EP2208802B1 - Aluminium enthaltende, bleifreie Automatenmessinglegierung und deren Herstellungsverfahren - Google Patents

Aluminium enthaltende, bleifreie Automatenmessinglegierung und deren Herstellungsverfahren Download PDF

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EP2208802B1
EP2208802B1 EP09180653A EP09180653A EP2208802B1 EP 2208802 B1 EP2208802 B1 EP 2208802B1 EP 09180653 A EP09180653 A EP 09180653A EP 09180653 A EP09180653 A EP 09180653A EP 2208802 B1 EP2208802 B1 EP 2208802B1
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free
alloy
lead
bismuth
brass
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EP2208802A1 (de
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Chuankai Xu
Zhenqing Hu
Siqi Zhang
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Xiamen Lota International Co Ltd
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Xiamen Lota International Co Ltd
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    • 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 a lead-free free-cutting aluminum brass alloy, in particular a lead-free free-cutting aluminum brass alloy and its manufacturing method which is applicable in low pressure die castings and forgings.
  • Pub. No. CN101225487A to Xuhong Hu discloses an arsenic-containing low-lead brass alloy which comprises (wt%) 57-62 Cu, 36-43 Zn, 0.01-1.0 A1, 0.05-2.5 Bi, 0.005-0.3 As, ⁇ 0.2 Pb and ⁇ 0.65 Sn, wherein small amounts ofNi, Fe and S and minimum amounts of Si, Mg, Mn and Re (Rhenium) are selectively added. No P is added.
  • Arsenic is one of the main elements of such an alloy.
  • Pat. No. CN1045316C to Kohler discloses a low-lead bismuth brass alloy which comprises (wt%) 55-70 Cu, 30-45 Zn, 0.2-1.5 A1, 0.2-0.3 Bi, ⁇ 1.0 Pb, ⁇ 2.0 Ni, ⁇ 1.0 Fe, ⁇ 0.25 In, and 0.005-0.3 Ag, further comprising minimal amounts of one or more of the elements Ta, Ga, V, B, Mo, Nb, Co, and Ti. Zr is selectively added. No Si or P is added.
  • Pub. No. CN1710126A to Powerway discloses a lead-free free-cutting low-antimony bismuth brass alloy and its manufacturing method which comprises (wt%) 55-65 Cu, 0.3-1.5 Bi, 0.05-1.0 Sb, 0.0002-0.05 B, wherein elements such as Ti, Ni, Fe, Sn, P and rare earth elements are selectively added and the balance is Zn and impurities. No Si or Al is added. If the content of Sb is ⁇ 0.1, the amount of Sb released in the water will exceed the requirements of the NSF standard.
  • JP2000-239765A to Joetsu discloses a lead-free brass alloy with corrosion resistance for castings, which comprises (wt%) 64-68 Cu, 1.0-2.0 Bi, 0.3-1.0 Sn, 0.01-0.03 P, 0.5-1.0 Ni, 0.4-0.8 Al, ⁇ 0.2 Fe and the balance being Zn and impurities.
  • the content of Bi is higher and no Si is added.
  • the developed bismuth brasses are mainly deformation alloys and comprise more than 0.5wt% bismuth.
  • Lead-free or low-lead free-cutting antimony brass has excellent castability, weldability, hot working formability, and dezincification corrosion resistance.
  • antimony is more toxic than lead.
  • the NSF/ANSI61-2007 standard requires that Sb is released in drinking water in amounts ⁇ 0.6 ⁇ g/L and that Pb is released in amounts ⁇ 1.5 ⁇ g/L (NSF61-2005 requires that Pb release is ⁇ 5 ⁇ g/L).
  • Antimony brass is not suitable for components used in drinking water supply system.
  • Lead-free free-cutting silicon brass is a brass which has certain good developing prospects.
  • lead-free free-cutting silicon brasses are mainly low-zinc deformation silicon brass. Most of them comprise small amounts of bismuth and the cost of raw material is rather higher.
