US20140294665A1 - Cu-Ni-Zn-Mn Alloy - Google Patents

Cu-Ni-Zn-Mn Alloy Download PDF

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Publication number
US20140294665A1
US20140294665A1 US13/982,764 US201213982764A US2014294665A1 US 20140294665 A1 US20140294665 A1 US 20140294665A1 US 201213982764 A US201213982764 A US 201213982764A US 2014294665 A1 US2014294665 A1 US 2014294665A1
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United States
Prior art keywords
alloy
less
copper alloy
alloys
beta
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Abandoned
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US13/982,764
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English (en)
Inventor
Florian Dalla Torre
Jean-Pierre Tardent
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BAOSHIDA SWISSMETAL AG
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BAOSHIDA SWISSMETAL AG
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Assigned to BAOSHIDA SWISSMETAL AG reassignment BAOSHIDA SWISSMETAL AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TORRE, FLORIAN DALLA, TARDENT, Jean-Pierre
Publication of US20140294665A1 publication Critical patent/US20140294665A1/en
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    • 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
    • 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
    • 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
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • Copper Tellurium alloys (C14500) contain 0.4-0.7 wt. % Te with minor additions of P and Ag and the rest being Cu. They form CuTe-intermetallics with a satisfactory chip breaking effect.
  • the alloy is not an easy to manufacture alloy due to the high sensitivity of forming oxides causing embrittlement.
  • Te forms brittle ZnTe intermetallics as well results in unfavorable properties.
  • brasses or nickel-silver alloys having a certain range of Zn content exhibit a duplex alpha (face-centered cubic, fcc) and beta (body-centered-cubic, bcc) structure, which apart from representing a fifth mode of increasing strength, is also beneficially influencing the machinability, grain size stability and hot workability.
  • Current commercially available leaded Cu—Ni—Zn—Mn alloys range in the Ni content from 5 to 25 wt. %, a Mn 0-7 wt. %, Zn 25-40 wt. % and rest Cu and impurities typically ⁇ 1 wt. %. According to Guillet's rule [L. Guillet and A.
  • the invention relates to age hardenable high-strength Cu—Zn—Ni—Mn-based alloys with superior mechanical properties and excellent machinability suitable for applications, where intensive free-machining operations are required as for example for the production of pen tips and reservoirs for writing implants of reduced tip dimensions.
  • intensive free-machining operations are required as for example for the production of pen tips and reservoirs for writing implants of reduced tip dimensions.
  • the composition of the invented alloy is given as follows:
  • the invention of the alloy aims to satisfy the current needs for lead-free machinable Cu—Ni—Zn—Mn alloys suitable free-machining operations as required for example in writing applications.
  • the invented alloys exhibit an attractive combination of high strength with sufficient ductility required for subsequent operations or safety margins. While the flow stress reaches values comparable to those of typical stainless steels used for pen tip and other free-machining applications, sufficient cold-formability is often still required in order to perform further bending operations or other cold-deformation steps, such as the insertion of the pen ball onto the tip socket.
  • the machinability of this alloy family is superior due to the precipitation hardened phases. Additions of arsenic as well as minor additions of P, Si, Al and Sn demonstrate beneficial effects on the corrosion resistance.
  • FIG. 1 shows an optical microscopy images of samples heat treated at 350° C. ( FIG. 1 a ) and 450° C. ( FIG. 1 b ) of alloy No 1;
  • FIG. 8 shows optical microscopy image of a sample annealed at 540° C. followed by a second annealing process at 400° C. ( FIG. 8 a ); secondary electron microscopy image of alloy with NiSn preciptates in beta phase matrix and at boundary to alpha grains ( FIG. 8 b ) both of alloy No: 6.
  • thermodynamic software tool In order to determine the precise temperature range of heat treatments a special thermodynamic software tool has been applied, which allows calculating the phase stability fields in a multi-component system as a function of temperature and chemical composition [J. ⁇ gren, F. H. Hayes, L. Höglund, U. R. Kattner, B. Legendre, R. Schmid-Fetzer: Applications of Computational Thermodynamics. Z. Metallischen 93, (2002), 128-142].
  • One aim of the present alloy invention was to increase the beta content of the microstructure to a level, which shows good machinability suitable for turning operations. This is realized by an increased Zn content as compared to the alloy composition of the first and second alloy of the present invention.
  • FIG. 3 a shows the as-extruded microstructure of the duplex phased alloy.
  • Chip length is significantly longer than in the leaded alloys, however not affecting significantly the machining performance. Note that the surface quality is significantly better compared to the surface of the leaded alloy No: 1 (see FIG. 6 ).
  • FIGS. 6 a to 6 d represent machining tests with Mikron Multistar made at 100 Hz on alloy No 3 with composition A annealed at 450° C. ( FIGS. 6 a and 6 b ); and alloy No: 1 ( FIGS. 6 c and 6 d ). Chip length of the leaded alloy No: 1 is smaller than that in alloy No 3.
  • the main difficulty with this type of alloy is the avoidance of oxidation of Ca as it strongly reacts with oxygen. This can be avoided by pre-alloying of Ca with Zn in inert atmosphere. Subsequent alloying with a pre-alloy of Cu—Mn incl. the above mentioned amounts of Fe, Si, Al.
  • the fifth alloy of the present invention can be unleaded and has the following chemical composition: 43.5-48 wt. % Cu, 36-40 wt. % Zn, 9-12 wt. % Ni, 5-7 wt. % Mn, ⁇ 1.0 wt. % Al, ⁇ 0.5 wt. % Sn, ⁇ 0.5 wt. % Fe, ⁇ 0.03 wt. % P, ⁇ 0.15 wt. % As and ⁇ 2.0 wt. % Pb.
  • the tensile properties of the alloy show values ranging from 850-900 MPa with elongations of 2-12% (see Table 4).
  • the sixth alloy of the present invention is also age hardenable and has the following chemical composition: 43.5-48 wt. % Cu, 36-40 wt. % Zn, 9-12 wt. % Ni, 5-7 wt. % Mn, ⁇ 1.0 wt. % Al, ⁇ 2.0 wt. % Sn, ⁇ 0.5 wt. % Fe, Si ⁇ 0.2 wt. %, ⁇ 0.03 wt. % P, ⁇ 0.15 wt. % As and ⁇ 2 wt. % Pb.
  • the main focus of this alloy was to evaluate the influence Sn in the system, which has been added to provoke precipitation of NiSn phases.
  • the scanning electron microscopy (SEM) image shown in FIG. 8 shows the material in the overaged condition heat treated at 400° C., where NiSn precipitates are visible as white dots in the beta phase and localized to the phase boundary.
  • FIGS. 8 a and b show optical microscopy image of a sample annealed at 540° C. followed by a second annealing process at 400° C. ( FIG. 8 a ); Secondary electron microscopy image of alloy with NiSn preciptates in beta phase matrix and at boundary to alpha grains ( FIG. 8 b ) both of alloy No: 6.
  • Silicon has the strongest effect of all alloying elements on the alpha beta phase boundary in brasses and thus has to be added to the alloy with great care.
  • Thermodynamic simulations have shown that additions of up to ⁇ 0.5 wt. % are still tolerable with respect to the balance of alpha/beta ratio (3:1, at 800° C.), while a Si content of 1.0 wt. % reverses the fraction of alpha/beta completely for a Zn content of 37 wt. %.
  • the age hardened stage of these alloys show a high mechanical resistance reaching hardness values beyond 250 HV and tensile strength above 1000 MPa with tensile elongation of 1-5%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Adornments (AREA)
  • Heat Treatment Of Steel (AREA)
  • Conductive Materials (AREA)
US13/982,764 2011-02-04 2012-02-03 Cu-Ni-Zn-Mn Alloy Abandoned US20140294665A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH2112011 2011-02-04
CH00211/11 2011-02-04
PCT/EP2012/051890 WO2012104426A2 (en) 2011-02-04 2012-02-03 Cu-ni-zn-mn alloy

