EP2670876A2 - Cu-ni-zn-mn alloy - Google Patents

Cu-ni-zn-mn alloy

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Publication number
EP2670876A2
EP2670876A2 EP12710042.8A EP12710042A EP2670876A2 EP 2670876 A2 EP2670876 A2 EP 2670876A2 EP 12710042 A EP12710042 A EP 12710042A EP 2670876 A2 EP2670876 A2 EP 2670876A2
Authority
EP
European Patent Office
Prior art keywords
less
copper alloy
alloy
alloy according
beta
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.)
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Application number
EP12710042.8A
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German (de)
English (en)
French (fr)
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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Application filed by Baoshida Swissmetal AG filed Critical Baoshida Swissmetal AG
Publication of EP2670876A2 publication Critical patent/EP2670876A2/en
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Classifications

    • 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

  • the present invention generally relates to wrought Cu-Ni-Zn (nickelsilver) alloys, more particularly to Cu-Ni-Zn-Mn alloys mainly for the use in areas where machining operations are substantial. Description of related art
  • fire cracking describes a kind of liquid metal embrittlement, which occurs in certain leaded alpha phase alloys, when cold deformed and annealed, whereby an explosive intergranular fracture occurs during or after the annealing process.
  • microstructural design solutions for the alloy which allows having, even in the absence of lead as a chip breaker, good machinability performances in free-machining operations.
  • This can be solved on the one hand by adjusting the microstructure related to its partitioning of the alpha/beta phases and/or by additions of minor alloying elements forming precipitates with one of the major alloying elements.
  • the minor alloying elements foreseen for this task are Fe, Al, Ca, Sn, P, and Si.
  • Precipitation hardening is typically used in low-alloyed Cu- alloys where high electrical conductivity paired with moderate strength is requested.
  • Spinoidal decomposition can be regarded as a special variation of precipitation hardening out of a supersaturated solid solution and finds application in Cu-alloys mainly in alloys containing substantial amounts of Sn or Ti.
  • Cold deformation hardening is typically used for increasing the strength in rods, profile and wire products independent of the type of alloys.
  • Solution hardening can be regarded as a side-effect when adding additional elements for improving different properties of the alloys, but is as such not of great relevance.
  • grain size hardening is industrially and technically difficult to control and its hardening contribution becomes evident only at grain sizes smaller than about 10 micrometers, sizes difficult to achieve in industrial production.
  • Mn shows with a factor of 0.5 only a slight influence towards the beta rich side in the phase diagram, while Ni exhibits a factor of -1.2 keeping the phase diagram on the alpha-rich side, and thus almost in balance for a Mn content of 6 wt.% and Ni content of 12 wt.%.
  • the complicated 4 component system Cu-Zn-Ni-Mn can in this case be treated as the Cu-Zn binary phase diagram.
  • more advanced thermodynamic software tools are required. With increasing Ni and Mn content the strength increases.
  • Typical tensile strength values for cold drawn materials are 700 - 800 MPa, while in fewer cases values up to 900 MPa can be found for strongly cold drawn wires, however that typically goes at the expense of ductility, so that tensile elongations are limited to -1 %.
  • Dezincification is understood as the dissolution of Zn in Cu-Zn alloys and can be regarded as the most severe corrosion effect in Cu-alloys. More precisely Zn dissolves by a di-vacancy diffusion process leaving a "hole" in the crystal lattice of the surface layers [J.Y. Zou, D.H. Wang, W.C. Qiu, Electrochmica Acta, 43, (1997), 1733-1737].
  • Zn dissolves by a di-vacancy diffusion process leaving a "hole” in the crystal lattice of the surface layers [J.Y. Zou, D.H. Wang, W.C. Qiu, Electrochmica Acta, 43, (1997), 1733-1737].
  • Cu-alloys free of Zn show superior corrosion resistance than brasses.
  • alpha brasses are more corrosion and dezincification resistant than the Zn-rich beta-brasses.
