EP3128020B1 - Alliage de laiton à faible teneur en plomb pour élément de plomberie - Google Patents

Alliage de laiton à faible teneur en plomb pour élément de plomberie Download PDF

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EP3128020B1
EP3128020B1 EP15772552.4A EP15772552A EP3128020B1 EP 3128020 B1 EP3128020 B1 EP 3128020B1 EP 15772552 A EP15772552 A EP 15772552A EP 3128020 B1 EP3128020 B1 EP 3128020B1
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mass
content
alloy
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test
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EP3128020A1 (fr
EP3128020A4 (fr
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Hiroshi Yamada
Masaaki Yamamoto
Takeaki Miyamoto
Syohei MATSUBA
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Kurimoto Ltd
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Kurimoto 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

Definitions

  • the present invention relates to a material made of a brass alloy and having an erosion-corrosion resistance, designed for use in a member for water works.
  • Patent Document 1 discloses a brass alloy having a reduced risk of dezincification corrosion and improved mechanical properties and castability, while having a reduced lead content, which brass alloy containing, along with Zn, from 0.4 to 3.2% by mass of Al, from 0.1 to 4.5% by mass of Bi, and from 0.001 to 0.3% by mass of P.
  • Patent Document 2 discloses a brass alloy (for example, No. 6 or No. 20) capable of preventing water quality deterioration and having an excellent machinability and abradability at the time of plating pretreatment, which brass alloy containing from 0.3 to 1.0% of Sn, from 0.5 to 1.0% of Ni, from 0.4 to 8% of Al, from 0.01 to 0.03% of P, from 1.0 to 2.0% of Bi, and a trace amount of Sb.
  • Patent Document 2 also discloses a brass alloy further containing from 5 to 10 ppm by weight of B, in addition to containing the above mentioned elements within the above ranges.
  • a brass alloy which contains no Bi, and which is useful as a member for water works in terms of recyclability.
  • the alloy No. 20 disclosed as a Comparative Example in Patent Document 2 does not contain Bi, there is no need to carry out the sorting of alloys based on whether or not Bi is contained, at the time of recycling.
  • any brass alloy is susceptible to corrosion induced by the rapid flow of water, referred to as an erosion-corrosion.
  • an oxide film is gradually formed on the surface of the metallic material to prevent corrosion.
  • the alloy No. 20 disclosed as a Comparative Example in Patent Document 2 has an insufficient erosion-corrosion resistance.
  • Examples of the brass alloy having an erosion-corrosion resistance, as described above, include alloys disclosed in the below-identified Patent Documents 4 to 6.
  • Patent Document 4 discloses a copper alloy containing from 10 to less than 25 wt% of Zn, from 0.005 to 0.070 wt% of P, from 0.05 to 1.0 wt% of Sn, and from 0.05 to 1.0 wt% of Al; and any one or two of from 0.005 to 1.0 wt% of Fe and from 0.005 to 0.3 wt% of Pb in a total amount of from 0.005 to 1.3 wt%; with the balance being copper and an unavoidable impurity(ies); wherein the alloy has an excellent erosion-corrosion resistance.
  • Patent Document 6 discloses a copper alloy containing from 25 to 40 wt% of Zn, from 0.005 to 0.070 wt% of P, from 0.05 to 1.0 wt% of Sn, from 0.05 to 1.0 wt% of Al, and from 0.005 to 1.0 wt% of Si, as essential elements; and any one or two of from 0.005 to 1.0 wt% of Fe and from 0.005 to 0.3 wt% of Pb in a total amount of from 0.005 to 1.3 wt%; with the balance being copper and an unavoidable impurity(ies); wherein the alloy is characterized by being subjected to cold rolling at reduction of sectional area of 3 to 20%, after final annealing, and having an excellent dezincification corrosion resistance.
  • Patent Document 9 discloses a copper alloy having superior corrosion resistance which consists of 10-25% Zn, 0.005-0.07% P, 0.05-1.0% Sn, 0.005-1.0% Al and the balance being Cu and inevitable impurities.
  • the alloy may further contain 0.005-1.3% in total of Fe and/or Pb.
  • Patent Document 10 discloses an environmentally friendly brass alloy composed of 0.4-0.8% Al, 0.6-1.6% Ni, 0.8-2.0% Sn, 60-68 wt% Cu, 27.6-35.6% Zn and ⁇ 0.1 wt% of Fe, Pb, P and impurities.
  • Patent Document 11 discloses a lead-free copper alloy for casting which contains 25.0-33.0% Zn, 0.60-1.50% Sn, 0.30-3.0% Bi, 0.40-1.00% Si, 0.35-1.50% Al, 0.02-0.20% Sb, 0.0005-0.010% B, 0.20% or less Pb, with the remainder being Cu and unavoidable impurities.
  • Patent Document 12 discloses a copper alloy containing 69 to 79% Cu, 2.0 to 4.0% Si, 0.02 to 0.4% Pb, with the remainder being Zn.
  • Patent Documents 5 and 6 contain a large amount of Zn, they have problems that the elongation tends to be insufficient, and that the dezincification corrosion is likely to occur.
  • the alloys also have an insufficient erosion-corrosion resistance.
  • Patent Document 7 since the alloys disclosed in Patent Document 7 contain Zr and/or Te as an essential element(s), problems may occur when used as a mixture with other copper alloys. In particular, since Te is toxic, the use of this alloy as a member for water works is not desirable in the first place.