Publications (1)

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US20140294665A1 true US20140294665A1 (en) 2014-10-02

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US (1) US20140294665A1 (enExample)
EP (1) EP2670876A2 (enExample)
JP (1) JP2014512452A (enExample)
KR (1) KR20140021554A (enExample)
CN (1) CN103502488B (enExample)
AU (1) AU2012213342A1 (enExample)
BR (1) BR112013019625A2 (enExample)
CA (1) CA2826185A1 (enExample)
IL (1) IL227758A0 (enExample)
MX (1) MX2013008503A (enExample)
RU (1) RU2013140681A (enExample)
SG (1) SG192046A1 (enExample)
WO (1) WO2012104426A2 (enExample)
ZA (1) ZA201306143B (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10760146B2 (en) * 2012-08-09 2020-09-01 Ykk Corporation Fastening copper alloy
US10984931B2 (en) 2015-03-18 2021-04-20 Materion Corporation Magnetic copper alloys
US20210178461A1 (en) * 2019-12-11 2021-06-17 Ngk Insulators, Ltd. Article superior in design and method for producing the same
EP3971312A1 (en) * 2020-09-17 2022-03-23 Société BIC Brass alloy for writing instrument tips
US11447847B2 (en) 2018-04-20 2022-09-20 Wieland-Werke Ag Copper-zinc-nickel-manganese alloy
US11519055B2 (en) * 2014-10-28 2022-12-06 Advanced Alloy Holdings Pty Ltd Metal alloys including copper

