and / or addition compounds and / or mixed compounds consisting of both phases nucleate for static and dynamic recrystallization of the structure during said further processing of the alloy, whereby a homogeneous and fine-grained structure is obtained. Can be adjusted;
-A borosilicate and / or borophosphosilicate and / or aluminum oxide-a borosilicate and / or an aluminum oxide-borophosphosilicate, said Al-containing and B-containing phase, Si-containing and B-containing phase and / or both The addition compounds and / or mixed compounds of the phases (1), (2) and (3) together with the phosphosilicate and the aluminum oxide serve as antiwear and / or anticorrosion coatings on semi-finished products and parts of said alloys. And a high strength tin-containing copper alloy.

  Advantageously, the Sn-rich δ phase is at least 1% by volume.

  Further, the δ phase containing a large amount of Sn extends in islands and / or nets and / or rows and is uniformly distributed in the tissue. In this form, the alloy is present in a further processed state.

  The present invention, at this time, in the alloy form, using a sand mold casting method, shell mold casting method, precision casting method, full mold casting method, die casting method and chill casting method, or using a continuous or semi-continuous casting method. A tin-containing copper alloy in the cast and further processed state having an Al-containing and B-containing phase, an Si-containing and B-containing phase and / or an addition compound and / or a mixed compound consisting of both phases, which can be produced. It starts with the consideration of providing. While the use of process engineering expensive and costly primary forming techniques is certainly possible, it is not absolutely necessary for the production of the tin-containing copper alloys according to the invention. That is, for example, the use of the spray compression method may be omitted. The cast shape of the tin-containing copper alloy according to the present invention can be hot worked over the entire range of Sn content directly without homogenizing annealing, for example by hot rolling, extrusion or forging. Therefore, there existed significant restrictions on the processing technology that existed when manufacturing semi-finished products and parts from copper-tin alloys and classified this material group into wrought Cu-Sn alloys and casting Cu-Sn alloys. Disappears.

  The structure matrix of the tin-containing copper alloy in the as-cast state is such that as the Sn content of the alloy increases, depending on the casting process, the δ phase (Sn-rich) content and other α content containing it increase. It consists of phases (less Sn).

  As the Sn content of the alloy according to the present invention increases, not only the content of the δ phase in the structure increases, but also the arrangement shape of the δ phase in the structure changes. That is, it was confirmed that in the Sn content range of 4.0 to 9.0% by weight, the δ phase up to 40% by volume was mainly distributed in the structure in an island shape uniformly. When the Sn content of the alloy is 9.0 to 13.0 wt%, the δ-phase island shape existing up to 60 volume% in the structure shifts to a net shape. This delta network is also very evenly distributed in the structure of the alloy. When the Sn content is in the range of 13.0 to 17.0% by weight, up to 80% by volume of the δ phase is present in the structure almost exclusively in a uniform net shape. When the Sn content of the alloy is from 17.0 to 23.0% by weight, the structure ratio of the δ phase arranged in the structure as a dense network is up to 98% by volume.

  Due to the combination of the contents of boron, silicon, aluminum and phosphorus, in the melt of the alloy according to the invention various phenomena which decisively change its solidification properties compared to said copper-tin alloy and copper-tin-phosphorus alloy. Is promoted.

  In particular, the elements boron, silicon and phosphorus fulfill the deoxidizing function in the melt according to the invention. Therefore, the formation of tin oxide in the tin-containing copper alloy is prevented. By adding boron and silicon, it is possible to lower the phosphorus content without lowering the deoxidizing strength of the melt. This measure makes it possible to eliminate the detrimental effect of fully deoxidizing the melt with phosphorus additives. That is, a high P content, in any case, further extends the solidification period of already very long tin-containing copper alloys, which increases the tendency of cavities and segregation of this material type. In addition, it results in an increased formation of the copper-phosphorus phase. This phase type is considered to be the cause of the high temperature brittleness of tin-containing copper alloys. The detrimental effect of phosphorus addition is reduced by limiting the P content of the alloy according to the invention to the range 0.001 to 0.08% by weight.

The elements boron, silicon and aluminum have special meaning in the tin-containing copper alloy according to the invention. Al-B, Si-B based phases and / or their addition compounds and / or mixed compounds are already precipitated in the melt. SiB phase named silicon boride _is present in the form of SiB _3, SiB 4, SiB ₆ and SiB _n. The symbol "n" in the last-mentioned form is due to the fact that boron has a high solubility in the silicon lattice. The Al-B phase, named aluminum boride, is present in the structure mainly in the form of AlB ₂ and / or AlB ₁₂ .

  Said Al-containing and B-containing phases, Si-containing and B-containing phases and / or their forms formed as aluminum boride and silicon boride and / or as addition compounds and / or mixed compounds of aluminum boride and silicon boride. The addition compound and / or the mixed compound are hereinafter referred to as hard particles. These serve as crystal nuclei during solidification and cooling in the melt of the alloy according to the invention. As a result, it is no longer necessary to add so-called heterogeneous nuclei to the melt, whose homogeneous distribution in the melt can only be ensured inadequately.

  In particular, the lowering of the basic melting temperature due to the presence of the elemental boron and the hard particles acting as crystal nuclei decisively shortens the solidification period of the alloy according to the invention. As a result, the cast state of the present invention is very uniform in that the δ phase having a uniform and densely arranged island shape and / or a uniform and dense mesh structure shape is finely distributed according to the Sn content. Have an organization. Deposition of the Sn-rich δ phase, formed as so-called reverse block segregation and / or grain boundary segregation, is not visible in the cast structure of the invention.

  In the melt of the alloy according to the invention, the elements boron, silicon, aluminum and phosphorus reduce the metal oxides. These elements then oxidize themselves and rise to the surface of the casting, where they are said as borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate and / or aluminum oxide-borophosphosilicate. Together with the phosphosilicate and aluminum oxide, they form a protective film that prevents the cast part from absorbing gas. A very smooth surface of the castings made of the alloy according to the invention was identified, which indicates the formation of such a protective film. The as-cast structure of the present invention was free of blowholes throughout the cross-section of the cast part.

