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WO2011066581A1 - Copper corrosion resistant, machinable brass alloy - Google Patents

Copper corrosion resistant, machinable brass alloy Download PDF

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Publication number
WO2011066581A1
WO2011066581A1 PCT/US2010/058447 US2010058447W WO2011066581A1 WO 2011066581 A1 WO2011066581 A1 WO 2011066581A1 US 2010058447 W US2010058447 W US 2010058447W WO 2011066581 A1 WO2011066581 A1 WO 2011066581A1
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weight
copper
lead
brass
corrosion
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PCT/US2010/058447
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French (fr)
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Inho Song
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Moen Inc
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Moen Inc
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Priority to EP10834063A priority Critical patent/EP2507401A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent

Definitions

  • the present application is directed to a machinable silicon brass alloy, and more particularly to a copper (Cu) corrosion resistant, machinable silicon brass alloy with low amounts of lead (Pb).
  • Cu copper
  • Pb lead
  • lead (Pb) content references shall specify the lead (Pb) alloy percentages present as "no" or "low,” which when used in this context shall mean zero to low percentage amounts, as well as by using specific percentages. It should be understood that the govemmentally permitted use of small amounts of lead (Pb), as opposed to a lead (Pb)-free mandate, more readily enables the use of recycled materials, which are typically very difficult to ensure are entirely free of all lead (Pb). Moreover, the use of somewhat higher levels of lead (Pb), such as up to 1 % by weight, may continue to be acceptable in non-potable water conduit components.
  • % point variation in zinc (Zn) content within the two phase ( ⁇ + ⁇ ') phase field affects the amount of ⁇ ' by as much as 15 % points as shown in the binary phase diagram of copper (Cu) and zinc (Zn). This is because the two phase ( ⁇ + ⁇ ') field is only about 7 % point wide. As it is the ⁇ '-phase that is more susceptible to dezincification, it is a widely held belief that keeping the zinc (Zn) content low is the first easy step to mitigate the potential for dezincification.
  • the zinc (Zn)-rich ⁇ '- phase is in the trade commonly referred to as ⁇ -phase and as such, ⁇ -brass contains ⁇ '-phase as well as a matrix phase.
  • the prior art silicon (Si) brass alloys generally contain a small amount (less than 0.4 %) of tin (Sn) for certain types of non-copper corrosion resistance, but this is not considered enough to suppress the corrosion of copper (Cu).
  • the use of such silicon (Si) brass alloys, or lead (Pb)-free products for example, such as commercially available ECO BRASS® from Chase Brass & Copper Company, Inc. and Ingot Metal Company Limited of Toronto, Ontario, which was developed by Sambo Copper/Mitsubishi Shindoh Ltd., as set forth in numerous U.S. Patents, including, for example, Nos.
  • Such alloys certainly have resistance to zinc (Zn) corrosion or dezincification, and in many circumstances of water chemistry have some resistance to erosion corrosion, due to the creation of a skin or layer of oxidation at the internal diameter surface of the components.
  • Studies have not been conducted to determine the time line for potential risks of component failure due to copper (Cu) corrosion, and particularly in plumbing products where a thin walled, low lead (Pb) or no lead (Pb) product is under pressure and is required to be fit for passing potable water.
  • dezincification tests fail to address the corrosion of copper (Cu) because the tests are conducted in a highly concentrated aqueous solution of copper chloride (CuCl 2 ), and as such the high concentration of copper (Cu) ions in the test solution prohibits or suppresses the corrosion of copper (Cu) in the brass test articles.
  • This application provides an alloy for specifically improving copper
  • the application provides an alloy which reduces or replaces lead (Pb) in brass with metals with physical, mechanical, chemical and electrochemical properties that will improve the corrosion resistance and machinability of low lead (Pb) brass alloys.
  • Alloying element candidates are bismuth (Bi), antimony (Sb), tellurium (Te), phosphorous (P), silicon (Si), sulfur (S) for machinability improvement; and tin (Sn) for corrosion resistance improvement.
  • the alloy having an excellent machinability and exhibiting a high degree of copper (Cu) corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 2 to 4 %, by weight, of silicon (Si); 1 to 3 %, by weight, of tin (Sn); 0.01 to 1 %, by weight, of lead (Pb); and the remaining %, by weight, of zinc (Zn).
  • This copper (Cu) alloy will be called the "first alloy.” It is understood to those of skill in the art, and is likewise to be understood herein, that the stated amounts of the referenced components include a common margin of error resulting from the weight measurement calculation.
  • Tin (Sn) is effective in improving not only the machinability but also the copper (Cu) corrosion resistance properties of the alloy.
  • the first alloy is thus improved in copper (Cu) corrosion resistance by such properties of tin (Sn).
  • tin (Sn) would have to be added in an amount of at least 1 % by weight, and preferably about 2 % by weight.
  • tin (Sn) is higher than 2 % by weight, for example, about 3 % by weight or higher, additional alloy corrosion resistance and hardness may be obtained, but if it is added to between about 3 and 6 % by weight, the corrosion resistance and machinability will continue to improve, but the additional amounts of tin (Sn) may render the alloy uneconomical, depending on the application.
  • Bismuth (Bi) has a rhombohedral (R-3m) crystal structure that is structurally incompatible with copper (Cu, Fm-3m) or zinc (Zn, P63/mmc), and therefore has very low solid solubility into the brass (Fm-3m, Im-3m, Pm-3m). Furthermore, bismuth (Bi) does not even form any stoichiometric intermetallic compounds with either copper (Cu) or zinc (Zn). Consequently, the added bismuth (Bi) will solidify as independent grains, which embrittle the chips during machining and hence an improvement of the machining speed and productivity.
