EP2823077A2 - Alliage de cuivre-nickel-zinc contenant du silicium - Google Patents

Alliage de cuivre-nickel-zinc contenant du silicium

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Publication number
EP2823077A2
EP2823077A2 EP13704005.1A EP13704005A EP2823077A2 EP 2823077 A2 EP2823077 A2 EP 2823077A2 EP 13704005 A EP13704005 A EP 13704005A EP 2823077 A2 EP2823077 A2 EP 2823077A2
Authority
EP
European Patent Office
Prior art keywords
nickel
silicides
copper
weight
zinc alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13704005.1A
Other languages
German (de)
English (en)
Other versions
EP2823077B1 (fr
Inventor
Hans-Achim Kuhn
Rudolf Liebsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
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Filing date
Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Publication of EP2823077A2 publication Critical patent/EP2823077A2/fr
Application granted granted Critical
Publication of EP2823077B1 publication Critical patent/EP2823077B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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 a-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 have an increased electrical resistance compared to copper and accordingly also a lower thermal conductivity.
  • Nickel silver alloys correspond in their microstructure about the a- and the (a + ß) brass rings, since nickel replaces copper practically equivalent.
  • CuNi25Zn15, CuNi18Zn20, CuNi12Zn24, CuNi18Zn19Pb and CuNi12Zn30Pb form a homogeneous ⁇ -microstructure.
  • the two-phase wrought alloy CuNi10Zn42Pb is in the (a + ß) area.
  • copper-nickel-zinc alloys with 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 ⁇ phases. For better machinability of the manganese-containing nickel silver alloys to a substantial proportion of the element Pb as a chip breaker
  • a lead additive is always a better machinability can be effected.
  • the biphasic alloy having (a + ⁇ ) 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 a structure instead of. This structure is then suitable for further cold forming steps in which, for example, tips are made for writing instruments. However, while a machining, such as drilling, only be economically useful with a lead additive.
  • the document EP 0 222 004 B1 discloses copper alloys of composition 43 to 57% Cu, 23 to 37% Zn, 7 to 13% Ni and 7 to 13% Mn, which additionally contain 0.05 to 2% Si.
  • the alloy is to be used in the form of wire material, strips, powder or paste for brazing.
  • a preferred composition for wire material is 55% Cu, 8% Ni, 12% Mn, 0.15% Si, balance Zn.
  • This brazing material is preferably used to bond carbide composition to steel.
  • the solder is inserted between the parts to be joined and connected above its melting temperature with the joining partner.
  • copper alloys of composition 15 to 50% Cu, 10.2 to 18% Ni and 0, 1 to 15% Mn are known, which also contain 0.1 to 1% Si, balance Zn.
  • Ni nickel and silicon
  • Ni nickel silicides having a volume content of about 35% being present in the matrix.
  • Additions of iron, manganese and lead worsen wear resistance in these alloys From the document DE 1 120 151 high-strength nickel silver alloys with favorable properties in terms of castability and hot workability are known. These alloys consist of 0.01 to 5% Si, about 10 to 30% Ni, 45 to 70% Cu, 0.3 to 5% Mn, balance at least 10% zinc. Small additions of Si serve to deoxidize the alloy and improve castability. The manganese addition has the task of increasing the toughness and thus the cold workability of the alloy, and it also serves nickel savings.
  • manganese can be completely replaced by aluminum, and nickel in part by cobalt.
  • the alloying of iron should be avoided as iron reduces the corrosion resistance of the alloy. With a manganese content of 1%, strength values of approx. 400 MPa are achieved. To improve the mechanical properties, a heat treatment is proposed.
  • the document JP 1 177 327 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. From the document DE 10 2009 021 336 A1 copper-nickel-zinc alloys are known, which due to their special properties in terms of cold workability, strength, machinability and corrosion resistance for
  • Mine tips are used by pens.
  • the alloys consist of 40 to 48% Cu, 8 to 14% Ni, 4 to 6.5% Mn, 0.05 to 1.5% Si, balance Zn and unavoidable impurities.
  • up to 1.5% AI or up to 2.5% Pb can be added.
  • the wear resistance is ensured by a relatively large proportion of incorporated in the structure of Ni-Mn Mischsiliziden.
  • 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 isobutyl
  • nickel-, iron- and manganese-containing and / or nickel-, cobalt- and manganese-containing mixed silicides are embedded 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 a and ß phase of the matrix structure. In principle, to improve the cold and hot working fortune and to increase the strength of manganese.
  • manganese acts deoxidizing and desulfurizing.
  • mixed silicides In the presence of manganese, iron and nickel, silicon forms mixed silicides of approximate composition predominantly between (Mn, Fe, Ni) 2 Si and (Mn, Fe, Ni) 3 Si. Similarly, in the simultaneous presence of manganese, cobalt and nickel, silicon forms mixed silicides of approximate composition (Mn, Co, Ni) x Si y , where x> y. Furthermore, 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 ⁇ . 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 nucleation 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
  • 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 ß-phase.
  • Lead is as chip-breaking structural component in the smallest droplets distributed in the structure. This makes the wrought alloy easier to machine, 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. By the minimum content of one of the two elements becomes
  • thermodynamic equilibrium Ausscheidungskeime ensures that even with small deviations from the thermodynamic equilibrium Ausscheidungskeime be formed in sufficient density.
  • the sum of the iron content and eight times the cobalt content is at least
  • 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%,
  • nickel, iron and manganese-containing mixed silicides are incorporated as spherical or ellipsoidal particles in a structure consisting of ⁇ and ⁇ phase.
  • 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 pm.
  • 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 .-%:
  • 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.
  • Composition and process control during production and processing may also result in slightly different mixed silicides 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 concentration ratios, favorable properties of the alloy result. In an advantageous embodiment of the invention, 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 pm.
  • the surface density of the silicides having 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 .-%:
  • mixed silicides containing nickel, cobalt and manganese are incorporated as spherical or ellipsoidal particles.
  • the preferred selection of the cobalt content brings about a suitable formation of cobalt-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 2 pm.
  • 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 .-%:
  • 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 of 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. Overall, about the preferred manganese and
  • 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.
  • Composition and process control during production and processing may also result in slightly different mixed silicides 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 ⁇ .
  • 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 pm may be at least 20 per 5000 pm 2 . This ensures that enough silicides are available in a favorable size.
  • Another aspect of the invention relates to a method for producing wires, rods and profiles of the copper-nickel-zinc alloy according to the invention. The invention includes a method in which the following steps are performed:
  • 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.
  • the duration of the heat treatment may preferably be between one minute and three hours.
  • Cold forming in step d) can be increased. With this approach, depending on the annealing temperature, an increase in hardness between 10% and 20% could be achieved.
  • Another aspect of the invention relates to an alternative method for
  • the invention includes a method in which the following steps are performed:
  • 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 crimping 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.
  • 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:
  • the silicon-containing variants CC and CD are harder and achieve higher strength values than the comparative material CA. Accordingly, micrographs of the alloys CC and CD show a much finer grain structure than the microstructures of the 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. They represent, so to speak, the background signal of the matrix.
  • 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 deduced from the local Cu content with the aid of
  • the weight ratio (Ni + Fe) / Mn always assumes values greater than 4. Based on the images of the scanning electron microscope, the number of
  • Silicides per unit area determined. For the variant CC, at least 20 particles with a diameter smaller 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. Due to the small size of the silicides, these proportions are interpreted as the background signal of the matrix in which the silicide is embedded.
  • the signals for Cu and Zn are in this case very precisely in the ratio obtained for the pure ⁇ -phase or the pure ⁇ -phase.
  • the X-ray signal for the element Ni was - as described in variant CC - adjusted by the contribution of the background signal of the nickel in the Cu-Ni-Zn matrix and the thus determined nickel content of the silicide then with the elements Mn, Co and Si in Relationship set. Values between 2.5 and 4.5 were determined for the weight ratio (Ni + Co + Mn) / Si in the silicide using this method.
  • the weight ratio (Ni + Co) / Mn always assumes values greater than 10.
  • the ratio of nickel bound in silicides to cobalt bound in silicides always assumes values between 1, 5 and 2.5.
  • the number of silicides per unit area was determined.
  • at least 20 particles with a diameter of less than 2 ⁇ m were determined to 5000 ⁇ m 2 .
  • the pure metals copper, zinc, nickel and lead were melted together with a corresponding amount of binary master alloys of copper and iron, copper and silicon and copper and manganese in a medium frequency furnace and cast into steel chill molds with a diameter of 220 mm.
  • Composition of a pressed wire was wet-chemically analyzed with ICP-OES (in% by weight): Cu Zn Ni Mn Si Pb Fe Co
  • 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.
  • a three hour aging process at temperatures between 350 ° C and 500 ° C resulted in a hardening of the