  The basic idea of the present invention is that the effect of borosilicate and phosphosilicate on the adjustment of different thermal expansion coefficients of the joining materials in the diffusion soldering is considered during the casting, hot working and heat treatment of copper-tin material. Is to be diverted to the phenomenon of. The long solidification period of these alloys may lead to large mechanical stresses between the low Sn and high Sn structural regions, which may lead to cracks and so-called shrinkage cavities. . Furthermore, these damage characteristics are due to different hot-working behaviors and different thermal expansion coefficients of the Sn-less structural component and the Sn-rich structural component even in the case of hot working and high-temperature annealing of the copper-tin alloy. May happen on the basis of.

  By adding boron, silicon, aluminum and phosphorus in combination to the tin-containing copper alloy according to the invention, on the other hand, while the melt solidifies, it has a different Sn content due to the action of said hard particles as crystal nuclei. A uniform texture results with a fine distribution of tissue constituents. In addition to the hard particles, borosilicates and / or borophosphosilicates and / or aluminum oxide-borosilicates and / or aluminum oxide-borophosphosilicates, which occur especially during solidification of the melt, are Together, they ensure the necessary adjustment of the coefficient of thermal expansion of the Sn-poor phase and the Sn-rich phase. In this way cavities as well as stress cracks are prevented from forming between the phases with different Sn contents.

  Alternatively, the alloy according to the invention may be further processed by annealing, or by at least one anneal together with hot working and / or cold working.

  Of the borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate and / or aluminum oxide-borophosphosilicate and of the phosphosilicate, a low Sn phase and a high Sn phase The effect of the hard particles as crystal nuclei for adjusting the coefficient of thermal expansion could likewise be observed during the process of hot working of the tin-containing copper alloy according to the invention. In the case of hot working, the hard particles are used as recrystallization nuclei. For this reason, thanks to the hard particles, dynamic recrystallization is advantageously carried out in the hot working of the alloy according to the invention. This further improves the uniformity and fineness of the structure.

  As with casting, it was possible to see a very smooth part surface even after hot working of the casting. This observation is carried out in the material during hot working by borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate and / or aluminum oxide-borophosphosilicate and phosphosilicate and aluminum oxide. Shows the formation of. In particular, the silicate and the hard particles adjust the different thermal expansion coefficients of the Sn-poor component and the Sn-rich component even during hot working. Therefore, the structure was free of cracks and cavities after hot working as it was after casting.

  The role of hard particles as nuclei for static recrystallization was found during the annealing process after cold working. The excellent function of the hard particles as nuclei for static recrystallization was manifested in that it was possible to reduce the recrystallization temperature required. This makes it easier to control the fine-grained structure of the alloy according to the invention.

This allows a higher degree of cold work during the further processing of the alloy according to the invention, whereby particularly high values of tensile strength R _m , yield strength R _p0.2 and hardness can be adjusted. . In particular, the height of the parameter of R _p0.2 is determined in an internal combustion engine, a valve, a turbocharger, a transmission, an exhaust gas aftertreatment device, a lever system, a brake system and a connection system, a hydraulic unit, or a machine for general machine manufacturing. And for sliding and guide members in the device. Furthermore, the high value of R _p0.2 is a prerequisite for the required spring properties of plug connectors in electronics and electrical engineering.

  The Sn content of the present invention varies in the range between 4.0 and 23% by weight. Tin contents below 4.0% by weight result in too low strength and hardness values. Moreover, the sliding load has insufficient motion characteristics. The resistance of the alloy to abrasive and adhesive wear does not meet the above requirements. At Sn contents above 23.0% by weight, the toughness of the alloy according to the invention deteriorates rapidly, which reduces the dynamic load capacity of parts made of this material.

  Due to the precipitation of the hard particles, the alloy according to the invention has a hard phase content which, due to the high hardness, contributes to the improvement of the material resistance to abrasive wear. Furthermore, the content of the hard particles improves the resistance to cohesive wear, since these phases show a low welding tendency with the metallic counterparts under sliding load. Therefore, they are used as important wear supports in the tin-containing copper alloys according to the invention. Furthermore, the hard particles enhance the heat resistance and stress relaxation resistance properties of the component according to the invention. This is an important prerequisite for the use of the alloys according to the invention, in particular for sliding members and for electronic / electrical components, wiring members, guide members and connecting members.

  The formation of borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate and / or aluminum oxide-borophosphosilicate and phosphosilicate in the alloy according to the invention leads to the formation of cavities and cracks in the tissue. Not only does it lead to a significant reduction. These silicate phases, together with aluminum oxide, also serve as antiwear and / or anticorrosion coatings on the part.

  The alloy according to the invention therefore guarantees a combination of properties of wear resistance and corrosion resistance. This combination of properties results in high resistance to sliding wear mechanisms and high material resistance to frictional corrosion. In this way, the present invention is highly suitable for use as sliding members and plug connectors as it has a high degree of resistance to sliding wear and vibration friction wear / fretting.

  The action of the hard particles as crystal nuclei and recrystallization nuclei, the action of wear supports, and the action of Al oxides and silicate phases for the purpose of corrosion protection are such that the silicon content is at least 0.05% by weight and the aluminum content is Only at least 0.01% by weight and a boron content of at least 0.005% by weight can reach technical significance in the alloy according to the invention. On the other hand, if the Si content exceeds 2.0% by weight and / or the Al content exceeds 1.0% by weight and / or the B content exceeds 0.6% by weight, this results in castability. Becomes worse. If the content of hard particles is too high, the viscosity of the melt will be decisively high. Moreover, the toughness of the alloy according to the invention is reduced.

  A range of Si contents lying between 0.05 and 1.5% by weight, in particular between 0.5 and 1.5% by weight, has been found suitable.

  Furthermore, the preferred Al content of the alloy according to the invention is 0.1 to 0.8% by weight.

  For the elemental boron, a content of 0.01 to 0.6% by weight is considered suitable. A boron content of 0.1 to 0.6% by weight has proved to be particularly suitable.

  In order to ensure a sufficient content of hard particles and borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate and / or aluminum oxide-borophosphosilicate and phosphorus silicate, the elemental silicon and It has proved to be important to control the specific elemental ratio of boron. For this reason, the ratio Si / B of the elemental contents of the elements silicon and boron (% by weight) of the alloy according to the invention lies between 0.3 and 10. Ratios Si / B of 1 to 10 and even 1 to 6 have proven suitable.