  • Aluminum brass has good corrosion resistance, but its cuttability is inadequate. Few patents and other literature exists relating to lead-free free-cutting aluminum brasses. United States Patent No. 3,773,504 ( 1973 ) discloses a Cu-Zn-Al-P series alloy having wear resistance. Japanese Patent 2003-253358 discloses a lead-free free-cutting low-zinc aluminum brass (containing vanadium and boron, etc.)
  • Figures 1A , 1B and 1C show the chip shape of example alloy 1 obtained at a cutting speed of 40 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 1D , 1E and 1F show the chip shape of alloy CuZn40Pb1A10.6 obtained at a cutting speed of 40 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 2A , 2B and 2C show the chip shape of example alloy 1 obtained at a cutting speed of 60 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 2D , 2E and 2F show the chip shape of alloy CuZn40Pb1A10.6 obtained at a cutting speed of 60 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 3A , 3B and 3C show the chip shape of example alloy 1 obtained at a cutting speed of 80 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 3D , 3E and 3F show the chip shape of alloy CuZn40Pb1A10.6 obtained at a cutting speed of 80 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 4A , 4B and 4C show the chip shape of example alloy 1 obtained at a cutting speed of 100 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • Figures 4D , 4E and 4F show the chip shape of alloy CuZn40Pb1A10.6 obtained at a cutting speed of 100 m/minute, at feeding quantities of 0.1, 0.2, and 0.3 mm/revolution, respectively.
  • the object of the present invention is to solve the technical problems of current aluminum brass alloys, including bad cuttability, a tendency of hot cracking and difficulty in welding.
  • the object of the invention also includes the provision of an environment-friendly lead-free free-cutting aluminum brass alloy, which is applicable for low pressure die casting, gravity casting, horizontal continuous casting, forging and welding.
  • the object of the present invention is realized by selection of the following elements and their composition design as defined in claim 1.
  • the present invention provides a lead-free free-cutting aluminum brass alloy which comprises (wt%): 57.0 ⁇ 63.0 Cu, 0.3 ⁇ 0.7 Al, 0.1 ⁇ 0.5 Bi, 0.1 ⁇ 0.5 Si, 0.2 ⁇ 0.4 Sn, 0.01 ⁇ 0.15 P, and which further comprises at least two elements selected from Mg, B and rare earth elements, with the balance being Zn and unavoidable impurities.
  • the at least two selected elements are present in amount of 0.01 ⁇ 0.15wt% Mg, 0.001 ⁇ 0.05wt% rare earth elements and 0.0016 ⁇ 0.0020wt% B.
  • aluminum is the main alloy element, except for zinc.
  • Al can improve corrosion resistance and strength of common brass.
  • bismuth can form compact oxide film for preventing melt oxidation, and for reducing the loss of zinc, which is prone to volatilize and oxidize.
  • oxidation characteristics of aluminum are unfavorable for castability and weldability.
  • aluminum will coarsen the grain of common brass.
  • the zinc equivalent coefficient of aluminum is rather great, and can substantially enlarge the ⁇ phase zone. If combined with silicon, aluminum is prone to increase the ⁇ phase rate, and promote the formation of the ⁇ phase. Therefore, it is beneficial for improving the cuttability of brass.
  • the surface tension of aluminum (860 dyne/cm) is less than that of copper. It can form solid solutions in copper resulting in decreasing the surface tension of copper. It is favorable for spherifying bismuth, which is distributed in the grain boundary.
  • the surface tension of zinc (760dyne/cm) is less than that of copper. It can form solid solutions in copper. It is also favorable for spherifying bismuth which is distributed in the grain boundary.
  • aluminum content is lower than common commercialized aluminum brass, and is limited in the range of 0.3 ⁇ 0.7wt%, more preferably in the range of 0.4 ⁇ 0.6wt%. Higher aluminum content is not beneficial for castability and weldability.
  • Bismuth is added to improve the cuttability of aluminum brass.
