EP2823077B1 - Alliage de cuivre-nickel-zinc contenant du silicium - Google Patents

Alliage de cuivre-nickel-zinc contenant du silicium Download PDF

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Publication number
EP2823077B1
EP2823077B1 EP13704005.1A EP13704005A EP2823077B1 EP 2823077 B1 EP2823077 B1 EP 2823077B1 EP 13704005 A EP13704005 A EP 13704005A EP 2823077 B1 EP2823077 B1 EP 2823077B1
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Prior art keywords
nickel
silicides
copper
weight
zinc alloy
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German (de)
English (en)
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EP2823077A2 (fr
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Hans-Achim Kuhn
Rudolf Liebsch
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Wieland Werke AG
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Wieland Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/04—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rails
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21K—MAKING FORGED OR PRESSED METAL PRODUCTS, e.g. HORSE-SHOES, RIVETS, BOLTS OR WHEELS
    • B21K1/00—Making machine elements
    • B21K1/44—Making machine elements bolts, studs, or the like

Definitions

  • the invention relates to a copper-nickel-zinc alloy according to the preamble of claim 1 and to processes for producing semi-finished products from this alloy.
  • Alloys of copper, nickel and zinc are called because of their silver-like colors because of German silver. Commonly used alloys have between 47 to 64% by weight of copper and between 10 to 25% by weight of nickel. In turnable and drillable alloys usually up to 2.5 wt .-% lead are added as a chip breaker, in casting alloys even up to 9 wt .-%. The rest is zinc. These are single-phase materials that form only an ⁇ -phase.
  • nickel silver alloys may also contain 0.5 to 0.7 wt .-% manganese to reduce the Glühbrüchmaschine. Also, the manganese additive acts deoxidizing and desulfurizing.
  • Nickel silver alloys in their microstructure correspond approximately to the .alpha. Or the .alpha. + .Beta. Brass rings, since nickel replaces copper virtually equivalently.
  • CuNi25Zn15, CuNi18Zn20, CuNi12Zn24, CuNi18Zn19Pb and CuNi12Zn30Pb form a homogeneous ⁇ -microstructure.
  • the two-phase wrought alloy CuNi10Zn42Pb is in the ( ⁇ + ⁇ ) area.
  • copper-nickel-zinc alloys having a significantly increased manganese content beyond a deoxidizing effect are also known.
  • a known alloy CuNi12Zn38Mn5Pb2 has a significantly lower copper content and an increased zinc content.
  • Such alloys are again biphasic materials consisting of ⁇ - and ⁇ -phase.
  • the element Pb is present as a chip breaker in the manganese-containing nickel silver alloys to a significant extent.
  • Lead makes wrought alloys more easily machinable, but reduces toughness and increases hot tear sensitivity during annealing.
  • the hot workability of ⁇ -alloys is strongly affected by lead, so that they are usually only cold formed. In contrast, the good hot workability of the ( ⁇ + ⁇ ) alloys by lead is not significantly affected.
  • nickel silver alloys are already described with manganese.
  • EP 1 608 789 B1 Nickel silver alloys of composition 43 to 48% Cu, 33 to 38% Zn, 10 to 15% Ni and 3.5 to 6.5% Mn known.
  • it can still contain up to 4% Pb.
  • a lead additive is always a better machinability can be effected.
  • the biphasic alloy having ( ⁇ + ⁇ ) structure is subjected to hot working and then a temperature treatment is preferably carried out in the range of 630 to 720 ° C. This temperature treatment converts the alloy into a pure ⁇ -structure instead of.
  • This structure is then suitable for further cold forming steps in which, for example, tips are made for writing instruments.
  • a machining, such as drilling only be economically useful with a lead additive.
  • the publication JP 1177327 describes easily machinable nickel silver alloys with good hot and cold workability. These alloys consist of 6 to 15% Ni, 3 to 8% Mn, 0.1 to 2.5% Pb, 31 to 47% Zn, balance Cu with unavoidable impurities. Optionally, small amounts of Fe, Co, B, Si or P may be added to prevent grain growth on warming prior to hot working.
  • the invention has for its object to further develop nickel silver alloys with respect to their mechanical properties, their workability and their material costs.
  • the alloy should be comparable in strength and ductility to CrMo ferritic steels and at the same time be easy to machine and resistant to water-based writing gels.
