US20100135848A1 - Lead-free free-cutting silicon brass alloy - Google Patents

Lead-free free-cutting silicon brass alloy Download PDF

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Publication number
US20100135848A1
US20100135848A1 US12/407,720 US40772009A US2010135848A1 US 20100135848 A1 US20100135848 A1 US 20100135848A1 US 40772009 A US40772009 A US 40772009A US 2010135848 A1 US2010135848 A1 US 2010135848A1
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Prior art keywords
free
alloy
lead
alloys
cutting
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Abandoned
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US12/407,720
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English (en)
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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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Assigned to XIAMEN LOTA INTERNATIONAL CO., LTD. reassignment XIAMEN LOTA INTERNATIONAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HU, ZHENQING, XU, CHUANKAI, ZHANG, SIQI
Priority to CA2662814A priority Critical patent/CA2662814C/en
Priority to JP2009197611A priority patent/JP5399818B2/ja
Priority to ES09174544T priority patent/ES2398184T3/es
Priority to DK09174544.8T priority patent/DK2194150T3/da
Priority to PT91745448T priority patent/PT2194150E/pt
Priority to EP09174544A priority patent/EP2194150B1/en
Priority to US12/651,723 priority patent/US8273193B2/en
Publication of US20100135848A1 publication Critical patent/US20100135848A1/en
Abandoned legal-status Critical Current

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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