  • Cu-Ni-Zn alloys show in comparison to brasses similar corrosion resistance as alpha brasses, but have due to the higher nickel content a better tarnish resistance and resistance to stress corrosion cracking. Little information is available on the corrosion properties and the influence of minor alloying elements in Cu-Ni-Zn alloys, but can be extrapolated from the effects known to brasses. There different alloying elements have been reported to improve corrosion resistance and retard dezincification in brasses as summarized in Ref. [D.D. Davies, "A note on the dezincification of brass and the inhibiting effect of elemental additions", Copper Development Association Inc., 260 Madison Avenue, New York, NY 10016, (1993), 7013- 0009].
  • the present invention aims also for applications where corrosion properties can be of crucial importance, in particular in solutions where crevice conditions are present. This is for instance the case in ball pen tips where the gap between the ball and the surrounding pen socket is of the order of few micrometers distance and the ink is not constantly stirred (during storage of the pen tip). In water-based gel-inks this may locally lower the pH of the ink and cause local corrosion attack. The right choice of elements and the appropriate microstructure to reduce corrosion is thus detrimental to the lifetime of a pen tip.
  • 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
  • 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. However, in contrary to stainless steels 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.
  • the copper alloy disclosed herein exhibits machinability performance (easier chip handling, less tool consumption) superior to that of stainless steel used in pen tip and also other applications allowing for a higher production rate of parts per hour.
  • machinability performance easier chip handling, less tool consumption
  • the alloy When subjected to a special low- temperature heat treatment, the alloy has a unique microstructure, which even in absence of lead, is leading to a good machinability performance superior to that of typical stainless steels used in pen tips.
  • the alloy that is an ecologically friendly, lead-free free-machining Cu-Ni-Zn-Mn alloy free of harmful elements.
  • Fig1 shows an optical microscopy images of samples heat treated at 350°C (Fig. 1 a) and 450°C (Fig. 1 b) of alloy N a 1 ;
  • Fig. 2 shows an optical image of the longer screw-like chips of alloy N° 1 produced with the Citizen long turning machine
  • Fig. 3 shows an optical microscopy images of the as-cast structure (Fig. 3a) and the cold deformed annealed (450°C) (Fig. 3b) of alloy N ⁇ 3;
  • Fig. 4 shows pseudo-binary phase diagram (Fig. 4a) and phase fraction diagram for a specific composition (Fig. 4b) of alloy N e 3.
  • Fig. 5 represents a screw-type and curly type chips shown for two types of alloys of the alloy N° 3;
  • Fig. 6 shows machining tests with Mikron Multistar made at 100 Hz on alloy N°3 with composition A annealed at 450°C (Fig. 6a and 6b); and alloy N°: 1 (Fig. 6c and 6d), chip length of the leaded alloy N°: 1 being smaller than that in alloy N°3;
  • Fig. 7 shows as-extruded microstructure (Fig. 7a) and after 2 cycles of cold deformation and annealing at 650°C) (Fig. 7b) of alloy N e 5; heat treated alloy at 540°C followed by 350°C (Fig. 7c) and 400°C (Fig. 7d) low temperature heat treatment of alloy N° 5; and Fig. 8 shows optical microscopy image of a sample annealed at 540°C followed by a second annealing process at 400°C (Fig. 8a); secondary electron microscopy image of alloy with NiSn preciptates in beta phase matrix and at boundary to alpha grains (Fig. 8b) both of alloy l ⁇ P: 6.
  • the present invention generally relates to wrought Cu-Ni-Zn (nickel-silver) alloys, more particularly to Cu-Ni-Zn-Mn alloys mainly for the use in areas where machining operations are substantial.
  • the present invention relates also to leaded, leadless or lead-free free-machining Cu- Ni-Zn-Mn alloys particularly suited for applications in areas where free machining operations are heavily involved, such as writing instruments, eye glass frames, medical tools, electrical connectors, locking systems, fine tooling, fasteners and bearing for automotive industry, without restriction to other fields of application.