  • the invention includes a copper-nickel-zinc alloy having the following composition in% by weight: Cu 47.0 to 49.0%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, pb 1.0 to 1.5%, Fe and / or Co up to 0.8%,
  • Residual Zn as well as unavoidable impurities wherein the sum of Fe content and twice the Co content is at least 0.1% by weight and wherein in a microstructure consisting of ⁇ - and ⁇ -phase nickel-, iron- and manganese-containing and / or nickel-, cobalt- and manganese-containing mixed silicides are incorporated as spherical or ellipsoidal particles.
  • the invention is based on the consideration that the microstructure of nickel silver materials by alloying of silicon is varied so that silicide precipitates are formed.
  • Silicides as intermetallic compounds have a considerably higher hardness of about 800 HV than the ⁇ and ⁇ phase of the matrix structure.
  • manganese acts deoxidizing and desulfurizing.
  • silicon forms mixed silicides of approximate composition predominantly between (Mn, Fe, Ni) 2 Si and (Mn, Fe, Ni) 3 Si.
  • mixed silicides of approximate composition (Mn, Co, Ni) x Si y , where x ⁇ y.
  • mixed silicides may be formed which contain both iron and cobalt in addition to manganese and nickel.
  • the mixed silicides are finely distributed as spherical or ellipsoidal particles in the matrix structure. The diameter of the particles is usually less than 2 microns.
  • the microstructure does not contain large-area silicides which therefore easily break out of the matrix structure. This advantageous property is achieved in the alloy according to the invention in particular by the low levels of manganese and iron or cobalt.
  • Both iron and cobalt act as nucleating sites for silicide formation, ie, in the presence of iron and / or cobalt, even small deviations from the thermodynamic equilibrium are sufficient, so that small precipitates are formed.
  • These precipitation nuclei which may also contain nickel in the present alloy composition, are finely distributed in the microstructure. They are deposited on other silicides, which now also contain manganese, preferably on. Due to the low manganese content of the alloy, the size of the individual silicides is limited. Small amounts of iron and / or cobalt in combination with a small amount of manganese are therefore the prerequisite for the formation of the mixed silicides, which are relevant to the invention.
  • the minimum amount of iron or cobalt is defined by the fact that the sum of the iron content and twice the cobalt content is at least 0.1%.
  • nickel silver with a high element content of zinc and a comparatively low content of nickel and copper is preferred. These materials have a two-phase basic structure of good cold-formable ⁇ -phase and good heat formable ⁇ -phase.
  • Lead is as chip-breaking structural component in the smallest droplets distributed in the structure. This makes the wrought alloy more easily machinable, with good hot workability of the biphasic alloy not being significantly affected by lead.
  • either the iron content or the cobalt content is at least 0.1% by weight.
  • the content of the other element can then be chosen freely between 0 and 0.8% by weight.
  • the minimum content of one of the two elements ensures that even small deviations from the thermodynamic equilibrium precipitate germs are formed in sufficient density.
  • the sum of the iron content and eight times the cobalt content is at least 0.4% by weight.
  • Cobalt preferably forms excretory germs. This allows iron to be replaced by small amounts of cobalt. Depending on the exact requirements of the alloy, an optimum of properties and costs can be set.
  • a preferred embodiment of the invention includes a copper-nickel-zinc alloy having the following composition in% by weight: Cu 47.0 to 49.0%, Ni 8.0 to 10.0% Mn 0.2 to 0.6%, Si 0.05 to 0.4%, pb 1.0 to 1.5%, Fe 0.2 to 0.8%,
  • Iron increases the strength and hardness of the copper-nickel-zinc alloys.
  • the preferred selection of the iron content causes a suitable formation of iron-containing precipitation nuclei for the mixed silicides according to the invention, so that they are finely distributed as spherical or ellipsoidal particles in the matrix structure.
  • the diameter of the particles is usually less than 1 micron.
  • Particularly preferred is an iron content of 0.4 to 0.6% by weight.
  • the alloy can be modified by the addition of small amounts of cobalt while maintaining the favorable properties and so adapted to the operational requirements.
  • the copper-nickel-zinc alloy may have the following composition in wt .-%: Cu 47.0 to 49.0%, Ni 9.0 to 9.8%, Mn 0.3 to 0.4%, Si 0.1 to 0.3%, pb 1.0 to 1.5%, Fe 0.4 to 0.6%,
  • Residual Zn as well as unavoidable impurities optionally up to 0.6% Co.