Definitions

  • the present invention generally relates to a lead-free free-cutting silicon brass alloy, in particular a lead-free free-cutting silicon brass alloy with high zinc which is applicable in low pressure die castings and forgings.
  • the internal construction of faucet bodies is very complex.
  • the faucet bodies typically are hollow castings with slim walls whose thickness can vary.
  • the cooling intensity of the mold for low pressure die casting is large.
  • the alloy must have excellent castability, especially excellent mold filling performance and hot crack resistance.
  • These kinds of castings also are subjected to cutting processes including, for example, sawing, lathing, milling, drilling and polishing. All these processes require the alloy to have excellent cuttability.
  • standards for drinking water such as NSF/ANSI61-2007 strictly restrict the amount of elements such as Sb, Pb, Cd, and As that can be released into the water.
  • the maximum acceptable release amount of Sb and Pb is 0.6 ug/L and 1.5 ug/L, respectively. If the Sb content in the brass alloy exceeds 0.2 wt %, the amount of Sb release into the water will exceed 0.6 ug/L. Thus, some antimony brass alloys are not suitable for use in drinking water system installations.
  • One object of the present invention is to provide a free-cutting silicon brass alloy with high zinc which is excellent in castability, forging performance, cuttability, weldability, mechanical properties, corrosion resistance and electroplatability and whose cost is rather lower, especially a free-cutting and weldable silicon brass alloy with high zinc which is applicable in low pressure die casting and forging.
  • This alloy will solve the limitations of conventional brass alloys discussed above especially the problem of lead contamination.
  • the object of the present invention is achieved by the novel selection and composition of elements comprising the alloy.
  • composition of the present alloys is to use the mutual interaction of multiple alloy elements in low amounts to form different multi-element intermetallic compound grains, which improve the cuttability of the alloys and ensure excellent castability, weldability, cuttability and corrosion resistance.
  • the present invention comprises: 35.0 to 42.0 wt % Zn, 0.1 to 1.5 wt % Si, 0.03 to 0.3 wt % Al, 0.01 to 0.36 wt % P, 0.01 to 0.1 wt % Ti, 0.001 to 0.05 wt % rare earth metals, 0.05 to 0.5 wt % Sn and/or 0.05 to 0.2 wt % Ni and the balance being Cu and unavoidable impurities.
  • the elongation rate of the casting alloy is more than 10%.
  • the hardness is in the range of HRB (Rockwell hardness scale B) 55 to 75.
  • the folding angle of the strip samples is larger than 55°.
  • Si is a main element along with Zn.
  • the alloys also contain Al, Mg, Sn and P.
  • the effects of using Si include, for example, deoxidization for improving castability, weldability, corrosion resistance, particularly improving dezincification corrosion resistance, increasing relative ratio of ⁇ phase and forming small amount of ⁇ phase and improving cuttability of the alloys.
  • the present invention demonstrates that Si has the effect of refining ⁇ phase grain, which is beneficial for improving the intensity, elongation rate and cracking resistance of the alloys. Grain refining is beneficial for mechanical properties and cuttability because the intermetallic compounds are further dispersed in the grain boundary, phase boundary and grain interior. For castings with relatively complex constructions and thick cross-sections, applicable in low pressure die casting.
  • ⁇ phase is the intermetallic compound with disordered body-centered crystal structure.
  • the plasticity of ⁇ phase at high temperatures is better than a phase, so it is beneficial for hot cracking resistance of the alloy.
  • ⁇ ′ phase is the intermetallic compound with ordered, body-centered crystal structure.
  • ⁇ ′ phase is harder and more brittle than ⁇ phase so it is beneficial for cuttability.
  • HRB 80 the hardness will be greater than HRB 80. This is bad for cuttability.
  • the total zinc equivalents of Zn, Al and Si must be lower than 45 wt %.
  • the content of Zn in the alloy is 40 wt %
  • Al is 0.2 wt %
  • the content of Si typically can't exceed 0.4 wt %.
  • the content of Si is preferably in the range of 0.6 to 1.5 wt %.
  • the content of Si is preferably in the range of 0.4 to 1.3 wt % so that small amount of ⁇ phase will be formed in the alloy for improving the cuttability.
  • the effects of adding Al include solid solution strengthening, corrosion resistance improvement, hot cracking resistance improvement and deoxidization.
  • the content of Al is preferably in the range of 0.03 to 0.3 wt %. If the content of Al is lower than 0.03 wt %, its beneficial effects are not apparent. If the content of Al is higher than 0.3 wt %, Al is prone to oxidizing and slag formation such that the fluidity of the alloy will be decreased. Castability and weldability are accordingly decreased. Moreover, Al will make the silicon brass alloy grain coarser and decrease the condensability of the castings and ingots.
  • This range of P improves deoxidization, which improves the castability and weldability of the alloy and decreases the oxidization loss of other useful elements.
  • the formed Cu 3 P further improves the cuttability of the alloys.
  • P is beneficial for cuttability, castability and weldability. Relatively small amounts of P also have the effect of grain refining.
  • Mg in the brass alloy is similar to the effect of P, that is, deoxidization and grain refining.
  • the intermetallic compound Cu 2 Mg which is formed by Mg and Cu is also beneficial for improving the cuttability of the alloy.
  • Cu 2 Mg is not hard and brittle like Cu 3 P but it is somewhat bad for the plasticity of the alloys.
  • Mg also will form Mg 2 Si with Si. It's found by SEM (scanning electron microscope) observation that Mg—Si particles are uniformly dispersed granularly in the interior of ⁇ phase grain, grain boundary and phase boundary. Mg—Si particles are not found in the interior of ⁇ phase grain.
  • Mg together with elements Sb, Cu and Zn also forms a complex intermetallic compound which is granularly dispersed in the interior of grains.
  • These multi-element intermetallic compound particles are not only beneficial for improving the cuttability of the alloys, but also beneficial for decreasing the loss of Mg during casting.
  • the content of Mg will be in the range of 0.05 to 0.4 wt %, if any in the inventive alloys. This amount of Mg is sufficient for deoxidization, grain refining and improving the castability of the alloys. If the content of Mg is in the middle to upper limits of the specified range, it is also beneficial for the cuttability.
  • Mg is better than P at improving the castability of the alloys. Mg improves the hot cracking resistance of the alloy and effectively eliminates the cracking of the castings.
  • Rare earth metals are a group of elements consisting of La and Ce. Ti and rare earth metals are effective grain refiners and also have the effect of deoxidization. Rare earth metals also have the effect of purifying the grain boundary. Rare earth metals will form high melting point intermetallic compounds with low melting point impurities in the grain boundary and therefore decrease the hot brittleness of the alloys or form intermetallic compounds with other harmful impurities in the grain boundary and therefore decrease the harmfulness of harmful impurities. Rare earth metals also could mutually interact with most alloying elements and form more stable intermetallic compounds. Therefore, rare earth metals and Ti are typically added to lead-free free-cutting brass alloys. However, rare earth metals are prone to oxidizing.
  • inventive alloys selectively add 0.001 to 0.05 wt % rare earth metals. This amount of rare earth metals will improve the mechanical performance, but is bad for the castability, as embodied in volume shrinkage samples wherein the face of the concentrating shrinkage cavity is not smooth and small visible shrinkage porosity in the bottom of the concentrating shrinkage appears.