  • bismuth will increase the hot and cold cracking tendency of copper alloys.
  • the thermodynamic reason for this is the large differential between the surface tension of bismuth and copper, with the result that the dihedral angle between liquid bismuth and solid copper grain tends to be zero.
  • Bismuth will fully wet copper grains. After solidification, bismuth will be distributed in the grain boundary in the form of a continuous film.
  • the present invention selects the elements which can form solid solutions in copper and decrease the surface tension of copper, such as the above-mentioned main alloy elements, zinc and aluminum.
  • bismuth content is limited in the range of 0.1 ⁇ 0.5wt%. Higher bismuth content will not only increase the tendency of hot cracking, which makes castings crack from time to time during low pressure die casting, but also increase cost, reduce corrosion resistance and increase the risk of thallium as an impurity in amounts beyond the standard.
  • the content of Bi is limited in the range of 0.1 ⁇ 0.5wt%, more preferably in the range of 0.1-0.3wt%, so that it can achieve castability, weldability, cuttability and low cost.
  • Tin mainly include strengthening the solid solution, and improving dezincification corrosion resistance of the alloy. If ⁇ phase is formed in the alloy, small amounts of tin will make ⁇ phase more effectively dispersed, uniformly distributed, and decrease the harmful effects of ⁇ phase on plasticity, and further improve cuttability.
  • the surface tension of tin is 570 dyne/cm.
  • the effect of zinc in promoting bismuth spheroidizing is greater than the spheroidizing effect of zinc and aluminum.
  • Tin content is limited to the range of 0.2 ⁇ 0.4wt%. Higher content of tin is helpful for bismuth spheroidizing, but cost will increase, and together with silicon and aluminum, more ⁇ phase will be produced resulting in increasing hardness, decreasing plasticity and unbeneficial effects for cutting and forming.
  • silicon is the main element for adjusting the composition of matrix phase. If there is an appropriate matching ratio among silicon and zinc and aluminum, silicon will promote the formation of ⁇ phase in the alloy and then improve the cuttability. With the increasing of silicon content, ⁇ phase will increase and cuttability will be improved. However, the plasticity will gradually decrease and tendency of hot cracking will increase. It is not beneficial for casting forming, especially for low pressure die casting forming.
  • silicon content is limited in the range of 0.1 ⁇ 0.5wt%, and is more preferably limited in the range of 0.2 ⁇ 0.5wt%.
  • the matrix phase of the alloy is ⁇ phase and minor amount of ⁇ phase.
  • the matrix phase of the alloy is ⁇ phase and minor amount of ⁇ phase and ⁇ phase.
  • Phosphorus is one of the main elements of the alloy. Its effects include deoxidation, improving castability and weldability of the alloy, reducing the oxidation loss of beneficial elements such as aluminum, silicon, tin and bismuth, and refining brass grains. If phosphorus content in the brass exceeds 0.05wt%, intermetallic compound Cu 3 P will be formed. It is beneficial for improving the cuttability of the alloy, but meanwhile, the plasticity will be decreased. Excessive Cu 3 P resulting from excessive phosphorus will increase the tendency of hot cracking during low pressure die casting.
  • the surface tension of phosphorus is 70 dyne/cm and phosphorus has bigger solid solubility in copper at high temperature; therefore it will obviously decrease the surface tension of copper and improve the effect of bismuth spheroidization. It is a "plasticizer" of bismuth-contained brass.
  • bismuth In the presence of phosphorus, tin, aluminum and zinc, bismuth will be spherically distributed in grain and in grain boundary. It will obviously decrease its unbeneficial influence for cold and hot plasticity and improve castability and weldability. Meanwhile, as bismuth is spherically, uniformly and dispersedly distributed, it is favorable for bismuth to play its beneficial influence on cuttability.
  • Phosphorus content is limited in the range of 0.01 ⁇ 0.15wt%. If it is used for horizontal continuous castings or forgings, its content is in the middle to upper limits of the specified range. If it is used for low pressure die casting products (such as the bodies of a faucet), its content is in the middle to lower limits of the specified range.