  The precipitation of hard particles affects the viscosity of the melt of the alloy according to the invention. This situation further emphasizes why the addition of phosphorus should not be omitted. Phosphorus renders the melt sufficiently viscous, regardless of the content of hard particles, which is very important for the castability of the invention. The phosphorus content of the alloy according to the invention is 0.001 to 0.08% by weight. Suitably, the P content is in the range of 0.001 to 0.05% by weight.

  The sum of the elemental contents of the elements silicon, boron and phosphorus is preferably at least 0.5% by weight.

  In particular, mechanical processing of semi-finished products and parts made of conventional wrought copper-tin alloys and copper-tin-phosphorus alloys with an Sn content of up to about 9% by weight results in a large cost due to insufficient machinability. It is possible only when you apply. In particular, if long coiled chips are generated, these chips must first be manually removed from the machining area of the machine, which leads to longer machine downtime.

  On the other hand, in the alloy according to the present invention, hard particles in which the elemental tin and / or the δ phase are crystallized or precipitated depending on the Sn content of the alloy are used as the chip breaker. Semi-finished products and parts made from the alloys according to the invention have improved machinability, since the short crushed and / or threaded tips so produced facilitate machinability.

In a preferred embodiment of the invention, the tin-containing copper alloy may consist of (in wt%):
Sn 4.0 to 9.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.01 to 0.6%,
P 0.001 to 0.08%,
The balance copper and inevitable impurities.

In another preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 4.0 to 9.0%,
Si 0.05 to 0.3%,
Al 0.01 to 0.15%,
B 0.1 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

In a particularly preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 4.0 to 9.0%,
Si 0.5 to 1.5%,
Al 0.1 to 0.8%,
B 0.01 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

  In the cast structure of this embodiment of the present invention, the δ phase containing a large amount of Sn is uniformly arranged in an island shape up to 40% by volume. At this time, the elemental tin and / or δ phase is mostly crystallized and / or covers the hard particles.

  The cast article of this embodiment has excellent hot workability at working temperatures in the range of 600 to 880 ° C.

  The significant strength increase and hardness increase after the hot working step can be utilized for parts that do not require cold working to manufacture. In this case, the hot work may advantageously be followed by a cooling boost, preferably in water.

  On the other hand, when it is necessary to carry out a cold working step, it has proved suitable to anneal the hot worked semi-finished product at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours. . This results in a very good cold workability with a cold workability ε of over 60%.

  The hard particles precipitated in the structure act as recrystallization nuclei when the cold-worked material state is heat-treated at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours. This further processing step makes it possible to adjust the texture with grain sizes up to 20 μm. Since the recrystallization temperature is lowered by the benefit of the recrystallization mechanism by the hard particles, it is possible to generate a structure having a particle size of up to 10 μm. It is possible to adjust the crystallite size in the material structure to less than 5 μm by a multi-step manufacturing process consisting of cold working and annealing and / or by lowering the recrystallization temperature depending on the purpose.

The mechanical properties of some embodiments are representative of the alloy composition as well as the entire range of manufacturing parameters. The investigation results of the corresponding examples described below _show that values for tensile strength R _m of more than 700 up to 800 MPa and yield strength R _p0.2 of more than 600 up to 700 MPa are obtained. Clearly show. At the same time, the toughness of the embodiments is at a very high level. This situation is represented by a high value for elongation at break A5.

In a preferred embodiment of the invention, the tin-containing copper alloy may consist of (in wt%):
Sn 9.0 to 13.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.01 to 0.6%,
P 0.001 to 0.08%,
The balance copper and inevitable impurities.

In another preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 9.0 to 13.0%,
Si 0.05 to 0.3%,
Al 0.01 to 0.15%,
B 0.1 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

In a particularly preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 9.0 to 13.0%,
Si 0.5 to 1.5%,
Al 0.1 to 0.8%,
B 0.01 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

  The texture of this embodiment of the invention is characterized by a δ-phase content of up to 60% by volume, the phase type being evenly distributed in the texture in island and net shapes. The elemental tin and / or δ-phase is then largely crystallized and / or covers the hard particles.

  The cast article of this embodiment has excellent hot workability at working temperatures of 600 to 880 ° C.

  Due to the dynamic recrystallization advantageously carried out by the hard particles, the structure after hot working of this embodiment is very finely divided. Since the strength value in the hot worked state is high, its cold workability is limited. This can be decisively improved by performing an annealing treatment at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours after the hot working process.

  The hard particles precipitated in the structure act as recrystallization nuclei when the cold-worked material state is heat-treated at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours. By this further processing step, the fine-grained structure can be adjusted. Since the recrystallization temperature is lowered due to the benefit of the recrystallization mechanism by the hard particles, a structure having a smaller grain size can be produced. A multi-step manufacturing process consisting of cold working and annealing can further optimize the fineness of the texture.

In a preferred embodiment of the invention, the tin-containing copper alloy may consist of (in wt%):
Sn 13.0 to 17.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.01 to 0.6%,
P 0.001 to 0.08%,
The balance copper and inevitable impurities.

In another preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 13.0 to 17.0%,
Si 0.05 to 0.3%,
Al 0.01 to 0.15%,
B 0.1 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

In a particularly preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 13.0 to 17.0%,
Si 0.5 to 1.5%,
Al 0.1 to 0.8%,
B 0.01 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

  The δ phase of the cast structure of this embodiment of the invention is present in the form of a uniformly arranged network up to 80% by volume. At this time, the structure may have a dendritic structure portion which also exhibits a net-like characteristic because the intervals between so-called dendrite branches are very small. Furthermore, the elemental tin and / or δ phases are predominantly crystallized and / or covered in the hard particles.

  The cast article of this embodiment has similarly good hot workability at working temperatures in the range of 600 to 880 ° C. Indeed, in this content range of 13.0 to 17.0% by weight for the alloying element tin, the conventional copper-tin alloy is extremely hot-workable without the occurrence of thermal cracking or thermal destruction. difficult.

  Due to the dynamic recrystallization advantageously carried out by the hard particles, the texture of this embodiment after hot working is very finely divided. Since the strength value in the hot worked state is high, its cold workability is strongly limited. The cold workability of the semi-finished product can be decisively improved by performing an annealing treatment at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours after the hot working process. After the step of hot working, a structural feature relating to the casting state, crystallization of the elemental tin and / or δ phase within the hard particles and / or coating of these hard particles with the elemental tin and / or δ phase. Is completely noticeable.