  • the amount of the metal addition may be considered small (preferably 2 % or less by weight, but may be as much as 5 %), but the net effect on the machinability is large enough to consider the alloys comparable to the leaded brass alloys.
  • a further improvement in machinability may be achieved by metallurgically forming or by directly adding particles of metal oxides, silicides, sulfides or phosphides (for example, cerium oxide, chromium oxide, manganese oxide, molybdenum silicide, molybdenum sulfide, copper phosphide, iron phosphide) in the melting and casting process of brass making.
  • metal oxides for example, cerium oxide, chromium oxide, manganese oxide, molybdenum silicide, molybdenum sulfide, copper phosphide, iron phosphide
  • phosphorous or sulfur from the addition of phosphides or sulfides for the desired machinability may be varied and selected for each different applications based on the optimum combination of mechanical, thermal, electrical, electrochemical, chemical and physical properties of the resulting brass.
  • the phosphorus or sulfur levels and the resulting degree of brittleness will be determined based on the applications of the brass. For oxide additions, maintaining the median particle size of the metal oxide particle size below 2 microns, a substantial improvement in the strength is also achieved.
  • zinc (Zn) in brass also may react with phosphorus (P) and sulfur (S) to form brittle compounds (zinc phosfides or zinc sulfides) and improve the machinability of brass. Further similar effects of improving machinability may be attempted by using selenium (Se) or arsenic (As), but the toxicity concerns make them unsuitable for potable water services even if they are not controlled under AB 1953.
  • An additional second formulation of the first alloy keeps the zinc (Zn) content to below 20 % by weight such that the fraction of beta' ( ⁇ ') phase is at 5 % or lower or approaches zero % by volume to minimize the potential risks of
  • the alloy having an excellent machinability and exhibiting a high degree of corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 0.01 to 1 %, by weight of lead (Pb); 2 to 4 %, by weight, of silicon (Si);
  • This third alloy will be called the "third alloy.”
  • the alloy having an excellent machinability and exhibiting a high degree of corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 0.01 to 1 %, by weight of lead (Pb); 2 to 4 %, by weight, of silicon (Si);
  • Tin (Sn) in particular, as can be noticed in the Potential-pH Diagram ( Figure 1 A), shows a widely extended corrosion resistance due to the immunity of tin (Sn) and passivity by tin oxide (Sn0 2 ) within the range of pH (6.5 - 8.5) of potable water defined by US EPA. Tin (Sn) being electrochemically much more stable than zinc (Zn), the mixed potential theory of corrosion supports the practical improvement of corrosion resistance. Additional elements (for example, at least one of Bi, P, S, Te, and Se) may be added in for machinability improvement and may also bring positive effect in improving the corrosion resistance of brass alloys.
  • Figure 1A is a Potential-pH Diagram of tin (Sn).
  • Figure IB illustrates a potentiodynamic anodic polarization curve of commercial alloys— where the results of a test sample of silicon brass, C69300, is shown by the solid line; and a common brass alloy, C27450, is shown by the dashed line. Measurements were done in simulated tap water (Schock's 4, EPA); the electrode potentials in volts versus saturated Calomel Electrode (SCE); the electrode potential was scanned at 0.2 mV/s.
  • SCE saturated Calomel Electrode
  • Figure 2 illustrates chronoamperometric corrosion test results of the commercial alloys tested— where the results of a test sample of silicon brass, C69300, is shown by the solid line; and a common brass alloy, C27450, is shown by the dashed line. Measurements were done in simulated tap water (Schock's 4, EPA); the electrode potentials in volts versus saturated Calomel Electrode (SCE); the electrode potential held at +250 mV versus SCE while collecting the current data with respect to time.
  • SCE saturated Calomel Electrode
  • Figure 3 illustrates chronoamperometric corrosion test results of the alloys in the test series No. 1, where the black solid line illustrates 0 % Sn & 0 % Pb; black dashed line illustrates 0 % Sn & 0.1 % Pb; black dotted line illustrates 0 % Sn & 0.25 % Pb; gray solid line illustrates 0 % Sn & 0.5 % Pb; and gray dotted line illustrates 0 % Sn & 1 % Pb.
  • Figure 4 illustrates chronoamperometric corrosion test results of the alloys in the test series No 2, where the black solid line illustrates 3 % Sn & 0 % Pb; black dashed line illustrates 3 % Sn & 0.1 % Pb; black dotted line illustrates 3 % Sn & 0.25 % Pb; gray solid line illustrates 3 % Sn & 0.5 % Pb; and gray dotted line illustrates 3 % Sn & 1 % Pb.
  • Figure 5 illustrates chronoamperometric corrosion test results of the alloys in the test series No. 3, where the black solid line illustrates 6 % Sn & 0 % Pb; black dashed line illustrates 6 % Sn & 0.1 % Pb; black dotted line illustrates 6 % Sn & 0.25 % Pb; gray solid line illustrates 6 % Sn & 0.5 % Pb; and gray dotted line illustrates 6 % Sn & 1 % Pb.
  • Figure 6 illustrates the effects of lead (Pb) and tin (Sn) on the hardness of the test series brass alloys, where the numbers on the contour lines represent hardness valued measure in Rockwell B-scale (HRB).
  • Figure 7 is a bar graph showing the time taken to cut through test series samples of 1.125 inch diameter bar stock on a lathe with a saw blade at 840 rpm.
  • Figures 8A, 8B and 8C illustrate the chips resulting from a cutting test of samples of C36000, C36500 and C69300, respectively.
  • Figures 9A, 9B and 9C illustrate chips resulting from a cutting test of samples of test series nos. 1-1, 2-1 and 3-1 in Tables 1, 2 and 3, respectively.
  • Figures 10A, 10B and IOC illustrate chips resulting from a cutting test of samples of test series nos. 1-2, 2-2 and 3-2 in Tables 1, 2 and 3, respectively.