  • Magnesium is a selectively added element. Its main effects include further deoxidizing before horizontal continuous casting and preventing castings from cracking during low pressure die casting and welding. If magnesium content exceeds 0.1wt%, the effect on preventing castings from cracking is still obvious. However, the elongation rate will be decreased. This effect also appears in lead-free free-cutting high-zinc silicon brass. Magnesium also has the effect of grain refinement with the result that bismuth and hard-brittle intermetallic compounds grain is more dispersedly and uniformly distributed and is beneficial for improving cuttability, castability and weldability.
  • magnesium content is larger than 0.1wt%, it will form intermetallic compound Cu 2 Mg with copper and is also beneficial for improving cuttability. If magnesium is added, its content is preferably limited in the range of 0.01 ⁇ 0.15wt%.
  • the main effect of selectively adding boron and rare earth metal is for grain refinement.
  • the solid solubility of boron in copper is very small, but it will be reduced with the temperature decrease.
  • Precipitated boron also has the effect of improving cuttability.
  • Boron also could suppress dezincification.
  • rare earth metal also can clean the grain boundary and reduce the unbeneficial effects resulting from the impurities in the grain boundary.
  • Cerium and bismuth can form intermetallic compound BiCe whose melting point reaches up to 1525°C so that bismuth can enter into the grain boundary in the form of such intermetallic compound. It is favorable for eliminating the hot and cold brittleness caused by bismuth, but meanwhile the contribution of bismuth on cuttability is reduced.
  • Magnesium, boron, and the rare earth elements are added in small amounts as defined in claim 1.
  • Zr and C are present only as unavoidable impurities. Zr and C are not required in the alloy. If Zr is present as an unavoidable impurity, the amount ofZr at most at 0.0007wt%. IfC is present as an unavoidable impurity, the amount of C will be less than 0.0015wt%. The alloy does not require Ni.
  • lead, iron and antimony may be present as unavoidable impurities, but their content should be limited in the range of ⁇ 0.1wt%, ⁇ 0.1wt% and ⁇ 0.03wt%, respectively. If Pb ⁇ 0.2wt%, Pb released will exceed government standards. If Sb>0.05wt%, Sb released will exceed the standard. Therefore, the alloy containing such larger content is not applicable for the components used in drinking water systems.
  • Trace antimony can improve dezincification corrosion resistance of the alloy, like tin and arsenic.
  • the allowed iron content is larger than 0.2wt%.
  • aluminum and silicon are present and iron will form hard-brittle iron-aluminum intermetallic compounds and iron silicide, which will decrease the plasticity, corrosion resistance and castability.
  • the hard particles formed by these intermetallic compounds are placed on the surface of the products, after polishing and electroplating, a "hard spots" defect characterized by inconsistent brightness will appear. Any such products must be scrapped.
  • Alloys containing small amounts of such impurities are beneficial for collocation using lead brass, antimony brass, phosphorus brass, magnesium brass and other old brass materials, saving resource and cost.
  • the features of selection of the above alloy elements and their composition design include making bismuth be spherically, uniformly and dispersedly distributed in the grain and in the grain boundary, instead of continuous film distribution in the grain boundary.
  • the invented alloy and old bismuth brass alloy can be recycled.
  • Lead brass, antimony brass, phosphorus brass, magnesium brass and other old brass materials can be used for saving resources and cost.
  • the manufacturing method is easily operated, and current lead brass manufacturing equipment can be used.
  • the volume shrinkage samples should ensure that the surface of concentrating shrinkage cavities is smooth, there is no porosity in depth, the elongation rate of as-cast is larger than 6%, the hardness HRB is in the range of 55 ⁇ 75, and the bending angle of the strip samples is larger than 55°.