  • Ni is for solid solution strengthening, corrosion resistance improvement and especially the stress corrosion resistance improvement of the alloys.
  • Al is also added to the alloys, Ni together with Al will form hard and brittle intermetallic compounds with high melting points. This will decrease the alloy's plasticity.
  • Sn improves the corrosion resistance of the alloys, especially the dezincification corrosion resistance of the alloys. Sn also can form intermetallic compounds with Sb. With increased addition of Sn, Sb release amount into the water will decrease. When the content of Sb exceeds 0.2 wt %, however, even if the content of Sn increases, the Sb release amount into the water will exceed the NSF/ANSI61-2007 standard as well as result in grain coarsening. The cracking resistance, intensity and elongation rate will decrease. The effect that Sn decreases Sb release amount into the water is very limited. Since Ni and Sn are very expensive, their levels are better kept around lower limit.
  • Fe is a common impurity in copper and copper alloys. It has the effect of refining ⁇ phase grain in copper and brass.
  • the solid solution of Fe at room temperature is very low.
  • Fe without solid solution or Fe precipitated from solid solution will decrease the plasticity and corrosion resistance of the alloys and form hard and brittle hard spots with Al, Si and B.
  • the hard spots may be located in the face of castings and forgings and then influence the facial quality of the electroplated products.
  • the facial glossiness of products is affected by these spot discrepancies. Therefore, the content of Fe should be equal or lower than 0.1 wt %.
  • the content of Pb should be equal or lower than 0.1 wt %. This level is beneficial for cuttability improvement and the release amount into the water will not exceed the standard NSF/ANSI61-2007. (1.5 ug/L)
  • Sb as an unavoidable impurity should be equal or lower than 0.04 wt %. At this level, the Sb release amount into the water will not exceed the standard NSF/ANSI61-2007(0.6 ug/L).
  • the alloy composition should meet the following requirements: the elongation rate of As-Cast alloy should be larger than 5%, the hardness is in the range of HRB 55 to 75, and the bending angle of strip samples is preferably larger than 55°.
  • the advantages of the invented alloy include, but are not limited to: excellent castability and weldability, satisfactory performance in processes such as casting, forging, welding, sawing, lathing, milling, drilling, polishing and electroplating, and desirable properties for faucet bodies including stress corrosion and salt spray corrosion resistance, dezincification corrosion resistance, low Pb release amounts, low Sb release amounts, low water leakage, and improved mechanical performance and hardness.
  • the inventive alloys have excellent forging performance and the range of forging temperature is large. Ingots rather than extruded bars could be disposably die forged to components with complex structure. This is beneficial for recycling and re-use of Pb brass alloy, phosphorus brass alloys, magnesium brass alloys, antimony brass alloys, silicon brass alloys and common brass alloys. Furthermore, metal materials cost and total production costs are lower.
  • the steps of manufacturing of the invented alloy are as follows: Material proportioning—melting in the intermediate frequency induction electric furnace (with flux for refining)—pouring to be ingots—remelting—low pressure die casting to be castings or horizontal continuous casting to be rod—flaying—forging.
  • the temperature for low pressure die casting is in the range of 970° C. to 1000° C.
  • the temperature for horizontal continuous casting is in the range of 990° C. to 1030° C.
  • the temperature for forging is in the range of 600° C. to 720° C.
  • the advantages of the present manufacturing method include strong operability.
  • the present universal production equipments and tool and die and even low pressure die casting mold and sand core for brass continuous casting, low pressure die casting and forging may be used without a redesign or revision.
  • FIG. 1 shows the characteristics of volume contraction samples formed in Example 1 of Table 1.
  • FIG. 2 shows the characteristics of volume contraction samples formed in Example 14 of Table 1.
  • FIG. 3 shows the shapes of the cutting chips formed in Example 1 of Table 1.
  • FIG. 4 shows the shapes of the cutting chips formed in Example 6 of Table 1.
  • FIG. 5 shows the shapes of the cutting chips formed in Example 14 of Table 1.
  • FIG. 6 shows the shapes of the cutting chips formed in cutting lead-contained brass alloy C36000 for comparison.
  • alloys according to the present invention are shown in Table 1.
  • the raw materials used in the alloys include: No. 1 Cu, No. 1 Zn, A00 Al, No. 1 Ni, No. 1 Sn, Cu—Si master alloy, Cu—P master alloy, Cu—Ti master alloy, misch metal, magnesium alloys, old materials of No. 1 Pb ingots or C36000, the covering agent, and flux as the refining agent.
  • One method of manufacturing the alloys is as follows. First, No. 1 Cu, Cu—Si master alloys, No. 1 Ni, and the covering agent that enhances slag removal efficiency are added to the furnace. These materials are heated until they have melted to form a melt mixture and are thereafter stirred. Then the No. 1 Zn is added to the melt mixture, melt and be stirred. Slag is skimmed from the melt and is covered. Then flame throw is processed. Thereafter, Cu—P master alloys and Magnesium alloys are added and the mixture is stirred. The left metal materials are added. These materials are again heated until melted, and are thereafter stirred. The flux for refining is added and the mixture stands until the ingots are formed.
  • the low pressure die casting occurs at the temperature in the range of 970 to 1000° C. or horizontal continuous casting occurs at the temperature in the range of 990° C. to 1030° C. after the ingots are remelted.
  • the hot forging is processed at the temperature in the range of 600 to 720° C.
  • Examples 1, 6 and 14 were used to make 3 different types of faucet bodies by low pressure die casting and weld-forming. The formability was acceptable.
  • the temperature for low pressure die casting of the example alloy is in the range of 970 to 1000° C.
  • the pouring temperature for testing castability is 1000° C.
  • the lead-free brass alloy of present invention has been tested with results as follows:
  • volume shrinkage samples are for evaluating the characteristics of concentrating shrinkage, dispersed shrinkage and porosity.
  • Spiral samples are for measuring the flow length of the alloy melt.
  • Strip samples are for measuring linear shrinkage rate and bend angle of the alloy.
  • the cylindrical samples with different wall thickness are for measuring shrinkage crack resistance of the alloy.
  • Relative ⁇ ⁇ cutting ⁇ ⁇ ratio Cutting ⁇ ⁇ resistance ⁇ ⁇ of ⁇ ⁇ alloy ⁇ ⁇ C ⁇ 36000 Cutting ⁇ ⁇ resistance ⁇ ⁇ of ⁇ ⁇ the ⁇ ⁇ invented ⁇ ⁇ alloy ⁇ 100 ⁇ %
  • the samples for testing cuttability are selected from the sprue portions of the castings made for tensile testing.
  • the feeding quantity is 0.5 mm.
  • Other cutting parameters are the same. The results are shown in Table 3.
  • the samples for testing corrosion resistance are As-Cast.
  • the samples of Examples 1, 6 and 14 are from faucet bodies formed by low pressure die casting.
  • the samples of other Examples are ring samples which are typically for measuring the castability, as they cannot free shrink in the process of solidification and cooling and their internal stress is relatively large.
  • the samples for testing salt spray corrosion and stress corrosion resistance are electroplating products.
  • the stress corrosion resistance test was conducted according to GSO481.1.013-2005 standard (Ammonia fumigation).
  • the salt spray corrosion resistance test was conducted according to ASTMB368-97(R2003)E1 standard.
  • the dezinfication corrosion resistance test was conducted according to GB10119-1988 standard.
  • the test of metal release amount was conducted according to NSF/ANSI61-2007 standard. The test results are shown in Table 4.