  • Figures 11A, 1 IB and 11C illustrate chips resulting from a cutting test of samples of test series nos. 1-3, 2-3 and 3-3 in Tables 1, 2 and 3, respectively.
  • Figures 12 A, 12B and 12C illustrate chips resulting from a cutting test of samples of test series nos. 1-4, 2-4 and 3-4 in Tables 1, 2 and 3, respectively.
  • Figures 13 A, 13B and 13C illustrate chips resulting from a cutting test of samples of test series nos. 1-5, 2-5 and 3-5 in Tables 1, 2 and 3, respectively.
  • Figure 14 schematically illustrates a plumbing fixture of the copper (Cu) corrosion resistant, machinable brass allow of the present application having a thin wall and pressurized for carrying potable water.
  • the present application provides an improved copper (Cu) corrosion resistant, machinable brass alloy with at least low amounts of lead (Pb), such as 0.01 to 1 %, by weight, and between 1 and 3 %, by weight, of tin (Sn), to resist copper (Cu) corrosion during use, and particularly during use in high pressure, thin walled plumbing fixtures.
  • Pb lead
  • tin tin
  • Figure 1 illustrates the results of measurements done with 2
  • C69300 (75 % Cu; 3 % Si, 0.09 % P and 21 % Zn) and C27450 (60-65 % Cu, ⁇ 0.25 % max. Pb, ⁇ 0.35 % Fe, remainder Zn).
  • C69300 is a commercially available wrought product, a comparable ingot product for casting applications, C87850, has a similar silicon brass composition.
  • the electrode potentials E are graphed in Figure 1 in volt versus Saturated Calomel Electrode (SCE) V-SCE; where the potential scan rate was at 0.2 mV per second.
  • SCE Saturated Calomel Electrode
  • the current is displayed in logarithmic scale and the current unit is in mA.
  • the result (solid line) is compared with free cutting brass alloy data for C36000 (dashed line) which comprises: 61.5 % nominal Copper (Cu), 2.5 % minimum Lead (Pb), 0.35 % maximum Iron (Fe), and 35.4 % nominal Zinc (Zn).
  • the data indicates that silicon (Si) brass in oxidizing conditions (i.e, anodic polarization conditions) exhibits corrosion current higher than free cutting brass by approximately 5 - 10 times.
  • Test series No. l comprised the test alloys listed in Table 1 below, where 0 % by weight of tin (Sn) was included in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples.
  • Test series No. 2 shown in Table 2 below, the weight % of tin (Sn) was 3 % in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples.
  • test series No. 1 comprised the test alloys listed in Table 1 below, where 0 % by weight of tin (Sn) was included in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples.
  • test series No. 2 shown in Table 2 below, the weight % of tin (Sn) was 3 % in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples.
  • test results shown in Figures 3, 4 and 5 enable a direct comparison of the impact of including tin (Sn) and lead (Pb) on copper (Cu) corrosion resistance in the test samples as well as to the prior art samples.
  • tin (Sn) and lead (Pb) on copper (Cu) corrosion resistance in the test samples as well as to the prior art samples.
  • the addition of tin (Sn) to alloys in test series 2-1 to 2-5 in Figure 4 show the corrosion dramatically decreases or drops to nearly 0, much sooner in time than any of the alloys in test series No. 1-1 to 1-5.
  • a still further dramatic drop is seen in the test series 3-1 to 3-5 results of Figure 5, over the results of test series No.
  • a desirable hardness for machinability which is about 78 HRB (or between 75 and 80), is generally obtained at between 1 and 3 weight % of tin (Sn) within the test series alloys, and at about 2 weight % of tin (Sn), where lead (Pb) is used in the test alloys at a weight % of between 0.1 and 0.5.
  • Cutting tests were also conducted to review the machinability of applicant's alloys in comparison with the conventional alloys. In the cutting tests, evaluations were made on the basis of chip color, size and shape. The tests were conducted by mounting the cylindrical test samples on a lathe, where a tool cut the samples at a cutting speed of 250 feet per minute, and a feed of 0.01 inches per revolution.
  • Chips from the cutting work were examined and are shown for example, for the conventional brass alloys, C36000 (a free-cutting brass having the components previously described), C36500 (a brass composed of 60 % Copper (Cu), 0.6 % Lead (Pb), and 39.4 % Zinc (Zn)) and C69300 (a lead (Pb)-free silicon brass having the components previously described), in Figures 8A, 8B and 8C, respectively.
  • the larger sized chips for example in Figure 8B, are not generally preferred, as they can hamper machining, tool life and the productivity.
  • Chips in the form of a needle- like arc, as in Figures 8 A indicate a material which provides the desired ease of machinability.
  • Figures 9A, 9B and 9C illustrate chips from a cutting test of a sample of test series nos. 1-1, 2-1 and 3-1 in Tables 1, 2 and 3, respectively.
  • Figures 10A, 10B and IOC illustrate chips from a cutting test of a sample of the test series nos. 1-2, 2-2 and 3-2 in Tables 1, 2 and 3, respectively.
  • Figures 11A, 1 IB and 11C illustrate chips from a cutting test of a sample of the test series nos. 1-3, 2-3 and 3-3 in Tables 1, 2 and 3, respectively.
  • Figures 12 A, 12B and 12C illustrate chips from a cutting test of a sample of test series nos. 1-4, 2-4 and 3-4 in Tables 1, 2 and 3, respectively.
  • Figures 13 A, 13B and 13C illustrate chips from a cutting test of the sample of the test series nos. 1-5, 2-5 and 3-5 in Tables 1, 2 and 3, respectively. Chips which lack arc, are too short, hard, flaky or grainy, such as those in Figures 9C, 12C and 13C, have less desirable machinability and may also cause difficulty to machinery or the operator. As can be seen upon comparison, the silicon brass chips of Figure 8C are comparable to those of test series no. 2-2 in Figure 10B, for example, in the arc shown in their appearance.
  • Amounts of lead (Pb) under 0.25 % are provided for potable water plumbing fixture applications, while amounts of lead (Pb) over 0.25 % are only provided to the upper limit of 1 %, and such higher amounts are only considered in non-potable water applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
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Abstract