  • the inventive alloy is a new environment-friendly aluminum brass, especially applicable for low pressure die casting or gravity casting or forging products which are subject to cutting and welding, such as components for drinking water supply systems.
  • the manufacturing method of the inventive alloy is as follows:
  • Castability of the inventive alloy is measured by four kinds of common standard test samples for casting alloys.
  • volume shrinkage test samples are used for measuring the shrinkage condition. If the face of the concentrating shrinkage cavity is smooth, and there is no visible shrinkage porosity in depth, it will be shown as "O.” It indicates the alloy has good fluidity, strong feeding capacity and high casting compactability. If the face of the concentrating shrinkage cavity is smooth but the height of visible shrinkage porosity is less than 3mm in depth, it indicates castability is good, and will be shown as " ⁇ " If the face of the concentrating shrinkage cavity is not smooth and the height of visible shrinkage porosity is more than 5mm in depth, it will be shown as "x.” It indicates the alloy has bad fluidity, weak feeding capacity and bad casting compactability. Leakage will appear if water test is done.
  • Strip samples are used for measuring linear shrinkage rate and bending angle of the alloy. If the bending angle is larger than 55°, it indicates it is excellent. If it is less than 40°, it indicates the plasticity of the alloy is too low and it is poor. If it is larger than 100°and even unpliant, it indicates the plasticity of the alloy is good and is not beneficial for cutting.
  • Circular samples are used for measuring shrinkage crack resistance of the alloy. If there is no crack, it is rated as excellent, and will be shown as "O.” If there is a crack, it is rated as poor, and will be shown as "x.”
  • Spiral samples are used for measuring the melt fluid length and evaluating the fluidity of the alloy.
  • the pieces for welding are low pressure die castings and CuZn37 brass pipes and are processed by brazing and flame heating at a temperature of 350 ⁇ 400°C.
  • Weldability measuring standards relate to whether cracks and porosity appear in the welding seam and the heat affected zone. If there is no crack and no porosity, it is qualified; otherwise it is unqualified.
  • the common method is fixing the cutting process parameters, measuring the cutting resistance, energy consumption or spindle torque of the machine motor and so on, comparing with free-cutting lead brass such as C36000 and finally obtaining the relative cutting rate.
  • good or poor materials' cuttability is very closely related to the cutting process parameters.
  • the cuttability of the material is "good” or “poor,” is always judged by the shape and size of the chips, smooth degree of chip discharging and wear speed of the tools.
  • the cutting process parameters can be adjusted on the base of different materials or different states of the same material for getting successful cutting operation. The influence of the cutting process parameters on chip shape is shown in Table 4.
  • feeding quantity has great influence on chip shape and size, while linear speed has little influence on chip shape and size.
  • the chip shape of example alloy 1 is a thin sheet or thin tile. It indicates cuttability is good, but not better than lead brass which contains 1wt% Pb.
  • Cutting depth is 4mm.
  • Example alloy 1 CuZn40Pb1Al0.6 feeding quantity/mm ⁇ r -1 feeding quantity/mm ⁇ r -1 0.1 0.2 0.3 0.1 0.2 0.3 40 See Fig. 1A See Fig. 1B See Fig. 1C See Fig. 1D See Fig. 1E See Fig.
  • Dezincification corrosion testing is carried out according to GB10119-1988 standard.
  • Salt-spray corrosion testing is carried out according to ASTMB368-97 standard.
  • Release amount Value Q is measured according to NSF/ANSI61-2007 standard.

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Claims (5)

  1. Bleifreie Automaten-Aluminiummessinglegierung, umfassend:
    57,0 bis 63,0 Gew.-% Cu,
    0,3 bis 0,7 Gew.-% Al,
    0,1 bis 0,5 Gew.-% Bi,
    0,2 bis 0,4 Gew.-% Sn,
    0,1 bis 0,5 Gew.-% Si,
    0,01 bis 0,15 Gew.-% P,
    mindestens zwei Elemente, ausgewählt aus der Gruppe von 0,01 bis 0,15 Gew.-% Mg, 0,0016 bis 0,0020 Gew.-% B, 0,001-0,05 Gew.-% Seltene Erdelemente, und
    wobei der Rest Zn und unvermeidbare Verunreinigungen ist,
    wobei unter die Verunreinigungen fällt: Pb ≤ 0,1 Gew.-%, Fe ≤ 0,1 Gew.-%, Sb ≤ 0,03 Gew.-%, Zr höchstens 0,0007 Gew.-% und C weniger als 0,0015 Gew.-%.