  • the present invention aims to replace wrought steel products in various applications where high strength and sufficient ductility combined with excellent free-machinability are required with or without the presence of lead.
  • the present invention has among the above mentioned various fields of applications particular focus on writing instruments, where the tip material is in direct contact with the ink and the ball material.
  • ball materials such as various types of tungsten carbide hard- metal balls with different binders (Co, Co+Ni+Cr), different types of steels and different types of ceramic balls are on the market, while the type of inks can be separated into mainly gel-based and oil-based inks and to a lesser extent inks based on other liquids.
  • the Cu-Ni-Zn-Mn alloy family presented here can be combined with all possible combinations of ball or ink materials.
  • the objective of the present invention is to provide a new high- strength Cu-Ni-Zn-Mn alloy family that thanks to a special thermo- mechanical treatment and an optimized alloy composition reaches mechanical properties comparable with those of wrought stainless steel alloys.
  • the leaded variations exhibit excellent machinability and are thus promising candidates for all applications, where high strength, good ductility and excellent machinability are of utmost importance, i.e. writing instruments, eye glass frames, keys, applications in watch industry, fittings and other fine tooling and free-machining applications, without restricting other fields of application.
  • the lead-free variations do not contain any user unfriendly amounts of elements, which either may be harmful for human and/or environment.
  • the present invention is realized by providing seven different Cu- Ni-Zn-Mn alloys on a basis of copper, zinc, nickel, manganese and other elements.
  • the compositions of the alloys presented here and in the granted patent family EP1608789B 1 are optimized for special applications, where apart from production costs the appearance of the alloy is as important as the mechanical properties, machinability and corrosion properties.
  • Different dimensions and geometrical forms can be produced from these alloys, such as wires, strips, rods, tubes and various profiles and square shapes.
  • wire drawn products such as pen tips for writing instruments are addressed, which after a hot deformation process are typically drawn down to the final diameter in successive cold drawing and heat treatment steps.
  • Mn content of the alloy is limited to the range of 4 - 7 wt.%.
  • Higher levels of Mn show a negative effect during cold-forming, while a lower M n content increases the risk of fire cracking and too low beta content during warm extrusion processes.
  • a higher Ni content >14 wt.%) is pushing the phase diagram towards a purely mono-phase alloy even at elevated temperatures.
  • a lower Ni content ⁇ 9.0 wt.
  • the Zn content is chosen in a range that allows to vary the microstructure (fraction of beta content) from 0% to approximately 50% ⁇ 10%.
  • Zn content > 40 wt.% show a to high amount of beta suitable for cold drawing, while a lower content than 34 wt.% makes hot extrusion processing difficult.
  • the content of Pb is kept at a minimum level to assure good to excellent machinability.
  • the copper alloy is of grey or silver color / appearance typical for Cu-Ni-Zn-Mn alloys sometimes having a nuance of a pale yellowish tone.
  • the first alloy is based on the granted patent EP1608789 applications and consists of 42 - 48 wt.% Cu, 34 - 40 wt.% Zn, 9 - 14 wt.% Ni, 4 - 7 wt.% Mn, ⁇ 0.5 wt.% Fe, ⁇ 0.03 wt.% P and ⁇ 2.0 wt.% Pb.
  • thermodynamic calculations in the multi-component system shows that for minor elements such as Fe a content of 0.5 wt. % increases the beta phase fraction of the alloy by about -5-10%, without changing the slope of the curves, while at intermediate temperatures of about 400°C Fe provokes a co-existence of the gamma phase ( ⁇ 5 % volume fraction) in an alpha/beta matrix. Phosphorous is added in order to increase the corrosion resistance.
  • Table 1 Machining test parameters used for the alloys included in the present invention.