An alloy which reduces lead (Pb) in brass with metals with physical, mechanical, chemical and electrochemical properties that will improve the copper (Cu) corrosion resistance and machinability of low lead (Pb) brass alloys. Such metal candidates are bismuth (Bi), antimony (Sb), tellurium (Te), phosphorous (P), silicon (Si), sulfur (S) for machinability improvement; and tin (Sn) for corrosion resistance improvement. The alloy composition has an excellent machinability and a high degree of copper corrosion resistance, and is composed of: 69 to 79 %, by weight, of copper (Cu); 2 to 4 %, by weight, of silicon (Si); 1 to 3 %, by weight, of tin (Sn); 0.01 to 1 %, by weight, of lead (Pb); and the remaining %, (but less than 20 %) by weight, of zinc (Zn).

Description

COPPER CORROSION RESISTANT, MACHINABLE BRASS ALLOY CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority from U.S. Patent Application
Nos. 61/265,208 and 61/265,215, both of which having a filing date of November 30, 2009, and the entire disclosures of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present application is directed to a machinable silicon brass alloy, and more particularly to a copper (Cu) corrosion resistant, machinable silicon brass alloy with low amounts of lead (Pb).
BACKGROUND
[0003] In the continuing effort to reduce the health hazards due to heavy metals such as lead (Pb), Assembly Bill 1953 ("AB 1953") by the State of California has mandated a substantial reduction of lead (Pb) in plumbing hardware. As a result, the use of low or no lead (Pb) materials (especially in brass) is now essential for continued sale of products starting in year 2010. It is noted that statutory and legal references to "no lead (Pb)" requirements, in fact do not require zero lead (Pb) content, but permit small amounts of lead (Pb), such as amounts less than 0.25 % by weight, while still allowing the alloy to be commercialized as a "no lead (Pb)" product. As set forth herein, lead (Pb) content references shall specify the lead (Pb) alloy percentages present as "no" or "low," which when used in this context shall mean zero to low percentage amounts, as well as by using specific percentages. It should be understood that the govemmentally permitted use of small amounts of lead (Pb), as opposed to a lead (Pb)-free mandate, more readily enables the use of recycled materials, which are typically very difficult to ensure are entirely free of all lead (Pb). Moreover, the use of somewhat higher levels of lead (Pb), such as up to 1 % by weight, may continue to be acceptable in non-potable water conduit components.
[0004] The reduction or elimination of lead (Pb) has also brought new challenges to manufacturing. That is, the reduction or removal of lead (Pb) greatly reduces the machinability, and this adds significant cost burden to the manufacturing operations due to the increased cycle times. Furthermore, because the amount of lead (Pb) removed is typically replaced with corresponding amounts of zinc (Zn) at fixed (Cu) contents in the brasses, the additional zinc (Zn) increases the amount of zinc (Zn)-rich beta' (β') phase and hence the susceptibility of the brass to a dezincification failure.
[0005] It may be easily noted in the copper-zinc (Cu-Zn) phase diagram, a one
% point variation in zinc (Zn) content within the two phase (α + β') phase field affects the amount of β' by as much as 15 % points as shown in the binary phase diagram of copper (Cu) and zinc (Zn). This is because the two phase (α + β') field is only about 7 % point wide. As it is the β'-phase that is more susceptible to dezincification, it is a widely held belief that keeping the zinc (Zn) content low is the first easy step to mitigate the potential for dezincification. The zinc (Zn)-rich β'- phase is in the trade commonly referred to as β-phase and as such, β-brass contains β'-phase as well as a matrix phase.
[0006] In the brass and plumbing industry, in order to address such potential dezincification effects, a low zinc (Zn), high copper (Cu) brass is often used. The zinc (Zn) concentration is kept at 20 % by weight or lower, compared to 35 - 40 % zinc (Zn) of more commonly used brasses. However, low zinc (Zn) brasses have extremely poor machinability. This has emerged as a major barrier to process transferability from highly machinable conventional leaded brass to a variety of no or low lead (Pb) brass options. In the recent years, a new class of brass alloys has become available as an answer to the machinablity and dezincification concerns. The alloys contain 2.5 - 3.5 % silicon (Si) by weight. The addition of silicon (Si) is believed to improve machinability.
[0007] Laboratory studies, however, have found that such silicon (Si) brasses have serious weaknesses in other types of corrosion. Naturally, due to the low zinc (Zn) level in the brass, the tendency of dezincification has greatly reduced; but the tendency for corrosion of copper (Cu) has increased so much to the point that the silicon (Si) brass may be inappropriate or unfit for certain applications where corrosion of copper (Cu) may, under some circumstances, over time, compromise the functionality of the component made of such brass.
[0008] The prior art silicon (Si) brass alloys generally contain a small amount (less than 0.4 %) of tin (Sn) for certain types of non-copper corrosion resistance, but this is not considered enough to suppress the corrosion of copper (Cu). The use of such silicon (Si) brass alloys, or lead (Pb)-free products, for example, such as commercially available ECO BRASS® from Chase Brass & Copper Company, Inc. and Ingot Metal Company Limited of Toronto, Ontario, which was developed by Sambo Copper/Mitsubishi Shindoh Ltd., as set forth in numerous U.S. Patents, including, for example, Nos. 6,413,330 and 7,056,396, focus on the environmental advantages and governmental requirements of lead (Pb)free alloys, but have yet to address the potential risks associated with structural weakness due to copper (Cu) corrosion. It is noted that such prior art materials focus on zinc (Zn) corrosion or de- zincification and erosion corrosion, which is the acceleration or increase in rate of deterioration or attack on a metal because of relative movement between a corrosive fluid and the metal surface. Copper (Cu) corrosion is not addressed. In erosion corrosion, metal is removed from the surface as dissolved ions, or it forms solid corrosion products that are mechanically swept from the metal surface. Such alloys certainly have resistance to zinc (Zn) corrosion or dezincification, and in many circumstances of water chemistry have some resistance to erosion corrosion, due to the creation of a skin or layer of oxidation at the internal diameter surface of the components. Studies have not been conducted to determine the time line for potential risks of component failure due to copper (Cu) corrosion, and particularly in plumbing products where a thin walled, low lead (Pb) or no lead (Pb) product is under pressure and is required to be fit for passing potable water. Commonly conducted
dezincification tests fail to address the corrosion of copper (Cu) because the tests are conducted in a highly concentrated aqueous solution of copper chloride (CuCl2), and as such the high concentration of copper (Cu) ions in the test solution prohibits or suppresses the corrosion of copper (Cu) in the brass test articles.