  The hard particles precipitated in the structure act as recrystallization nuclei when the cold-worked material state is heat-treated at a temperature of 200 to 880 ° C. for a period of 10 minutes to 6 hours. This further processing step makes it possible to adjust the texture with grain sizes up to 35 μm. Since the recrystallization temperature is lowered by the benefit of the recrystallization mechanism by the hard particles, it is possible to produce a structure having a particle size of up to 25 μm. The reticular arrangement of delta phase in the tissue is maintained.

  It is also possible to adjust the size of the microcrystals in the material structure to be smaller than 10 μm by a multi-step manufacturing process including cold working and annealing and / or by decreasing the recrystallization temperature depending on the purpose.

In a preferred embodiment of the invention, the tin-containing copper alloy may consist of (in wt%):
Sn 17.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.01 to 0.6%,
P 0.001 to 0.08%,
The balance copper and inevitable impurities.

In another preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 17.0 to 23.0%,
Si 0.05 to 0.3%,
Al 0.01 to 0.15%,
B 0.1 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

In a particularly preferred embodiment of the present invention, the tin-containing copper alloy may consist of (in wt%):
Sn 17.0 to 23.0%,
Si 0.5 to 1.5%,
Al 0.1 to 0.8%,
B 0.01 to 0.6%,
P 0.001 to 0.05%,
The balance copper and inevitable impurities.

  A very dense mesh of the δ phase uniformly distributed in the cast structure up to 98% by volume is a feature of this embodiment of the invention. The structure may then have reinforced dendritic structural parts which likewise have reticulate features due to the very small spacing of so-called dendrite branches. Furthermore, the elemental tin and / or δ phases are predominantly crystallized and / or covered in the hard particles.

  Due to the homogeneity of the dense δ mesh, the castings of this embodiment have equally good hot workability at operating temperatures in the range of 600 to 880 ° C.

  During the cohesive wear loading of parts made of tin-containing copper alloys according to the invention, the alloying element tin contributes particularly to the formation of so-called friction layers between sliding members. Especially under mixed friction conditions, this mechanism is important for strongly pushing the material's resistance to galling to the front. The friction layer reduces the purely metallic contact surface between the sliding members, which prevents welding or seizing of the members.

  Increasing the efficiency of modern engines, machines and units results in higher and higher operating pressures and temperatures. This is especially the case with newly developed internal combustion engines, which aim for a constant, complete combustion of the fuel. In addition to the high temperatures in the space of the internal combustion engine, the heat generation that occurs during the operation of the plain bearing system also appears. Due to the high temperature during the bearing operation, the parts made of the alloy according to the invention are similar to those in casting and hot working in borosilicate and / or borophosphosilicate and / or aluminum oxide-borosilicate. And / or the formation of aluminum oxide-borophosphosilicate and phosphosilicate and aluminum oxide is carried out. These compounds further strengthen the friction layer, which results in an increased resistance to cohesive wear of the sliding element made of the alloy according to the invention.

  Already during the casting process of the invention, precipitation of hard particles takes place in the structure. These phases protect the material from the consequences of abrasive wear loading, i.e. from chipping of the material by cutting wear. Furthermore, the hard particles, together with the complicatedly formed friction layer, ensure the high adhesion wear resistance of the present invention, since they have a low tendency to weld with metallic sliding members.

  In addition to its function as a wear support, the hard particles increase the temperature stability of the structure of the copper alloy according to the present invention. This results in high heat resistance as well as improved resistance of the material to stress relaxation.

  The cast form and further processed form of the alloy according to the invention may contain the following optional elements:

  The elemental zinc may be added to the tin-containing copper alloy according to the invention in a content of 0.1 to 2.0% by weight. It has been found that the alloying element zinc, depending on the Sn content of the alloy, increases the content of the Sn-rich phase of the invention, which leads to an increase in strength and hardness. No indication could be found that the addition of zinc had a beneficial effect on the homogeneity of the structure and on further reducing the content of cavities and fissures in the structure. In this respect, the combined effect of the alloy contents of boron, silicon and phosphorus clearly outweighs this. When Zn was lower than 0.1% by weight, the effect of increasing strength and hardness could not be observed. When the Zn content exceeds 2.0% by weight, the toughness of the alloy is reduced to a low level. Moreover, the corrosion resistance of the tin-containing copper alloy according to the present invention deteriorated. Suitably a zinc content in the range of 0.5 to 1.5% by weight may be added to the present invention.

  In order to further improve mechanical material properties such as strength and hardness and stress relaxation resistance at high temperature, alloying elements of iron and magnesium may be added alone or in combination.

  The alloy according to the invention may contain 0.01 to 0.6% by weight of Fe. In this case, up to 10% by volume of Fe boride, Fe phosphide and Fe silicide and / or Fe-rich particles are present in the structure. Furthermore, in the structure, an Fe-containing phase and an addition compound and / or a mixed compound of the Al-containing and B-containing phase, the Si-containing and B-containing phase and / or the Si-Al-B phase are formed. These phases and compounds contribute to improved strength, hardness, heat resistance, stress relaxation resistance, electrical conductivity, and improved resistance of the alloy to abrasive and cohesive wear loads. If the Fe content is lower than 0.01% by weight, improvement in these properties cannot be obtained. If the Fe content exceeds 0.6% by weight, there is a risk of forming iron clusters in the structure. This is associated with a significant reduction in processing and service properties.

  In addition, 0.01 to 0.5% by weight of the elemental magnesium may be added to the alloy according to the invention. In this case, up to 15% by volume of Mg boride, Mg phosphide and Cu-Mg and Cu-Sn-Mg phases are present in the structure. Furthermore, in the structure, the Mg-containing phase, the Al-containing and B-containing phase, the Si-containing and B-containing phase and / or the Si-Al-B phase addition compound and / or mixed compound are formed. These phases and compounds likewise contribute to the improvement of strength, hardness, heat resistance, stress relaxation resistance, conductivity, and resistance of the alloy to abrasive and cohesive wear loads. If the Mg content is lower than 0.01% by weight, improvement in these properties cannot be obtained. If the Mg content exceeds 0.5% by weight, the castability of the alloy deteriorates. Moreover, if the content of the Mg-containing compound is too high, the toughness of the alloy according to the present invention will be significantly reduced.