  • the first invention presented here builds-up on the processing parameters used for the above mentioned granted patents, i.e. EP1608789, which allow the formation of a mono-phase alpha Cu-Ni-Zn-Mn alloy. Its primary aim was to develop an alloy suitable for pen tip applications, where the corrosion resistance is superior with respect to duplex phased Cu-Ni-Zn-Mn alloys. This can only be guaranteed in purely mono-phase state not allowing for microstructural conditions allowing galvanic corrosion leading to localized microstructural determined crevice conditions. [0030] Compared to aforementioned alloys developed in the patent family EP1608789, the alloy presented here is in addition subjected to heat treatments at lower temperatures of 300-450°C (also called " low
  • Figs. 1 a and 1 b shows micrographs with the low temperature heat treated alloys having fine precipitates of beta ' and beta, respectively. Note that the phase boundary between beta and beta ' (its tetragonal distorted variation) lies between 400 and 450°C. More
  • Figs. 1 a and 1 b shows samples heat treated at 350°C (a) and 450°C (b) of alloy N s 1.
  • 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. Agren, F. H. Hayes, L. Hoglund, U.R. Kattner, B. Legendre, R. Schmid-Fetzer: Applications of Computational Thermodynamics. Z.Metallischen 93, (2002), 128-142].
  • Said alloy results in improved hardness and tensile strength of 850 - 950 MPa with remaining elongation levels of 2-10 % compared to the same alloy not subjected to the low temperature heat treatment (see Table 2). Even higher strength and ductility might be reachable by further optimization of thermo-mechanical treatment as it was done for unleaded alloys (see further down).
  • the second alloy of the present invention has a very similar chemical composition as the first mentioned alloy, however including arsenic, i.e. of 42 - 48 wt.% Cu, 34 - 40 wt.% Zn, 9 - 14 wt.% Ni, 4 - 7 wt.% Mn, ⁇ 0.5 wt.% Fe, ⁇ 0.03 wt.% P, ⁇ 2.0 wt.% Pb and 0.01 - 0.15 wt.% As.
  • arsenic i.e. of 42 - 48 wt.% Cu, 34 - 40 wt.% Zn, 9 - 14 wt.% Ni, 4 - 7 wt.% Mn, ⁇ 0.5 wt.% Fe, ⁇ 0.03 wt.% P, ⁇ 2.0 wt.% Pb and 0.01 - 0.15 wt.% As.
  • Table 2 Vickers hardness tests on samples annealed at 350 and 400°C for 1 , 5, 10 and 24 hours compared to normal annealing temperatures for recrystallisation.
  • the low level As additions does not exhibit any difference in the microstructural appearance of the alloy and it exhibits the same mechanical properties and machinability performance as the version without As (First alloy).
  • the third alloy of the present invention is unleaded and contains the following chemical composition: 45 - 48 wt.% Cu, 37 - 40 wt.% Zn, 9 - 14 wt.% Ni, 4 - 7 wt.% Mn, ⁇ 0.5 wt.% Fe, ⁇ 0.03 wt.% P, ⁇ 0.15 wt.% As and ⁇ 0.1 wt.% Pb.
  • 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. 3a shows the as-extruded microstructure of the duplex phased alloy.
  • a second goal of the invention of this alloy was to increase the mechanical properties of the alloy by low temperature heat treatment steps during wire cold deformation.
  • Fig. 3b shows the microstructure of such a cold deformed and annealed microstructure, where a heat treatment of 450°C has been applied.
  • Zn content below 37.5 % reduces the amount of beta during hot extrusion ( ⁇ 800°C) to a volume fraction close to zero percent, while with a content of Zn > 39% the beta phase fraction reaches about 30% at this temperature.
  • annealing its content increases to almost 50% and thus reduces the ability to strongly cold deform the material.
  • Increasing the Mn content and reducing the Ni content at the same Cu : Zn ratio increases stability of the beta phase at high temperatures suitable for hot extrusion, which can be reversed at intermediate annealing temperatures ( ⁇ 600°C). More particularly, an optical microscopy images of the as-cast structure is shown in Fig. 3a and the cold deformed annealed (450°C) is shown if Fig. 3b for alloy N° 3.
  • Figs. 4a and 4b show pseudo-binary phase diagram (a) and phase fraction diagram for a specific composition (b) of alloy N° 3.
  • Said microstructure has been achieved with a Zn content of 38 and 39 wt.%. Lower Zn content lowers the amount of beta phase significantly, while Zn larger than 40 wt.% are showing a too low density of alpha grains.
  • 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 N°:1 (see Figure 6).
  • Figs. 6a to 6d represent machining tests with Mikron Multistar made at 100 Hz on alloy N°3 with composition A annealed at 450°C (Figs. 6a and 6b); and alloy N°:1 (Fig. 6c and 6d). Chip length of the leaded alloy N°:1 is smaller than that in alloy N°3.