SUMMARY
[0009] This application provides an alloy for specifically improving copper
(Cu) corrosion resistance, with a particular interest in dezincification resistance and resistance to copper (Cu) corrosion, of low lead (Pb) brass materials; and at the same time, enhancing the machinability of the low lead (Pb) brasses. The application provides an alloy which reduces or replaces lead (Pb) in brass with metals with physical, mechanical, chemical and electrochemical properties that will improve the corrosion resistance and machinability of low lead (Pb) brass alloys. Alloying element candidates are bismuth (Bi), antimony (Sb), tellurium (Te), phosphorous (P), silicon (Si), sulfur (S) for machinability improvement; and tin (Sn) for corrosion resistance improvement. These elements along with other elements of brass alloy become metallurgically integral such that some parts of the added metals form solid solution with brass to impart corrosion resistance, and some stay as an isolated metallurgical phase(s) to facilitate good machinability.
[0010] It is further understood that the use of the following alloy composition, along with the specific additions mentioned to reduce copper (Cu) corrosion, is preferred. The alloy having an excellent machinability and exhibiting a high degree of copper (Cu) corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 2 to 4 %, by weight, of silicon (Si); 1 to 3 %, by weight, of tin (Sn); 0.01 to 1 %, by weight, of lead (Pb); and the remaining %, by weight, of zinc (Zn). This copper (Cu) alloy will be called the "first alloy." It is understood to those of skill in the art, and is likewise to be understood herein, that the stated amounts of the referenced components include a common margin of error resulting from the weight measurement calculation.
[0011] Tin (Sn) is effective in improving not only the machinability but also the copper (Cu) corrosion resistance properties of the alloy. The first alloy is thus improved in copper (Cu) corrosion resistance by such properties of tin (Sn). To raise the copper (Cu) corrosion resistance, tin (Sn) would have to be added in an amount of at least 1 % by weight, and preferably about 2 % by weight. If the addition of tin (Sn) is higher than 2 % by weight, for example, about 3 % by weight or higher, additional alloy corrosion resistance and hardness may be obtained, but if it is added to between about 3 and 6 % by weight, the corrosion resistance and machinability will continue to improve, but the additional amounts of tin (Sn) may render the alloy uneconomical, depending on the application.
[0012] Additional improvements to the first alloy may be had by addition of the various metals indicated. Bismuth (Bi) has a rhombohedral (R-3m) crystal structure that is structurally incompatible with copper (Cu, Fm-3m) or zinc (Zn, P63/mmc), and therefore has very low solid solubility into the brass (Fm-3m, Im-3m, Pm-3m). Furthermore, bismuth (Bi) does not even form any stoichiometric intermetallic compounds with either copper (Cu) or zinc (Zn). Consequently, the added bismuth (Bi) will solidify as independent grains, which embrittle the chips during machining and hence an improvement of the machining speed and productivity. The amount of the metal addition may be considered small (preferably 2 % or less by weight, but may be as much as 5 %), but the net effect on the machinability is large enough to consider the alloys comparable to the leaded brass alloys.
[0013] A further improvement in machinability may be achieved by metallurgically forming or by directly adding particles of metal oxides, silicides, sulfides or phosphides (for example, cerium oxide, chromium oxide, manganese oxide, molybdenum silicide, molybdenum sulfide, copper phosphide, iron phosphide) in the melting and casting process of brass making. The optimum level of
phosphorous or sulfur from the addition of phosphides or sulfides for the desired machinability may be varied and selected for each different applications based on the optimum combination of mechanical, thermal, electrical, electrochemical, chemical and physical properties of the resulting brass. The phosphides and sulfide phases that forms within brass embrittles brass and as a result the brass becomes easily machinable. The phosphorus or sulfur levels and the resulting degree of brittleness will be determined based on the applications of the brass. For oxide additions, maintaining the median particle size of the metal oxide particle size below 2 microns, a substantial improvement in the strength is also achieved.
[0014] Similar to copper (Cu), zinc (Zn) in brass also may react with phosphorus (P) and sulfur (S) to form brittle compounds (zinc phosfides or zinc sulfides) and improve the machinability of brass. Further similar effects of improving machinability may be attempted by using selenium (Se) or arsenic (As), but the toxicity concerns make them unsuitable for potable water services even if they are not controlled under AB 1953.
[0015] An additional second formulation of the first alloy keeps the zinc (Zn) content to below 20 % by weight such that the fraction of beta' (β') phase is at 5 % or lower or approaches zero % by volume to minimize the potential risks of
dezincification failure during service in the widely varying ranges of water chemistry.
[0016] It is further understood that the use of the following third alloy composition, along with the specific additions mentioned above to reduce copper (Cu) corrosion, is preferred. The alloy having an excellent machinability and exhibiting a high degree of corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 0.01 to 1 %, by weight of lead (Pb); 2 to 4 %, by weight, of silicon (Si);
2 to 3 %, by weight, of tin (Sn); and the remaining %, by weight, of zinc (Zn), but less than 20%. This third alloy will be called the "third alloy."
[0017] It is further understood that the use of the following fourth alloy composition, along with the specific additions mentioned above to reduce copper corrosion, is preferred. The alloy having an excellent machinability and exhibiting a high degree of corrosion resistance, which is composed of: 69 to 79 %, by weight, of copper (Cu); 0.01 to 1 %, by weight of lead (Pb); 2 to 4 %, by weight, of silicon (Si);
3 to 6 %, by weight, of tin (Sn); and, and the remaining %, by weight, of zinc (Zn), but less than 20%. This alloy will be called the "fourth alloy."
[0018] Desired improvement in copper (Cu) corrosion resistance is achieved by the addition of tin (Sn) into the brass alloy. Tin (Sn) in particular, as can be noticed in the Potential-pH Diagram (Figure 1 A), shows a widely extended corrosion resistance due to the immunity of tin (Sn) and passivity by tin oxide (Sn02) within the range of pH (6.5 - 8.5) of potable water defined by US EPA. Tin (Sn) being electrochemically much more stable than zinc (Zn), the mixed potential theory of corrosion supports the practical improvement of corrosion resistance. Additional elements (for example, at least one of Bi, P, S, Te, and Se) may be added in for machinability improvement and may also bring positive effect in improving the corrosion resistance of brass alloys.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1A is a Potential-pH Diagram of tin (Sn).