  Alternatively, the tin-containing copper alloy may have a low lead content. A lead content of up to 0.25% by weight is then still just acceptable and above the impurity range. In a particularly advantageous and preferred embodiment of the invention, the tin-containing copper alloy contains no lead, in addition to any impurities that may be present. In this relationship, the maximum lead content is 0.15% by weight of Pb.

  A particular advantage of the present invention is that the as-cast structure is broadly free of blowholes, shrinkage cavities, voids, segregations and cracks. This gives rise to the particular suitability of the alloy according to the invention as an antiwear layer which is fused onto a substrate, for example made of steel. The alloy composition according to the invention makes it possible in particular to suppress the formation of open pores during the fusing process, which increases the pressure resistance of the sliding layer.

  Another particular advantage of the present invention is the absolute need to implement special primary processing techniques such as spray compression or strip casting in order to provide a uniform, wide area void- and segregation-free structure. There is no. For such texture adjustment, conventional casting methods can be used for the primary working process of the alloy according to the invention. That is, one aspect of the present invention is that a tin-containing copper alloy according to the present invention is used to produce a final product using a sand casting method, a shell mold casting method, a precision casting method, a full mold casting method, a die casting method or a lost foam method. Includes a method of manufacturing parts that are close to the final product.

  Moreover, one aspect of the present invention is to use the tin-containing copper alloy according to the present invention to tape, sheet, disc, bolt, round wire, profile wire, round wire, using chill casting or continuous or semi-continuous casting. Includes methods for making bars, profile bars, hollow bars, pipes and profiles.

  It should be noted that after chill or continuous casting of alloy shapes according to the invention, expensive forging or upsetting processes are required to weld or close the cavities and cracks in the material. It does not have to be carried out at temperature.

  Moreover, in the present invention, in order to ensure sufficient hot workability, the δ phase containing a large amount of Sn existing according to the Sn content is further finely distributed in the structure by homogenization annealing or solution annealing, Or it is no longer absolutely necessary to dissolve and then remove it. In any case, the δ phase, which is already uniformly finely distributed in the cast structure of the alloy according to the invention with a corresponding Sn content, fulfills an essential function for the working properties of the alloy.

  In an advantageous form of the invention, the further processing of the as-cast state may comprise carrying out at least one hot working in the temperature range of 600 to 880 ° C.

  Cooling of the semi-finished products and parts after hot working may be carried out, preferably with quiet or accelerated air or with water.

  Due to the dynamic recrystallization advantageously carried out by the hard particles, the structure of the above-mentioned embodiments is very homogeneous and in the form of fine particles after hot working. In addition, it was confirmed that the hot-worked state of the present invention had extremely high values for strength and hardness. Obviously, during hot working, the precipitation of smaller size hard particles continued. Due to the precipitation inertia of Al-containing hard particles, they are produced on a larger scale during hot working.

  Preferably, the cast state and / or hot worked state of the present invention is annealed at least once in a temperature range of 200 to 880 ° C. for a period of 10 minutes to 6 hours, or in a quiet or accelerated air atmosphere. It may be carried out with or without cooling with water.

  One aspect of the present invention relates to a preferred method for further processing in a cast condition, or a hot worked condition, or an annealed cast condition, or an annealed and hot worked condition, the method comprising: Including at least one cold work run.

  Advantageously, at least one annealing treatment in the cold worked state according to the invention may be carried out in the temperature range of 200 to 880 ° C. for a period of 10 minutes to 6 hours.

  Suitably, the stress relief annealing / aging heat treatment may be carried out in the temperature range of 200 to 650 ° C. for a period of 0.5 to 6 hours.

  The matrix of the uniform structure of the present invention is composed of a ductile α phase and a δ phase portion depending on the Sn content of the alloy. Due to its high strength and hardness, the δ phase increases the resistance of the alloy to abrasive wear. Moreover, the δ phase increases the resistance of the material to cohesive wear due to its high Sn content which causes its tendency to form a friction layer. Hard particles are mixed in the metallic base material. Another embodiment of the invention additionally comprises a Fe- and / or Mg-containing phase deposited in the metallic base material.

  Due to this inhomogeneous structure consisting of α- and δ-phase metallic base materials with a mixture of high-hardness precipitates, the subject of the invention is provided with an excellent combination of properties. The following are mentioned in this connection: very good toughness with high strength and hardness values, excellent hot workability, sufficient cold workability, high temperature stability of the structure and the resulting High heat resistance and high stress relaxation resistance, sufficient conductivity for many applications, high corrosion resistance, and great resistance to abrasive wear, adhesive wear, surface crushing wear mechanisms and to vibration friction wear, so-called fretting.

  Due to the wide range of void-free, crack-free, segregation-free and uniform fine-grained structure containing hard particles, the alloy according to the invention already has a high degree of strength, hardness, ductility and composite in the cast state. Wear resistance and corrosion resistance. For this reason, the alloy according to the invention already has a wide range of use in the cast state.

  A particular suitability of the alloys according to the invention arises as an antiwear layer which is fused onto a substrate, for example made of steel. In this regard, it should be emphasized that the tempering steels (hardening 820 to 860 ° C., tempering 540 to 660 ° C .; DIN EN 10083-1) are within the heat treatment range of the invention. This means that, after fusion of the tin-containing copper alloy on a tempered steel substrate, the mechanical properties of both joining members can be optimized in only one treatment step. Another advantage is that the formation of open pores is suppressed during the fusing process, which increases the pressure resistance of the antiwear layer.

  Other than fusion bonding, other joining methods are possible. Conceivable in this connection is a composite production using forging, soldering or welding, which comprises selectively carrying out at least one annealing in the temperature range from 200 to 880 ° C. Similarly, for example, bearing-composite shells or bearing-composite bushes can be produced by roll coating, induction or conduction rolling coating or by laser rolling coating.

  Already, from tape type, thin plate type, disk type, bolt type, wire type, bar type, pipe type and profile shape casting shape, internal combustion engine, valve, turbocharger, transmission, exhaust gas aftertreatment device, lever system, It is possible to manufacture sliding members and guide members in brake and coupling systems, hydraulic units or in common machine-making machines and devices. Further processing of the as-cast condition allows the production of semi-finished products and parts with complex shapes and improved mechanical and optimum wear properties for these purposes. Thereby, the high component demands in the dynamic load are taken into account.