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US12/407,720 2008-12-02 2009-03-19 Lead-free free-cutting silicon brass alloy Abandoned US20100135848A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CA2662814A CA2662814C (en) 2008-12-02 2009-04-16 Lead-free free-cutting silicon brass alloy
JP2009197611A JP5399818B2 (ja) 2008-12-02 2009-08-28 鉛を含まない快削性ケイ素真鍮合金
ES09174544T ES2398184T3 (es) 2008-12-02 2009-10-29 Aleación de latón al silicio de fácil mecanización, libre de plomo y con alto contenido de zinc, y método de producción de la misma
DK09174544.8T DK2194150T3 (da) 2008-12-02 2009-10-29 Blyfri silicium-messing-automatlegering med høj zink og dets fremgangsmåder til fremstilling
PT91745448T PT2194150E (pt) 2008-12-02 2009-10-29 Liga de latão de silício de corte rápido isenta de chumbo com alto teor de zinco e o seu método de fabrico
EP09174544A EP2194150B1 (en) 2008-12-02 2009-10-29 Lead-free free-cutting silicon brass alloy with high zinc and its manufacturing method
US12/651,723 US8273193B2 (en) 2008-12-02 2010-01-04 Lead-free, bismuth-free free-cutting silicon brass alloy

Applications Claiming Priority (2)

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CN200810180201A CN101440444B (zh) 2008-12-02 2008-12-02 无铅易切削高锌硅黄铜合金及其制造方法
CN200810180201.9 2008-12-02

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EP (1) EP2194150B1 (enrdf_load_stackoverflow)
JP (1) JP5399818B2 (enrdf_load_stackoverflow)
CN (1) CN101440444B (enrdf_load_stackoverflow)
CA (1) CA2662814C (enrdf_load_stackoverflow)
DK (1) DK2194150T3 (enrdf_load_stackoverflow)
ES (1) ES2398184T3 (enrdf_load_stackoverflow)
PT (1) PT2194150E (enrdf_load_stackoverflow)

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