  • the preferred selection of the iron content causes a suitable formation of ferrous precipitate for the mixed silicides according to the invention.
  • a nickel content 9.0 to 9.8 wt .-%
  • a low-cost and easy machinable alloy is created.
  • the proportions by weight of silicon and manganese ultimately determine the extent and topology of silicide formation.
  • the manganese content should not exceed 0.4% by weight.
  • the preferred manganese and silicon fractions can ultimately be used to create a material optimized for mechanical properties in conjunction with good machinability.
  • the ratio of the sum of the weight fractions of the elements bound in silicides Ni, Fe and Mn to the weight fraction of silicon bonded in silicides may be between 3 and 6.5.
  • mixed silicides having approximate compositions between (Mn, Fe, Ni) 2 Si and (Mn, Fe, Ni) 3 Si are preferably formed.
  • slightly different mixed silicides may also be formed in the stoichiometry, which may also contain, for example, small proportions of other alloying elements such as copper and zinc.
  • the ratio of the sum of the weight fractions of the elements bound in silicides Ni, Fe and Mn to the weight fraction of silicon bonded in silicides can be between 4 and 6. In this range of the concentration ratios, favorable properties of the alloy result.
  • the ratio of the sum of the weight fractions of elements bound in silicides Ni and Fe to the proportion by weight of manganese bound in silicides may be at least 4. Due to the low manganese content, small mixed silicides form as spherical or ellipsoidal particles that do not break out of the matrix structure. The diameter of the particles is usually less than 1 micron.
  • the areal density of the silicides with a particle diameter of at most 1 ⁇ m can be at least 20 per 100 ⁇ m 2 . This ensures that enough silicides are available in a favorable size.
  • Another aspect of the invention includes a copper-nickel-zinc alloy having the following composition in wt .-%: Cu 47.0 to 49.0%, Ni 8.0 to 10.0%, Mn 0.2 to 0.6%, Si 0.05 to 0.4%, pb 1.0 to 1.5%, Co 0.1 to 0.8%,
  • the preferred selection of the cobalt content brings about a suitable formation of cobalt-containing precipitation germs for the mixed silicides according to the invention, so that they are finely distributed as spherical or ellipsoidal particles in the matrix structure.
  • the diameter of the particles is usually less than 2 microns.
  • the alloy can be modified by the addition of small amounts of iron while retaining the favorable properties and so adapted to the operational requirements.
  • the copper-nickel-zinc alloy may have the following composition in wt .-%: Cu 47.0 to 49.0%, Ni 9.0 to 9.8%, Mn 0.3 to 0.4%, Si 0.1 to 0.3%, pb 1.0 to 1.5%, Co 0.2 to 0.6%,
  • Residual Zn as well as unavoidable impurities optionally up to 0.6% Fe.
  • the preferred selection of the cobalt content causes a suitable formation of cobalt-containing excretion nuclei for the mixed silicides according to the invention.
  • a nickel content 9.0 to 9.8 wt .-%
  • a low-cost and easy machinable alloy is created.
  • the proportions by weight of silicon and manganese ultimately determine the extent and topology of silicide formation. In order to obtain particularly fine-grained silicides, the manganese content should not exceed 0.4% by weight.
  • the preferred manganese and silicon fractions can ultimately be used to create a material optimized for mechanical properties in conjunction with good machinability.
  • the ratio of the sum of the weight fractions of the elements bound in silicides Ni, Co and Mn to the weight fraction of silica bound in silicides may be between 2.5 and 5.
  • slightly different mixed silicides may also be formed in the stoichiometry, which may also contain, for example, small proportions of other alloying elements such as copper and zinc.
  • the ratio of the sum of the weight fractions of the elements bound in silicides Ni, Co and Mn to the weight fraction of silicon bonded in silicides can be between 3 and 4.5. In this range of concentration ratios, favorable properties of the alloy result.
  • the ratio of the sum of the weight fractions of elements bound in silicides Ni and Co to the proportion by weight of manganese bound in silicides may be at least 10. Due to the low manganese content, small mixed silicides form as spherical or ellipsoidal particles that do not break out of the matrix structure. The diameter of the particles is usually less than 2 microns.