  Another aspect of the invention comprises the use of the tin-containing copper alloy according to the invention for electronic / electrical components, wiring members, guide members and connecting members.

  Due to the excellent strength properties and wear resistance and corrosion resistance of the tin-containing copper alloy according to the present invention, other possible uses are considered. That is, the present invention is suitable for a metal article in a structure for rearing (aquaculture) of an organism that lives in seawater. Another aspect of the invention is the stators, rotors and impellers for pumps and hydraulic turbines, for watercraft propellers, blades, ship screws and hubs, for water pump, oil pump and fuel pump casings. Of tin-containing copper alloys according to the invention for gears, worm gears, helical gears, and for pressure nuts and spindle nuts, and for pipes, gaskets and connecting bolts in the marine and chemical industries. To do.

  This material is of great importance for the use of the alloy according to the invention in the production of percussion instruments. In particular, high-quality concave discs, so-called cymbals, are produced from tin-containing copper alloys by hot working and at least one annealing, usually before shaping into final shapes with bells or pots. . Subsequently, the cymbals are annealed again before the final machining by cutting. To produce various types of cymbals, for example, ride cymbals, hi-hats, crash cymbals, china cymbals, splash cymbals and effect cymbals, it is therefore necessary to ensure that the special material Suitable hot workability is required. Within the range of the chemical composition of the present invention, various texture contents can be adjusted in a very wide range for the δ phase and the hard particles. In this way, it is possible to influence the way the cymbal resonates already on the alloy side.

It is a figure which shows the organization | tissue of Example 1 in 200 times the magnification. It is a figure similarly showing at the magnification of 500 times. It is a figure which shows the structure of alloy type 2 at the magnification of 200 times. It is a figure similarly showing at the magnification of 500 times. It is a figure which shows the structure | tissue after annealing at 500 degreeC of Example 2 for 3 hours. It is a figure which shows the structure | tissue after similarly annealing at 600 degreeC / 3h.

  Another important embodiment of the invention will be explained by means of Tables 1 to 11. The tin-containing copper alloy casting block according to the present invention was manufactured by chill casting. The chemical composition of the castings is apparent from Tables 1 to 3.

  Table 1 shows the chemical composition of alloy type 1. This material has a Sn content of 7.35% by weight, a Si content of 0.74% by weight, an Al content of 0.34% by weight, a boron content of 0.33% by weight, a content of 0.015% by weight. It is characterized by a P content and the balance copper.

  After casting, the structure of Example 1 is formed such that a relatively low content of the δ phase (1, about 20% by volume) and the hard particles 2 are distributed very uniformly in the copper solid solution 3 in the form of islands. (Figure 1). The hardness of this alloy is 108 HB (Table 2).

  From Table 3, other alloy type 2 chemistries are apparent. In addition to Sn15.09 wt% and P0.027 wt%, this material contains other elements Si (0.80 wt%), Al (0.54 wt%), boron (0.24 wt%), and The balance contains copper.

  The invention is notably characterized in that the as-cast structure consists of a δ-phase content which increases according to the casting / cooling process as the Sn content of the alloy increases. The arrangement of the δ phase containing a large amount of Sn shifts from a finely distributed island shape to a mesh shape with a high density as the Sn content of the alloy increases.

  In the alloy type 2 structure, the δ phase is present at a significantly higher content (up to 70% by volume). This tissue is apparent from FIG. 3 at 200 × and FIG. 4 at 500 ×. Reference numeral 1 indicates a δ phase containing a large amount of Sn and arranged in a mesh structure in each tissue. Furthermore, the hard particles 2 covered with the δ phase rich in tin and / or Sn are observed. Reference numeral 3 indicates the tissue component of the copper solid solution.

  The fact that the hardness of the material increases with increasing Sn content is indicated by the apparently high value of 210 HB of alloy 2 (Table 4).

  The uniform distribution of island and / or mesh arranged δ phases in the texture of the tin-containing copper alloy according to the invention underscores the action of hard particles as crystal nuclei to form the δ phase.

  One aspect of the invention relates to a method of making tapes, sheets, disks, bolts, wires, bars, pipes and profiles from the tin-containing copper alloys according to the invention using chill casting or continuous or semi-continuous casting. .

The alloy according to the invention can additionally be subjected to further processing. On the one hand, it makes it possible to produce specific, often complex shapes. On the other hand, in this way, the need to improve the composite operating properties of materials, especially for wear-loaded parts, and for components and binders in electronics / electrics, is addressed. This is because the load on system components in the corresponding machines, engines, transmissions, units, structures and devices is significantly increased. During this further processing, a significant improvement in toughness and / or a significant increase in tensile strength R _m , yield strength R _p0.2 and hardness are achieved.

  Due to the excellent hot workability of the alloys according to the invention, further processing in the as-cast state may comprise carrying out at least one hot work, preferably in the temperature range 600 to 880 ° C. Hot rolling can be used to produce disks, sheets and tapes. Extrusion allows the production of wires, bars, pipes and profiles. After all, the forging method is suitable for producing a part close to the final shape having a partially complicated shape.

Other suitable methods of further processing in the as-cast, or hot-worked, or annealed, cast, or annealed and hot-worked states include performing at least one cold work. Good. This step results in a particularly high material property values R _m , R _p0.2 and hardness. This is significant for applications in which mechanical and / or strong abrasive and cohesive wear loads of the component occur. Moreover, the spring properties of the parts made of the alloy according to the invention are improved considerably by cold working.

  In order to correspondingly recrystallize the structure of the present invention after cold working, at least one annealing treatment may be carried out in the temperature range of 200 to 880 ° C. for a period of 10 minutes to 6 hours. The so-obtained very fine-grained structure is an important premise for producing a combination of high strength and hardness and properties of sufficient toughness of the material.

  In order to reduce the residual stress of the part, a stress relief anneal may preferably be additionally carried out in the temperature range of 200 to 650 ° C. for a period of 0.5 to 6 hours.