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  • Crystallography & Structural Chemistry (AREA)
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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract

L'invention concerne un alliage de cuivre-nickel-zinc contenant du silicium, présentant la composition suivante en % en poids: 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 %, reste de Zn et impuretés inévitables, la somme de la teneur en Fe et du double de la teneur en Co représentant au moins 0,1 % en poids. Dans une structure composée de phase α et ß, des siliciures mixtes contenant du nickel, du fer et du manganèse et/ou des siliciures mixtes contenant du nickel, du cobalt et du manganèse sont intégrés en tant que particules sphériques ou ellipsoïdales. L'invention concerne par ailleurs un procédé de préparation de produits semi-finis composés d'un alliage de cuivre-nickel-zinc.
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

Publications (2)

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

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Application Number Title Priority Date Filing Date
EP13704005.1A Active EP2823077B1 (fr) 2012-03-07 2013-02-08 Alliage de cuivre-nickel-zinc contenant du silicium

Country Status (7)

Country Link
US (2) US9617629B2 (fr)
EP (1) EP2823077B1 (fr)
JP (1) JP5850590B2 (fr)
DE (1) DE102012004725B4 (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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DE102012004725B4 (de) 2018-07-19
MY171496A (en) 2019-10-15
DE102012004725A1 (de) 2013-09-12
US9617629B2 (en) 2017-04-11
US20170016097A1 (en) 2017-01-19
WO2013131604A3 (fr) 2014-07-10
US20150041028A1 (en) 2015-02-12
JP2015514863A (ja) 2015-05-21
JP5850590B2 (ja) 2016-02-03
US9738961B2 (en) 2017-08-22
MX363002B (es) 2019-03-01
MX2014009958A (es) 2015-07-17
EP2823077B1 (fr) 2016-04-06
WO2013131604A2 (fr) 2013-09-12

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