  • the forth alloy of the present invention is also unleaded and contains the following chemical composition: 45 - 48 wt.% Cu, 36 - 40 wt.% Zn, 9 - 14 wt.% Ni, 4 - 7 wt.% Mn, ⁇ 0.5 wt.% Fe, ⁇ 1.5 wt.% Ca, ⁇ 1.0 wt.% Si, ⁇ 1.0 wt.% Al, ⁇ 0.03 wt.% P, ⁇ 0.15 wt.% As and ⁇ 0.1 wt.% Pb.
  • Additions of at least one of the other alloying elements Si, Al or Fe further improve the machinability of this alloy.
  • 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. [0054] Fifth alloy
  • 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 main focus of this alloy was to generate a variation of the aforementioned unleaded Cu-Ni-Zn-Mn alloy (N s : 3) that is on the one hand age hardenable, i.e. forms secondary precipitates from a supersaturated solid solution matrix and on the other hand is suitable for hot and cold deformation, i.e. allows to be transformed from a duplex rich in beta structure into a duplex structure poor in the beta phase fraction.
  • Figs. 7a to 7d show as-extruded microstructure (Fig. 7a) and after 2 cycles of cold deformation and annealing at 650°C) (Fig. 7b) of alloy N° 5. Heat treated alloy at 540°C followed by 350°C (Fig. 7c) and 400°C (Fig. 7d) low temperature heat treatment of alloy N a 5. [0059] Cycles of annealing ( ⁇ 600-700°C) and cold deformation treatments cause an alteration in the microstructure with an increasing content of the beta volume fraction to -50%, whereby the alpha grains form the matrix surrounded by beta grains. When successively annealed at lower temperatures ⁇ 450°C fine precipitates in form of needles nucleate (Fig. 7c and 7d).
  • Ni-Aluminides are formed right after having reached the solidus curve and maintain a constant level of about 0.02 % and thus act as strong grain growth inhibitors as mentioned before.
  • Al has a strong effect on the variation of the beta fraction reaching a minimum value at around 600°C which towards higher and lower temperatures is increasing.
  • the tensile properties of the alloy show values ranging from 850 - 900 MPa with elongations of 2-12 % (see Table 4). [0062] Sixth alloy
  • 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. [0063] 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.
  • Figs. 8a and b show optical microscopy image of a sample annealed at 540°C followed by a second annealing process at 400°C (Fig. 8a); Secondary electron microscopy image of alloy with NiSn preciptates in beta phase matrix and at boundary to alpha grains (Fig. 8b) both of alloy N ⁇ : 6.
  • Vickers hardness measurements revealed a hardness of 230 - 240 HV for the age hardening at 350°C, while values between 220 - 230 HV were measured for heat treatments at 300 and 400°C comparable with values given in Table 4 for alloy N°:5, but slightly lower.
  • the seventh alloy of the present invention is also an age-hardenable alloy and has the following chemical composition: 43.5 - 48 wt. % Cu, 36 - 40 wt. % Zn, 9 - 12 wt.% Ni, 5 - 7 wt.% M n, ⁇ 0.1 wt.% Al, ⁇ 0.1 wt. % Sn, ⁇ 0.5 wt. % Fe, ⁇ 1 .0 wt . % Si, ⁇ 0.3 wt.% P, ⁇ 0.15 wt. % As and ⁇ 2.0 wt. % Pb.
  • this invention aims for an age hardenable Cu-Ni-Zn-Mn alloy that apart from precipitations of alpha in beta or vice versa also contains typical alloying elements suitable for age hardenability.
  • Silicon and Phosphorus are chosen as
  • 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. %.
  • Ni 5Si2 precipitates are formed right after temperature has been lowered to below the solidus curve. However their detection is a non-trival task and was not successful with the instruments at hands. In low-alloyed copper the precipitates are nucleating and growing to rounded platelets [D. Zhao, Q.M. Dong, B.X. Kang, J.L. Huang, Z.H. Jin, Mater. Sci. Eng. A361 , (2003). 93-99].

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EP12710042.8A 2011-02-04 2012-02-03 Cu-ni-zn-mn alloy Withdrawn EP2670876A2 (en)

Applications Claiming Priority (2)

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PCT/EP2012/051890 WO2012104426A2 (en) 2011-02-04 2012-02-03 Cu-ni-zn-mn alloy

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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)
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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
US20140294665A1 (en) 2014-10-02
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CA2826185A1 (en) 2012-08-09
IL227758A0 (en) 2013-09-30

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