  For fields of use with particularly strong composite part loads, at least one cold work, or a combination of at least one hot work and at least one cold work, should be carried out at 200 to 800 ° C. Further processing may be selected, including in conjunction with at least one anneal in the temperature range for a period of 10 minutes to 6 hours, to recrystallize the structure of the alloy of the present invention. The fine-grained alloy structure thus prepared guarantees a combination of high strength, high hardness and good toughness. In addition, a stress relief anneal may be performed in the temperature range of 200 to 650 ° C. for a period of 0.5 to 6 hours to reduce residual stress in the component.

  Three different production sequences were chosen for producing the tape-shaped semi-finished products from Example 1 (Table 1). These differ, inter alia, in the cold work / anneal cycle and the degree of cold work and the annealing temperature used (Table 5).

  After chill casting and hot rolling, the corresponding blocks or semi-finished products featured a very smooth surface. Due to the dynamic recrystallization of the structure performed during the hot rolling process, the hot worked state of alloy type 1 had sufficient cold workability. In order to further improve the cold workability of the hot-worked semi-finished products, it has proven suitable to carry out annealing in the temperature range of 600 to 880 ° C. for a period of 3 hours. That is, the hot-worked disk could be cold-rolled at a cold workability ε of about 85% without cracking.

  In the process of Production 1, the cold rolled tape was annealed at a temperature of 280 ° C. for a period of 2 hours. The characteristic values of the tape thus stress-relieved are apparent from Table 6. Despite the high strength and hardness values, the alloy tapes have sufficient toughness, for which the value of the elongation at break A5 is indicative.

  In the frame of Production 2, the alloy type 1 tape was annealed at 680 ° C. for 3 hours after the first cold rolling. Subsequently, the tape was cold-rolled at a cold workability ε of about 60%. At the end of manufacture, the tape was heat stress relieved at various temperatures between 280 and 400 ° C. for periods of 2 hours and 4 hours. The resulting material state characteristic values are listed in Table 7.

  From Table 7, it can be seen that the value of the grain size could not be described because the structure of the tape that was stress-relieved at 280 ° C. contained deformation characteristics. At about 340 ° C, recrystallization of the structure begins, which causes a significant decrease in strength and hardness.

  For this reason, in the frame of Production 3, the annealing temperature after the first cold working was lowered to 450 ° C. After annealing at this temperature for 3 hours, the tape was cold-rolled at a cold workability ε of about 30%. Finally, stress relief annealing was performed for 2 hours at a temperature between 240 and 360 ° C., and the characteristic values shown in Table 8 were obtained.

  FIG. 2 shows the structure of the final state of the tape of Example 1 that was stress-relieved at 240 ° C./2 h at a magnification of 500 times. The fine-grained structure having the hard phase 2 mixed in the copper solid solution 3 is clear. The hard particles are covered with a δ phase rich in tin and / or Sn.

  The results show high values of strength and hardness. Moreover, the high value of the elongation at break A5 indicates the excellent ductility of the material state.

  The tape of Example 2 of the present invention whose chemical composition is known from Table 3 was manufactured according to the manufacturing program described in Table 9. Chill casting hot rolling was performed at a temperature of 750 ° C., followed by cooling in water. After chill casting and hot rolling, the corresponding blocks or semi-finished products featured a very smooth surface.

  Following hot rolling, the tape was cold rolled with a cold workability ε as low as about 3%. Some of these tapes, labeled 2-A, were subsequently annealed at temperatures of 500, 550 and 600 ° C. for 3 hours and investigated.

  A second portion of the 7.04 mm cold-rolled tape, labeled 2-B, was further produced by periodically performing annealing and cold working.

  Table 10 shows the grain size and hardness of the tape 2-A in the cold rolled state and in the cold rolled and annealed state. Due to the dynamic recrystallization of the structure carried out during the hot rolling of the casting block, the structure is already present after the initial cold working in a uniform shape with a grain size of 20 to 25 μm. The toughness can be further improved by annealing in the temperature range of 200 to 650 ° C. FIG. 5 shows the structure of Example 2 after annealing at 500 ° C. for 3 hours. The δ phase (colored black) is very evenly distributed in the structure of the material. By performing annealing at 600 ° C. for 3 hours, the δ phase portion can be further reduced (FIG. 6).

  The hard particles are completely contained within the δ phase range with respect to the cast state. This emphasizes the function of the hard particles as crystal nuclei / precipitation nuclei even in the thermomechanical processing of alloys.

  The texture of Tape 2-A finally heat-treated with the parameters of 500 ° C./3 h + air and 600 ° C./3 h + air is shown in FIGS. 5 and 6. In the textures in both states, in addition to the Sn-rich δ phase 1, there are hard particles 2 covered with tin and / or Sn-rich δ phase. In addition, a copper solid solution 3 composed of an α phase containing less tin is also recognized. After annealing at the higher temperature of 600 ° C., the texture of Tape 2-A has coarse particles (FIG. 6).

  The second portion of the tape, named 2-B, was subjected to further processing with multiple cold rolling / annealing cycles. Table 11 lists the final state characteristic values after stress relief at various temperatures.

  By each cycle consisting of one cold rolling step and one annealing treatment, the structure of Example 2 of the present invention gradually extends in rows. Due to the high Sn content of the alloy, the very high δ content was arranged in rows, resulting in a high hardness value close to 300 HV1. At the same time, the brittle properties of the alloy are increased.

  As a result, it is concluded that the alloy according to the invention has excellent castability and hot workability over the entire range of Sn content from Sn4 to 23%. Cold workability is also at a very high level. As a matter of course, the ductility of the present invention deteriorates as the Sn content increases due to the increase in the δ content of the structure.