[0020] Figure IB illustrates a potentiodynamic anodic polarization curve of commercial alloys— where the results of a test sample of silicon brass, C69300, is shown by the solid line; and a common brass alloy, C27450, is shown by the dashed line. Measurements were done in simulated tap water (Schock's 4, EPA); the electrode potentials in volts versus saturated Calomel Electrode (SCE); the electrode potential was scanned at 0.2 mV/s.
[0021] Figure 2 illustrates chronoamperometric corrosion test results of the commercial alloys tested— where the results of a test sample of silicon brass, C69300, is shown by the solid line; and a common brass alloy, C27450, is shown by the dashed line. Measurements were done in simulated tap water (Schock's 4, EPA); the electrode potentials in volts versus saturated Calomel Electrode (SCE); the electrode potential held at +250 mV versus SCE while collecting the current data with respect to time.
[0022] Figure 3 illustrates chronoamperometric corrosion test results of the alloys in the test series No. 1, where the black solid line illustrates 0 % Sn & 0 % Pb; black dashed line illustrates 0 % Sn & 0.1 % Pb; black dotted line illustrates 0 % Sn & 0.25 % Pb; gray solid line illustrates 0 % Sn & 0.5 % Pb; and gray dotted line illustrates 0 % Sn & 1 % Pb.
[0023] Figure 4 illustrates chronoamperometric corrosion test results of the alloys in the test series No 2, where the black solid line illustrates 3 % Sn & 0 % Pb; black dashed line illustrates 3 % Sn & 0.1 % Pb; black dotted line illustrates 3 % Sn & 0.25 % Pb; gray solid line illustrates 3 % Sn & 0.5 % Pb; and gray dotted line illustrates 3 % Sn & 1 % Pb.
[0024] Figure 5 illustrates chronoamperometric corrosion test results of the alloys in the test series No. 3, where the black solid line illustrates 6 % Sn & 0 % Pb; black dashed line illustrates 6 % Sn & 0.1 % Pb; black dotted line illustrates 6 % Sn & 0.25 % Pb; gray solid line illustrates 6 % Sn & 0.5 % Pb; and gray dotted line illustrates 6 % Sn & 1 % Pb.
[0025] Figure 6 illustrates the effects of lead (Pb) and tin (Sn) on the hardness of the test series brass alloys, where the numbers on the contour lines represent hardness valued measure in Rockwell B-scale (HRB).
[0026] Figure 7 is a bar graph showing the time taken to cut through test series samples of 1.125 inch diameter bar stock on a lathe with a saw blade at 840 rpm.
[0027] Figures 8A, 8B and 8C illustrate the chips resulting from a cutting test of samples of C36000, C36500 and C69300, respectively.
[0028] Figures 9A, 9B and 9C illustrate chips resulting from a cutting test of samples of test series nos. 1-1, 2-1 and 3-1 in Tables 1, 2 and 3, respectively.
[0029] Figures 10A, 10B and IOC illustrate chips resulting from a cutting test of samples of test series nos. 1-2, 2-2 and 3-2 in Tables 1, 2 and 3, respectively.
[0030] Figures 11A, 1 IB and 11C illustrate chips resulting from a cutting test of samples of test series nos. 1-3, 2-3 and 3-3 in Tables 1, 2 and 3, respectively.
[0031] Figures 12 A, 12B and 12C illustrate chips resulting from a cutting test of samples of test series nos. 1-4, 2-4 and 3-4 in Tables 1, 2 and 3, respectively. [0032] Figures 13 A, 13B and 13C illustrate chips resulting from a cutting test of samples of test series nos. 1-5, 2-5 and 3-5 in Tables 1, 2 and 3, respectively.
[0033] Figure 14 schematically illustrates a plumbing fixture of the copper (Cu) corrosion resistant, machinable brass allow of the present application having a thin wall and pressurized for carrying potable water.
DETAILED DESCRIPTION
[0034] The present application provides an improved copper (Cu) corrosion resistant, machinable brass alloy with at least low amounts of lead (Pb), such as 0.01 to 1 %, by weight, and between 1 and 3 %, by weight, of tin (Sn), to resist copper (Cu) corrosion during use, and particularly during use in high pressure, thin walled plumbing fixtures. To confirm the ideal desired combination of copper (Cu)corrosion resistance, machinability and hardness, a test series of sample alloys was used having the compositions set forth in Tables 1 , 2 and 3 below, in the form of cylindrical stock having a 1 -1.025 inch diameter.
Prior Art Test Examples:
[0035] A sample of prior art brass alloys were tested to obtain bench marks regarding corrosion resistance. During the testing, an electrode area of 0.25 cm2, was mounted in epoxy. An electrolyte of 80 mL of simulated tap water was used
(Schock's 4 Water, US EPA) having a pH of 8, alkalinity of 475 - 525 ppm, free chlorine (Cl2) of 2 ppm, and a temperature of 22° C. The reference electrode used was a Saturated Calomel Electrode separated by a cracked stopcock bridge and Luggin capillary tip. A counter electrode was platinum separated by glass frit. The test was open to the air with no active aeration. A 1 cm magnetic stir bar provided agitation at about 60 rpm.
[0036] Figure 1 illustrates the results of measurements done with 2
commercial brass alloys: C69300 (75 % Cu; 3 % Si, 0.09 % P and 21 % Zn) and C27450 (60-65 % Cu, < 0.25 % max. Pb, < 0.35 % Fe, remainder Zn). Although C69300 is a commercially available wrought product, a comparable ingot product for casting applications, C87850, has a similar silicon brass composition. The electrode potentials E are graphed in Figure 1 in volt versus Saturated Calomel Electrode (SCE) V-SCE; where the potential scan rate was at 0.2 mV per second. Such potentiodynamic polarization techniques are commonly used test methods for measuring corrosion resistance. As is shown, the current is displayed in logarithmic scale and the current unit is in mA. The result (solid line) is compared with free cutting brass alloy data for C36000 (dashed line) which comprises: 61.5 % nominal Copper (Cu), 2.5 % minimum Lead (Pb), 0.35 % maximum Iron (Fe), and 35.4 % nominal Zinc (Zn). The data indicates that silicon (Si) brass in oxidizing conditions (i.e, anodic polarization conditions) exhibits corrosion current higher than free cutting brass by approximately 5 - 10 times.
[0037] Still further chronoamperometric corrosion tests were also conducted. The results are presented in Ampere versus time, i.e., the variation of corrosion current with respect to time. In the chart, the corrosion current decreases rapidly with time in materials with higher corrosion resistance; whereas the curve will persist to stay at a higher current if the material is susceptible and stays susceptible to corrosion. The results of the commercial alloy silicon brass, C69300, shown by the solid line, and a common brass, C27450, indicated by the dashed line, as shown in Figure 2, indicate that the common brass experiences corrosion at lower levels, and that such corrosion ceases (reaches zero) much earlier in time than the silicon brass, C69300. In the corrosion testing, the open circuit potential ("OCP") was measured for 30 min as described above. An anodic sweep from OCP to +250 mV-SCE at 0.2 mV/s was taken, as well as a chronoamperometric measurement for about 12 hours at +250 mV-SCE, there after stop polarization and the OCP was measured for 30 min. The analysis was then conducted by integrating the chronoamperometric data over the test duration. The area under the chronoamperometric curve (Ampere-second) is taken as the total corrosion charge in Coulombs. Upon examination of the solution after the chronoamperometric tests, the solutions from the testing of silicon brass have developed a blue tint, indicating the presence of copper (Cu) ions in the solution; and the spectrophotometric analyses has shown that the copper (Cu) concentration in the solutions are as high as 3000 part per million by weight. Test Alloy Examples:
[0038] Chronoamperometric corrosion tests were also conducted on the applicant's improved copper (Cu) corrosion resistant, machinable brass alloys containing tin (Sn) samples in 3 test series. Test series No. l comprised the test alloys listed in Table 1 below, where 0 % by weight of tin (Sn) was included in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples. In test series No. 2, shown in Table 2 below, the weight % of tin (Sn) was 3 % in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over the 5 samples. In test series No. 3, shown in Table 3 below, the weight % of tin (Sn) was 6 % in all samples, and the weight % of lead (Pb) was varied as shown from 0 to 1 over 5 samples. Measurements were done in simulated tap water (Schock's 4, EPA); the electrode potentials in volt versus saturated calomel electrode (SCE); the electrode potential held at +250 mV versus SCE, with the further testing as described above.
[0039] The test results shown in Figures 3, 4 and 5, enable a direct comparison of the impact of including tin (Sn) and lead (Pb) on copper (Cu) corrosion resistance in the test samples as well as to the prior art samples. As can be readily seen, the addition of tin (Sn) to alloys in test series 2-1 to 2-5 in Figure 4, as compared to the results in Figure 3, show the corrosion dramatically decreases or drops to nearly 0, much sooner in time than any of the alloys in test series No. 1-1 to 1-5. Likewise, a still further dramatic drop is seen in the test series 3-1 to 3-5 results of Figure 5, over the results of test series No. 2 in Figure 4, where the time taken until corrosion drops to almost 0 is nearly cut in half from almost 40,000 s to almost 20,000 s. Still further, the comparison of either test series No. 2 or 3 (Figures 4 and 5), with the prior art brass alloy results in Figure 2, shows a marked improvement in copper (Cu) corrosion resistance.
[0040] In addition to copper (Cu) corrosion testing, hardness testing was also conducted by measuring the Rockwell B-scale hardness (HRB) of each test series sample at mid-radius of the test sample cylinder. The results, shown in Figure 6, illustrate the mean hardness at the mid-radius of the test samples, where Rockwell B- Scale hardness (HRB) is measured against the weight % of lead (Pb) and tin (Sn) within the test samples. As can be seen, a desirable hardness for machinability, which is about 78 HRB (or between 75 and 80), is generally obtained at between 1 and 3 weight % of tin (Sn) within the test series alloys, and at about 2 weight % of tin (Sn), where lead (Pb) is used in the test alloys at a weight % of between 0.1 and 0.5.
[0041] Cutting tests were also conducted to review the machinability of applicant's alloys in comparison with the conventional alloys. In the cutting tests, evaluations were made on the basis of chip color, size and shape. The tests were conducted by mounting the cylindrical test samples on a lathe, where a tool cut the samples at a cutting speed of 250 feet per minute, and a feed of 0.01 inches per revolution. The chips from the cutting work were examined and are shown for example, for the conventional brass alloys, C36000 (a free-cutting brass having the components previously described), C36500 (a brass composed of 60 % Copper (Cu), 0.6 % Lead (Pb), and 39.4 % Zinc (Zn)) and C69300 (a lead (Pb)-free silicon brass having the components previously described), in Figures 8A, 8B and 8C, respectively. The larger sized chips, for example in Figure 8B, are not generally preferred, as they can hamper machining, tool life and the productivity. Chips in the form of a needle- like arc, as in Figures 8 A, indicate a material which provides the desired ease of machinability.
[0042] Figures 9A, 9B and 9C illustrate chips from a cutting test of a sample of test series nos. 1-1, 2-1 and 3-1 in Tables 1, 2 and 3, respectively. Figures 10A, 10B and IOC illustrate chips from a cutting test of a sample of the test series nos. 1-2, 2-2 and 3-2 in Tables 1, 2 and 3, respectively. Figures 11A, 1 IB and 11C illustrate chips from a cutting test of a sample of the test series nos. 1-3, 2-3 and 3-3 in Tables 1, 2 and 3, respectively. Figures 12 A, 12B and 12C illustrate chips from a cutting test of a sample of test series nos. 1-4, 2-4 and 3-4 in Tables 1, 2 and 3, respectively. Figures 13 A, 13B and 13C illustrate chips from a cutting test of the sample of the test series nos. 1-5, 2-5 and 3-5 in Tables 1, 2 and 3, respectively. Chips which lack arc, are too short, hard, flaky or grainy, such as those in Figures 9C, 12C and 13C, have less desirable machinability and may also cause difficulty to machinery or the operator. As can be seen upon comparison, the silicon brass chips of Figure 8C are comparable to those of test series no. 2-2 in Figure 10B, for example, in the arc shown in their appearance.
[0043] Additionally a further qualitative tests for hardness and machinability was conducted. The test measured the time to cut the test series samples of bar stocks with a hack saw blade. The saw blade was kept at a constant load. As lead (Pb) content increases the machinability tended to increase, but only up to a certain point, beyond which the saw blade becomes less effective due to lead (Pb) stuck in the teeth of the blade. The results of the time to cut a sample with a hack saw test is shown in Figure 7. [0044] It should be understood that applicant's current corrosion resistant brass or copper (Cu) alloy generally contains a balance of components to achieve improved copper (Cu) corrosion resistance, and machinability as well as lower cost conduit applications and plumbing fixtures of the type shown in Figure 14, in which a thin walled pressurized fixture carries potable water. Thus, while very low amounts of lead (Pb) are included, to enable a stream of recycled products to be used, as well as the increase machinability, lower amounts of tin (Sn), which is currently expensive, are also preferred to reduce cost when possible. Amounts of lead (Pb) under 0.25 % are provided for potable water plumbing fixture applications, while amounts of lead (Pb) over 0.25 % are only provided to the upper limit of 1 %, and such higher amounts are only considered in non-potable water applications.
[0045] While the present brass alloy has been described with reference to certain preferred embodiments, one of ordinary skill in the art will recognize that additions, deletions, substitutions, modifications and improvements can be made while remaining within the spirit and scope of the present invention as defined by the appended claims.
Table 1 Test Series No. 1 Alloy Composition (weight %)
Figure imgf000014_0001
Table 2 Test Series No. 2 Alloy Composition (weight %)
Figure imgf000014_0002
Table 3 Test Series No. 3 Alloy Composition (weight %)
Figure imgf000014_0003