  • the ratio of the weight fraction of nickel bound in silicides to the weight fraction of cobalt bound in silicides can be between 1.5 and 2.5.
  • the silicides thus formed contribute to the advantageous properties of the alloy.
  • the surface density of the silicides with a particle diameter of not more than 2 ⁇ m may be at least 20 per 5000 ⁇ m 2 . This ensures that enough silicides are available in a favorable size.
  • the heat treatment in step c) may preferably be carried out at a temperature which is 85 to 95% of the melting temperature of the alloy, measured in ° C. is.
  • the duration of the heat treatment may preferably be between one minute and three hours.
  • the aging annealing in step e) can increase the strength of the material compared to the strength after cold working in step d). With this approach, depending on the annealing temperature, an increase in hardness between 10% and 20% could be achieved.
  • High-quality refill tips for ballpoint pens are made of nickel silver, not least for aesthetic reasons. These are made here of machinable nickel silver wire material as a kneading material.
  • machinable nickel silver wire material For the production of ballpoint pen refills, approximately 15 to 20 mm long wire sections are bored through the center. A stepped contour is inserted in the tip, that a ball of tungsten carbide is pressed in and fixed by a final crimp so that it can rotate without play, but does not detach itself from the lead tip.
  • the nickel silver alloy must have a cold workability of at least 40% to allow a crack-free crimping of the tip around the ball.
  • the ink consumption of a ballpoint pen is determined by the wear of the ball seat by the ball of tungsten carbide. Accordingly, the material should also be corrosion resistant to ink. Both the required cold workability and the corrosion resistance is ensured by the nickel silver alloy according to the invention.
  • the cast blanks were subsequently subjected to several rolling passes at 750 ° C 45% reduced.
  • 6 mm thick sheets prepared therefrom by milling on both sides were cold rolled to 4 mm, then soft annealed at 650 ° C. for three hours. Then these sheets were cold rolled to 2.88 mm, then again annealed at 650 ° C for three hours and cold rolled to final thickness 2.0 mm. Finally, the strips were stress relieved at 300 ° C.
  • Table 2 contains the mechanical properties obtained after annealing at 300 ° C: Table 2: Mechanical properties of alloys HV10 Rp0.2 / MPa Rm / MPa A5 /% CA 202 582 658 23 CC 242 712 769 6 CD 247 752 788 10
  • the silicon-containing variants CC and CD are harder and achieve higher strength values than the comparative material CA. Accordingly, microstructures of alloys CC and CD show a much finer grain structure than the microstructures of silicon-free alloy CA. The gain in mechanical strength is explained by the formation of fine silicides: In the scanning electron microscope, small spherical and ellipsoidal precipitates can be seen in alloys CC and CD.
  • the local elemental composition of the ⁇ -phase, the ⁇ -phase and the silicides was determined by means of energy-dispersive X-ray analysis in a scanning electron microscope.
  • the energy-dispersive X-ray analysis provides for the silicides a composition of the elements Cu, Zn, Ni, Mn, Si and Fe, each with significant proportions. Outside the silicides, weight fractions of less than 0.4% are obtained for the elements Mn, Si and Fe.
  • the high levels of Cu and Zn in the X-ray signal of the silicides are due to the small size of the silicides from the environment in which the silicide is embedded.
  • the signals for Cu and Zn are very precisely in the ratio obtained for the pure ⁇ phase or the pure ⁇ phase.
  • the X-ray signal for the element Ni is composed of the signal of the nickel bonded in the silicide and the background signal of the nickel in the Cu-Ni-Zn matrix.
  • the contribution of the nickel background signal can be determined from the local Cu content by means of the information about the phase ( ⁇ or ⁇ ) and of the phase-corresponding Cu: Ni ratio and subtracted from the Ni total signal.
  • the thus determined nickel content of the silicide can then be related to the elements Mn, Fe and Si. If the background signal represents a contribution greater than 50% of the total nickel signal, then the statement about the nickel content in the silicide is subject to great uncertainties. Values between 4 and 5.7 were determined for the weight ratio (Ni + Fe + Mn) / Si in the silicide using this method.
  • the weight ratio (Ni + Fe) / Mn always assumes values greater than 4.
  • the number of silicides per unit area was determined. For variant CC, at least 20 particles with a diameter of less than 1 ⁇ m were determined to be 100 ⁇ m 2 .