1 Sn-rich δ phase 2 Hard particles covered with tin and / or Sn-rich δ phase 3 Copper solid solution consisting of tin-poor α phase

Claims (18)

The following ingredients (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
A high-strength tin-containing copper alloy, characterized in that the ratio Si / B of the elemental contents of the elements silicon and boron is between 0.3 and 10. The following ingredients (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
-The elemental silicon and boron elemental content ratio Si / B is between 0.3 and 10;
-After casting, the following structural components in the alloy:
a) δ phase containing a large amount of Sn (1) 1 to 98% by volume,
b) Al-containing and B-containing phases, Si-containing and B-containing phases and / or addition compounds and / or mixed compounds consisting of both phases (2) from 1 to 20% by volume,
c) The remaining copper solid solution consisting of α phase with less tin (3)
(At this time, the addition compound and / or mixed compound (2) consisting of the Al-containing and B-containing phase, the Si-containing and B-containing phase, and / or both phases is a δ phase containing a large amount of tin and / or the above-mentioned Sn ( Covered by 1))
Exists;
-The aforementioned Al-containing and B-containing phases, Si-containing and B-containing phases formed during casting as aluminum boride and silicon boride and / or as addition compounds and / or mixed compounds of aluminum boride and silicon boride. And / or the addition compound and / or mixed compound (2) consisting of both phases form a nucleus for uniform crystallization during solidification / cooling of the melt, whereby the Sn-rich δ phase ( 1) is uniformly distributed in the tissue in islands and / or nets;
-A borosilicate and / or borophosphosilicate and / or aluminum oxide-a borosilicate and / or an aluminum oxide-borophosphosilicate, said Al-containing and B-containing phase, Si-containing and B-containing phase and / or both The addition compounds and / or mixed compounds (2) consisting of the phases (1), together with the phosphosilicates and aluminum oxides, serve as antiwear and / or anticorrosion coatings on semi-finished products and parts of said alloys. A high-strength tin-containing copper alloy characterized by the following. The following ingredients (in wt%):
Sn 4.0 to 23.0%,
Si 0.05 to 2.0%,
Al 0.01 to 1.0%,
B 0.005 to 0.6%,
P 0.001 to 0.08%,
Selectively, Zn up to 2.0%,
Selectively, Fe up to 0.6%,
Selectively, up to 0.5% Mg,
Selectively, Pb up to 0.25%,
The balance consists of copper and unavoidable impurities,
In a high strength 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 properties,
-The elemental silicon and boron elemental content ratio Si / B is between 0.3 and 10;
-After further processing of the alloy by at least one annealing, or by at least one hot working and / or cold working together with at least one annealing, the following structural constituents in the alloy:
a) δ phase containing a large amount of Sn (1) up to 75% by volume,
b) Al-containing and B-containing phases, Si-containing and B-containing phases and / or addition compounds and / or mixed compounds consisting of both phases (2) from 1 to 25% by volume,
c) The remaining copper solid solution consisting of α phase with less tin (3)
(At this time, the addition compound and / or mixed compound (2) consisting of the Al-containing and B-containing phase, the Si-containing and B-containing phase, and / or both phases is a δ phase containing a large amount of tin and / or the above-mentioned Sn ( Covered by 1))
Exists;
-Said contained Al- and B-containing phases, Si-containing and B-containing, formed as aluminum boride and silicon boride and / or as addition compounds and / or mixed compounds of aluminum boride and silicon boride The phase and / or the addition compounds and / or mixed compounds (2) consisting of both phases nucleate for static and dynamic recrystallization of the structure during said further processing of the alloy, so that it is homogeneous and fine-grained. It is possible to adjust the texture of
-A borosilicate and / or borophosphosilicate and / or aluminum oxide-a borosilicate and / or an aluminum oxide-borophosphosilicate, said Al-containing and B-containing phase, Si-containing and B-containing phase and / or both The addition compounds and / or mixed compounds (2) consisting of the phases (1), together with the phosphosilicates and aluminum oxides, serve as antiwear and / or anticorrosion coatings on semi-finished products and parts of said alloys. A high-strength tin-containing copper alloy characterized by the following.   The tin-containing copper alloy according to any one of claims 1 to 3, characterized in that it contains 0.05 to 1.5% of elemental silicon.   The tin-containing copper alloy according to any one of claims 1 to 4, characterized in that it contains 0.5 to 1.5% of elemental silicon.   The tin-containing copper alloy according to any one of claims 1 to 5, characterized in that it contains 0.1 to 0.8% of elemental aluminum.   The tin-containing copper alloy according to any one of claims 1 to 6, characterized in that it contains 0.01 to 0.6% of the elemental boron.   The tin-containing copper alloy according to any one of claims 1 to 7, characterized in that it contains 0.001 to 0.05% of elemental phosphorus. A final product from the tin-containing copper alloy according to any one of claims 1 to 8 by using a sand casting method, a shell mold casting method, a precision casting method, a full mold casting method, a die casting method or a lost foam method. And a method of manufacturing parts that are close to the final product. A tape, a thin plate, a disk, a bolt, a round wire, a deformed wire, or a round wire from the tin-containing copper alloy according to any one of claims 1 to 8 using a chill casting method or a continuous or semi-continuous casting method. Method for manufacturing bars, profile bars, hollow bars, pipes and profiles. The method according to claim 10, characterized in that the further processing of the as-cast state comprises carrying out at least one hot working in the temperature range of 600 to 880 ° C. The method according to any one of claims 9 to 11, characterized in that at least one annealing treatment is carried out in a temperature range of 200 to 880 ° C for a period of 10 minutes to 6 hours. Further processing of the as-cast, or hot-worked, or annealed, cast, or annealed and hot-worked state comprises performing at least one cold work. Item 13. The method according to any one of items 10 to 12. The method according to claim 13, characterized in that at least one annealing treatment is carried out in a temperature range of 200 to 880 ° C for a period of 10 minutes to 6 hours. The method according to claim 13 or 14, characterized in that the stress relief annealing / aging heat treatment is carried out in the temperature range of 200 to 650 ° C for a period of 0.5 to 6 hours. Internal combustion engines, valves, turbochargers, transmissions, exhaust gas aftertreatment devices, lever systems, brake systems for friction rings and friction discs for adjusting strips and sliding strips, for plain bearing surfaces in composite components And use of the tin-containing copper alloy according to any one of claims 1 to 8 for sliding members and guide members in connecting systems, hydraulic units, or in machines and equipment for general machine building. Law. Use of the tin-containing copper alloy according to any one of claims 1 to 8 for components, wiring members, guide members and connecting members in electronics / electrical engineering. Pumps for metal articles in the breeding of living organisms in seawater, for percussion instruments, for propellers for shipbuilding, for wings, ship screws and hubs, for casings of water pumps, oil pumps and fuel pumps And for stators, rotors and impellers for hydraulic turbines, for gears, worm gears, helical gears, for pressure nuts and spindle nuts, and for pipes, gaskets and connecting bolts in the marine and chemical industry, Use of the tin-containing copper alloy according to any one of claims 1 to 8.

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