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* Cited by examiner, † Cited by third party
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CN103042318B (zh) * 2013-01-16 2015-08-05 苏州金仓合金新材料有限公司 一种用于焊接的环保锡锌锰铜合金新材料及其制备方法
US10287653B2 (en) 2013-03-15 2019-05-14 Garrett Transportation I Inc. Brass alloys for use in turbocharger bearing applications
CN103741005A (zh) * 2014-01-27 2014-04-23 苏州乾雄金属材料有限公司 一种易导热金属材料
CN104911443A (zh) * 2014-03-15 2015-09-16 紫旭盛业（昆山）金属科技有限公司 一种玻璃模具
CN103972563A (zh) * 2014-04-03 2014-08-06 上海华篷防爆科技有限公司 带有铜基合金复合材料储氢瓶的发电装置
CN104264028B (zh) * 2014-10-09 2016-04-06 江苏航天动力机电有限公司 一种用于电机转子上铜合金护环
CN105059469A (zh) * 2015-07-13 2015-11-18 苏州金业船用机械厂 一种高韧性防锈船用钢板
CN105316521A (zh) * 2015-12-02 2016-02-10 苏州龙腾万里化工科技有限公司 一种便于铸造加工用黄铜合金
CN105568150A (zh) * 2016-01-27 2016-05-11 太仓捷公精密金属材料有限公司 一种金属材料的配方
DE202016102696U1 (de) 2016-05-20 2017-08-29 Otto Fuchs - Kommanditgesellschaft - Sondermessinglegierung sowie Sondermessinglegierungsprodukt
CN106086517A (zh) * 2016-08-31 2016-11-09 芜湖楚江合金铜材有限公司 一种镍锌高强度白铜合金及其制备方法
RU2622194C1 (ru) * 2016-10-10 2017-06-13 Юлия Алексеевна Щепочкина Сплав на основе меди
CN110004321B (zh) * 2018-01-05 2021-04-20 比亚迪股份有限公司 一种铜基微晶合金及其制备方法和一种电子产品
CN110004322B (zh) * 2018-01-05 2021-05-14 比亚迪股份有限公司 一种铜基微晶合金及其制备方法和一种电子产品
KR102120295B1 (ko) * 2018-12-26 2020-06-08 태원공업(주) 양백각선의 제조 방법

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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
US20060065336A1 (en) * 2003-03-21 2006-03-30 Swissmetal Ums Usines Metallurgiques Suisse Sa Copper-based alloy

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DE4006410C2 (de) 1990-03-01 1994-01-27 Wieland Werke Ag Halbzeug aus Kupfer oder einer Kupferlegierung mit Kohlenstoffzusatz
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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
US20060065336A1 (en) * 2003-03-21 2006-03-30 Swissmetal Ums Usines Metallurgiques Suisse Sa Copper-based alloy

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10760146B2 (en) * 2012-08-09 2020-09-01 Ykk Corporation Fastening copper alloy
US11519055B2 (en) * 2014-10-28 2022-12-06 Advanced Alloy Holdings Pty Ltd Metal alloys including copper
US10984931B2 (en) 2015-03-18 2021-04-20 Materion Corporation Magnetic copper alloys
US11447847B2 (en) 2018-04-20 2022-09-20 Wieland-Werke Ag Copper-zinc-nickel-manganese alloy
US20210178461A1 (en) * 2019-12-11 2021-06-17 Ngk Insulators, Ltd. Article superior in design and method for producing the same
EP3971312A1 (en) * 2020-09-17 2022-03-23 Société BIC Brass alloy for writing instrument tips
WO2022058466A1 (en) * 2020-09-17 2022-03-24 Societe Bic Brass alloy for writing instrument tips

Also Published As

Publication number Publication date
SG192046A1 (en) 2013-08-30
BR112013019625A2 (pt) 2017-01-31
JP2014512452A (ja) 2014-05-22
EP2670876A2 (en) 2013-12-11
WO2012104426A3 (en) 2012-09-27
AU2012213342A1 (en) 2013-08-22
WO2012104426A2 (en) 2012-08-09
CN103502488B (zh) 2016-01-06
KR20140021554A (ko) 2014-02-20
CN103502488A (zh) 2014-01-08
MX2013008503A (es) 2014-07-30
RU2013140681A (ru) 2015-03-10
ZA201306143B (en) 2014-10-29
CA2826185A1 (en) 2012-08-09
IL227758A0 (en) 2013-09-30

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