  • the X-ray analysis provides for the silicides a composition of the elements Cu, Zn, Ni, Mn, Si and Co, each with significant proportions. Outside the silicides, the elements Mn, Si are obtained and Co parts by weight less than 0.4%.
  • the X-ray signal of the silicides contains high proportions of Cu and Zn.
  • the number of silicides per unit area was determined.
  • at least 20 particles with a diameter of less than 2 ⁇ m were determined to be 5000 ⁇ m 2 .
  • the pure metals copper, zinc, nickel and lead were melted in a medium frequency furnace together with a corresponding amount of binary master alloys of copper and iron, copper and silicon and copper and manganese and cast into steel chill molds with a diameter of 220 mm.
  • the oxidized surfaces of the solidified cylindrical ingots were removed by machining.
  • 500 mm long ingots were pressed into wires with a diameter of 4 mm.
  • the chemical composition of a pressed wire was analyzed wet-chemically with ICP-OES (in% by weight): Cu Zn Ni Mn Si pb Fe Co Press wire 48.4 39.6 9.5 0.36 0.32 1.3 0.49 0.01
  • the melting point of the alloy is approximately 850 ° C.
  • the wire was subjected to a heat treatment at 800 ° C and then quenched.
  • a deformation with a degree of deformation of 28% was applied.
  • the hardness was 175 HV 10.

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Claims (18)

  1. Alliage de cuivre-nickel-zinc avec la composition suivante [en % en masse] : Cu 47,0 à 49,0 %, Ni 8,0 à 10,0 %, Mn 0,2 à 0,6 %, Si 0,05 à 0,4 %, Pb 1,0 à 1,5 %, Fe et/ou Co jusqu'à 0,8 %,
    le reste de Zn ainsi que d'impuretés inévitables, la somme de la teneur de Fe et du double de la teneur de Co étant d'au moins 0,1 % et dans une structure constituée de phases-α et -β des siliciures mixtes contenant du nickel, du fer et du manganèse et/ou contenant du nickel, du cobalt, et du manganèse étant insérés comme particules de forme sphérique ou ellipsoïdale.
  2. Alliage de cuivre-nickel-zinc selon la revendication 1, caractérisé en ce que soit la teneur de Fe, soit la teneur de Co est d'au moins 0,1 % en masse.
  3. Alliage de cuivre-nickel-zinc selon la revendication 1 ou 2, caractérisé en ce que la somme de la teneur de Fe et de huit fois la teneur de Co est d'au moins 0,4 % en masse.
  4. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 1 à 3 avec la composition suivante [en % en masse] : Cu 47,0 à 49,0 %, Ni 8,0 à 10,0 %, Mn 0,2 à 0,6 %, Si 0,05 à 0,4 %, Pb 1,0 à 1,5 %, Fe 0,2 à 0,8 %,
    le reste de Zn ainsi que d'impuretés inévitables,
    éventuellement jusqu'à 0,8 % de Co,
    dans une structure constituée de phases-α et -β des siliciures mixtes contenant du nickel, du fer et du manganèse étant insérés comme particules de forme sphérique ou ellipsoïdale.
  5. Alliage de cuivre-nickel-zinc selon la revendication 4 avec la composition suivante [en % en masse] : Cu 47,0 à 49,0 %, Ni 9,0 à 9,8 %, Mn 0,3 à 0,4 %, Si 0,1 à 0,3 %, Pb 1,0 à 1,5 %, Fe 0,4 à 0,6 %,
    le reste de Zn ainsi que d'impuretés inévitables,
    éventuellement jusqu'à 0,6 % de Co,
    dans une structure constituée de phases-α et -β des siliciures mixtes contenant du nickel, du fer et du manganèse étant insérés comme particules de forme sphérique ou ellipsoïdale.
  6. Alliage de cuivre-nickel-zinc selon la revendication 4 ou 5, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni, Fe et Mn liés dans les siliciures à la part massique du silicium lié dans les siliciures est comprise entre 3 et 6,5.
  7. Alliage de cuivre-nickel-zinc selon la revendication 6, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni, Fe et Mn liés dans les siliciures à la part massique du silicium lié dans les siliciures est comprise entre 4 et 6.