Claims

CLAIMS I claim:
1. A corrosion resistant, machinable brass alloy consisting essentially of 69-79 %, by weight of copper (Cu); 2 to 4 %, by weight, of silicon; 1 to 3 %, by weight, of tin; 0.01 to 1 %, by weight, of lead (Pb); and the remaining %, but less than 20 %, by weight, of zinc (Zn).
2. A copper (Cu) corrosion resistant, machinable brass alloy consisting
essentially of 69-79 %, by weight, of copper (Cu); 2 to 4 %, by weight, of silicon; 1.5 to 2.5 %, by weight, of tin, 0.01 to 1 %, by weight, of lead (Pb); and the remaining %, but less than 20 %, by weight, of zinc (Zn).
3. A copper (Cu) corrosion resistant, machinable brass alloy consisting
essentially of 69-79 %, by weight, of copper(Cu); 2 to 4 %, by weight, of silicon; 2 to≤ 6 %, by weight, of tin; 0.01 to 1 %, by weight of lead (Pb), and the remaining %, but less than 35 %, by weight, of zinc (Zn).
4. A plumbing product manufactured from a low lead (Pb), machinable brass alloy having lead (Pb) in an amount ranging from 0.01 to 1 % by weight, and tin (Sn) in an amount ranging from 1 to 6 % by weight, such that the plumbing product is resistant to copper (Cu) corrosion, and has a thin wall which is under pressure during use, which use includes the passage of water.
5. The plumbing product of Claim 4, wherein the low lead (Pb), machinable
brass alloy includes lead (Pb) in an amount from 0.01 to 0.25 % by weight and tin (Sn) in an amount ranging from 1 to 3 % by weight.
6. The plumbing product of Claim 5, wherein the low lead (Pb), machinable
brass alloy includes tin (Sn) in an amount of about 2 % by weight.
PCT/US2010/058447 2009-11-30 2010-11-30 Copper corrosion resistant, machinable brass alloy Ceased WO2011066581A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11427891B2 (en) 2019-07-24 2022-08-30 Nibco Inc. Low silicon copper alloy piping components and articles

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9829122B2 (en) * 2011-11-07 2017-11-28 Nibco Inc. Leach-resistant leaded copper alloys
US9246298B2 (en) * 2012-06-07 2016-01-26 Cymer, Llc Corrosion resistant electrodes for laser chambers
CN103114220B (en) * 2013-02-01 2015-01-21 路达(厦门)工业有限公司 Excellent-thermoformability lead-free free-cutting corrosion-resistant brass alloy
ES2856029T3 (en) * 2015-03-31 2021-09-27 Kurimoto Ltd Copper alloy for use in a member for hydraulic works

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050247381A1 (en) * 1998-10-09 2005-11-10 Sambo Copper Alloy Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
US20090263272A1 (en) * 2007-10-10 2009-10-22 Toru Uchida Lead-free free-machining brass having improved castability
US20090280026A1 (en) * 2004-10-11 2009-11-12 Diehl Metall Stiftung & Co. Kg Copper-zinc-silicon alloy, products using the alloy and processes for producing the alloy

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53106652A (en) * 1977-03-01 1978-09-16 Futoshi Matsumura Welding rod for burying bronze and brass cavity
US6383643B1 (en) * 1999-08-24 2002-05-07 Badger Meter, Inc. Leach-protective coatings for water meter components

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050247381A1 (en) * 1998-10-09 2005-11-10 Sambo Copper Alloy Co., Ltd. Copper/zinc alloys having low levels of lead and good machinability
US20090280026A1 (en) * 2004-10-11 2009-11-12 Diehl Metall Stiftung & Co. Kg Copper-zinc-silicon alloy, products using the alloy and processes for producing the alloy
US20090263272A1 (en) * 2007-10-10 2009-10-22 Toru Uchida Lead-free free-machining brass having improved castability

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11427891B2 (en) 2019-07-24 2022-08-30 Nibco Inc. Low silicon copper alloy piping components and articles

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