  2. Bleifreie Automaten-Aluminiummessinglegierung nach Anspruch 1, umfassend 0,4 bis 0,6 Gew.-% Al, 0,2 bis 0,5 Gew.-% Si und 0,1 bis 0,3 Gew.-% Bi.
  3. Bleifreie Automaten-Aluminiummessinglegierung nach Anspruch 1 oder 2, wobei die Verunreinigungen ≤ 0,1 Gew.-% Pb, ≤ 0,1 Gew.-% Fe und ≤ 0,03 Gew.-% Sb umfassen.
  4. Niederdruckspritzguss-Herstellungsverfahren, welches die bleifreie Automaten-Aluminiummessinglegierung nach Anspruch 1 oder 2 verwendet, wobei die Temperatur für Niederdruckspritzgießen 980 bis 1000°C beträgt.
  5. Horizontales Strangguss-Herstellungsverfahren, welches die bleifreie Automaten-Aluminiummessinglegierung nach Anspruch 1 oder 2 verwendet, wobei die Formschmiedetemperatur für horizontales Stranggießen 650 bis 710°C beträgt.
EP09180653A 2008-12-23 2009-12-23 Aluminium enthaltende, bleifreie Automatenmessinglegierung und deren Herstellungsverfahren Active EP2208802B1 (de)

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PL09180653T PL2208802T3 (pl) 2008-12-23 2009-12-23 Automatowy stop mosiądzowo-glinowy niezawierający ołowiu i sposób jego wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2008101882634A CN101440445B (zh) 2008-12-23 2008-12-23 无铅易切削铝黄铜合金及其制造方法
US12/643,513 US7776163B2 (en) 2008-12-23 2009-12-21 Lead-free free-cutting aluminum brass alloy and its manufacturing method

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WO2013145964A1 (ja) * 2012-03-30 2013-10-03 株式会社栗本鐵工所 水道部材用黄銅合金
CN105132739B (zh) * 2015-09-10 2017-03-22 孝感市元达新材料科技有限公司 一种无铅黄铜合金及其制备方法
CN115305381A (zh) * 2021-05-13 2022-11-08 湖南特力新材料有限公司 一种无铅易切削黄铜合金及其制造工艺
CN113604702A (zh) * 2021-07-20 2021-11-05 佛山市麦欧金属有限公司 一种激光切割925银版专用铜合金及加工方法
CN115044799B (zh) * 2022-06-02 2023-03-14 广东中欧卫浴用品有限公司 一种无铅dr抗脱锌铜合金的制作方法及其制作生产设备
CN115354188B (zh) * 2022-08-26 2023-09-15 宁波金田铜业(集团)股份有限公司 一种易焊接黄铜及其制备方法

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US5630984A (en) * 1992-06-02 1997-05-20 Ideal-Standard Gmbh Brass alloy
JP3374037B2 (ja) * 1997-04-02 2003-02-04 古河電気工業株式会社 半導体リードフレーム用銅合金
CN1916209B (zh) * 2006-08-25 2010-05-12 江西铜业集团(贵溪)新材料有限公司 一种稀土碲铋黄铜合金及其制备方法
CN101225487B (zh) * 2008-01-15 2011-04-06 胡旭红 含砷低铅黄铜合金
CN101343704B (zh) * 2008-09-03 2010-10-13 浙江天申铜业有限公司 一种适合重力铸造的无铅环保铋黄铜合金材料的制备方法

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