  8. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 4 à 7, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni et Fe liés dans les siliciures à la part massique du manganèse lié dans les siliciures est d'au moins 4.
  9. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 4 à 8, caractérisé en ce que la densité superficielle des siliciures avec un diamètre de particule de maximum 1 µm est d'au moins 20 par 100 µm2.
  10. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 1 à 3 avec la composition suivante [en % en masse] : Cu 47,0 à 49,0 %, Ni 8,0 à 10,0 %, Mn 0,2 à 0,6 %, Si 0,05 à 0,4 %, Pb 1,0 à 1,5 %, Co 0,1 à 0,8 %,
    le reste de Zn ainsi que d'impuretés inévitables,
    éventuellement jusqu'à 0,8 % de Fe,
    dans une structure constituée de phases-α et -β des siliciures mixtes contenant du nickel, du cobalt et du manganèse étant insérés comme particules de forme sphérique ou ellipsoïdale.
  11. Alliage de cuivre-nickel-zinc selon la revendication 10 avec la composition suivante [en % en masse] : Cu 47,0 à 49,0 %, Ni 9,0 à 9,8 %, Mn 0,3 à 0,4 %, Si 0,1 à 0,3 %, Pb 1,0 à 1,5 %, Co 0,2 à 0,6 %,
    le reste de Zn ainsi que d'impuretés inévitables,
    éventuellement jusqu'à 0,6 % de Fe,
    dans une structure constituée de phases-α et -β des siliciures mixtes contenant du nickel, du cobalt et du manganèse étant insérés comme particules de forme sphérique ou ellipsoïdale.
  12. Alliage de cuivre-nickel-zinc selon la revendication 10 ou 11, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni, Co et Mn liés dans les siliciures à la part massique du silicium lié dans les siliciures est comprise entre 2,5 et 5.
  13. Alliage de cuivre-nickel-zinc selon la revendication 12, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni, Co et Mn liés dans les siliciures à la part massique du silicium lié dans les siliciures est comprise entre 3 et 4,5.
  14. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 10 à 13, caractérisé en ce que le rapport de la somme des parts massiques des éléments Ni et Co liés dans les siliciures à la part massique du manganèse lié dans les siliciures est d'au moins 10.
  15. Alliage de cuivre-nickel-zinc selon l'une quelconque des revendications 10 à 14, caractérisé en ce que le rapport de la part massique du nickel lié dans les siliciures à la part massique du cobalt lié dans les siliciures est comprise entre 1,5 et 2,5.
  16. Alliage de cuivre-nickel-zinc selon l'une des revendications 10 à 15, caractérisé en ce que la densité superficielle des siliciures avec un diamètre de particule de maximum 2 µm est d'au moins 20 par 5 000 µm2.
  17. Procédé pour la préparation de fils, profilés et barres à partir d'alliages de cuivre-nickel-zinc selon l'une quelconque des revendications 1 à 16 avec les étapes suivantes de :
    a. préparation de boulons au moyen d'une coulée en coquille ou d'une coulée continue,
    b. extrusion,
    c. traitement thermique à des températures quelque peu inférieures à la température de fusion de l'alliage avec étirage subséquent,
    d. façonnage à froid avec un degré de déformation d'au moins 25 %,
    e. recuit de précipitation entre 350 °C et 500 °C, de sorte qu'une augmentation supplémentaire de la solidité de l'alliage est atteinte.
  18. Procédé pour la préparation de fils à partir d'alliages de cuivre-nickel-zinc selon l'une des revendications 1 à 16 avec les étapes suivantes de :
    a. préparation de fils coulés au moyen d'une coulée en lingotière,
    b. au moins une déformation à froid du fil,
    c. traitement thermique à des températures quelque peu inférieures à la température de fusion de l'alliage avec étirage subséquent,
    d. déformation à froid avec un degré de déformation d'au moins 25 %,
    e. recuit de précipitation entre 350 °C et 500 °C, de sorte qu'une augmentation supplémentaire de la solidité de l'alliage est atteinte.
EP13704005.1A 2012-03-07 2013-02-08 Alliage de cuivre-nickel-zinc contenant du silicium Active EP2823077B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012004725.8A DE102012004725B4 (de) 2012-03-07 2012-03-07 Siliziumhaltige Kupfer-Nickel-Zink-Legierung
PCT/EP2013/000373 WO2013131604A2 (fr) 2012-03-07 2013-02-08 Alliage de cuivre-nickel-zinc contenant du silicium

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EP2823077A2 EP2823077A2 (fr) 2015-01-14
EP2823077B1 true EP2823077B1 (fr) 2016-04-06

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JP (1) JP5850590B2 (fr)
DE (1) DE102012004725B4 (fr)
MX (1) MX363002B (fr)
MY (1) MY171496A (fr)
WO (1) WO2013131604A2 (fr)

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DE102015014856A1 (de) * 2015-11-17 2017-05-18 Wieland-Werke Ag Kupfer-Nickel-Zink-Legierung und deren Verwendung
CN110952019B (zh) * 2019-12-24 2021-09-14 宁波博威合金材料股份有限公司 一种易切削锌白铜及其制备方法和应用
CN113523266A (zh) * 2020-04-14 2021-10-22 江苏友和工具有限公司 一种陶瓷片及其加工工艺

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Publication number Priority date Publication date Assignee Title
BE519901A (fr) 1953-05-13
DE1120151B (de) 1954-04-26 1961-12-21 Dr Eugen Vaders Hochfeste Neusilber-Legierung
DE1238220B (de) 1959-05-06 1967-04-06 Dr Eugen Vaders Verwendung einer Kupfer-Mangan-Zink-Legierung als Werkstoff fuer einer Gleitbeanspruchung ausgesetzte Maschinenteile
DE1205285B (de) * 1962-12-28 1965-11-18 Ver Deutsche Metallwerke Ag Verwendung von mangan- und siliziumhaltigen Kupferlegierungen fuer auf Abnutzung beanspruchte Gegenstaende
DE1558817B2 (de) 1966-09-14 1975-02-27 Vereinigte Deutsche Metallwerke Ag, 6000 Frankfurt Verwendung einer Kupferlegierung
US3627593A (en) * 1969-10-30 1971-12-14 Int Nickel Co Two phase nickel-zinc alloy
US4631171A (en) 1985-05-16 1986-12-23 Handy & Harman Copper-zinc-manganese-nickel alloys
US4684052A (en) 1985-05-16 1987-08-04 Handy & Harman Method of brazing carbide using copper-zinc-manganese-nickel alloys
DE3735783C1 (de) 1987-10-22 1989-06-15 Diehl Gmbh & Co Verwendung einer Kupfer-Zink-Legierung
JPH01177327A (ja) 1988-01-06 1989-07-13 Sanpo Shindo Kogyo Kk 銀白色を呈する快削性銅基合金
JPH0368732A (ja) 1989-08-08 1991-03-25 Nippon Mining Co Ltd ラジエータープレート用銅合金および銅合金材の製造法
DE4339426C2 (de) 1993-11-18 1999-07-01 Diehl Stiftung & Co Kupfer-Zink-Legierung
JPH07166279A (ja) 1993-12-09 1995-06-27 Kobe Steel Ltd 耐食性、打抜き加工性及び切削性が優れた銅基合金及びその製造方法
US6064029A (en) 1997-06-04 2000-05-16 Institute For Advanced Engineering Apparatus for controlling the quality of a resistance spot weld and method therefor
CH693948A5 (fr) 2003-03-21 2004-05-14 Swissmetal Boillat Sa Alliage à base de cuivre.
DE102007029991B4 (de) 2007-06-28 2013-08-01 Wieland-Werke Ag Kupfer-Zink-Legierung, Verfahren zur Herstellung und Verwendung
DE102009021336B9 (de) 2009-05-14 2024-04-04 Wieland-Werke Ag Kupfer-Nickel-Zink-Legierung und deren Verwendung

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US20150041028A1 (en) 2015-02-12
MX363002B (es) 2019-03-01
MY171496A (en) 2019-10-15
MX2014009958A (es) 2015-07-17
US9617629B2 (en) 2017-04-11
EP2823077A2 (fr) 2015-01-14
WO2013131604A2 (fr) 2013-09-12
DE102012004725B4 (de) 2018-07-19
JP5850590B2 (ja) 2016-02-03
US20170016097A1 (en) 2017-01-19
US9738961B2 (en) 2017-08-22
DE102012004725A1 (de) 2013-09-12
WO2013131604A3 (fr) 2014-07-10

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