  • Patent Document 8 contains Bi, it cannot be recycled along with other common copper alloys containing Pb. This alloy also has a problem of insufficient erosion-corrosion resistance.
  • an object of the present invention is to provide a brass alloy, in which the contents of toxic elements are reduced while maintaining the dezincification corrosion resistance required for a member for water works; which is capable of exhibiting an erosion-corrosion resistance while having a reduced Bi content to secure a good recyclability; and which has excellent mechanical properties to be used as a member for water works.
  • Pb contributes to improving the machinability of the alloy, even in a small amount within the range in which its adverse effects on health are limited.
  • Pb and Al-P compounds work in combination to serve as chip breakers, and significantly contribute to improving the machinability. This allows the alloy to have a sufficient machinability, making it suitable for a member for water works.
  • the incorporation of a specified amount of Sn allows the alloy to exhibit mechanical properties required for a brass alloy having a high content of Zn, such as tensile strength, elongation, and 0.2% proof stress, while exhibiting durability against erosion-corrosion.
  • the brass alloy according to the present invention contains Si in an amount less than the amount contained as unavoidable impurities. This is because Si tends to produce an oxide which causes problems in recyclability and mechanical properties, particularly, in elongation. In addition, Si may potentially cause a reduction in the erosion-corrosion resistance.
  • the present invention allows for producing a member for water works made of a brass alloy which has a good machinability and erosion-corrosion resistance while having a reduced Bi content to improve the recyclability, and in which safety, durability, and convenience are ensured.
  • the present invention relates to a brass alloy for use in a member for water works which contains at least Zn, Sn, Al, P, Pb, and Ni.
  • the above mentioned brass alloy have a Sn content of 0.5% by mass or more. If the Sn content is less than 0.5% by mass, the resulting alloy has an insufficient resistance to erosion-corrosion.
  • a Sn content of 1.0% by mass or more is preferred, because the resulting alloy has a sufficient erosion-corrosion resistance and a sufficient 0.2% proof stress.
  • the Sn content be 1.7% by mass or less. Preferably, the content is 1.3% by mass or less. This is because too high a Sn content tends to results in too low an elongation. Further, in cases where the Sn content is less than 1.0% by mass, it is necessary that the relationship between the Sn content and the Al content satisfy Inequality (3) to be described later, in order to secure the erosion-corrosion resistance.
  • the above mentioned brass alloy have an Al content of 0.4% by mass or more.
  • the Al content is 0.6% by mass or more.
  • An Al content of less than 0.4% by mass results in an insufficient tensile strength and/or 0.2% proof stress, thereby causing problems in mechanical properties.
  • compounds formed between Al and P to be described later significantly contribute to the improvement in the machinability.
  • the Al content is deficient, the effect provided by the compounds will also be insufficient.
  • the content is 1.3% by mass or less.
  • An Al content exceeding 1.8% by mass may results in too low an elongation.
  • the above mentioned brass alloy have a Pb content of 0.01% by mass or more.
  • the Pb content is 0.03% by mass or more.
  • the presence of Pb contributes to an improved machinability of the alloy, along with the Al-P compounds, but if the Pb content is less than 0.01% by mass, there is a potential risk that the machinability may be insufficient.
  • the above mentioned brass alloy contains Sn, which leads to the formation of hard ⁇ -phase, in particular, the effect of improving the machinability provided by Pb is indispensable.
  • the Pb content exceeds 0.25% by mass, it becomes difficult to comply with the leaching standards for alloys for use in members for water works, depending on the district in which it is used. Accordingly, it is necessary that the Pb content be 0.25% by mass or less, at maximum.
  • the content of Si is less than 0.2% by mass, more preferably, less than 0.1% by mass, and still more preferably, less than the detection limit. Too high a Si content accelerates the entrainment of oxides, decrease in elongation, and occurrence of shrinkage cavities, resulting in a failure to produce a decent casting.
  • the content of Bi be less than 0.3% by mass.
  • the Bi content is preferably less than 0.1% by mass, and still more preferably, less than the detection limit. This is because, if the alloy contains an unignorable amount of Bi, the products made therefrom must be recycled separately, thereby complicating the recycling process. If the Bi content exceeds 0.3% by mass, the coexistence of Bi in combination with Pb contained in the brass alloy according to the present invention may cause an insufficient elongation, and there is a potential risk that problems in mechanical properties could occur.
  • the content of each of the elements which are considered as the unavoidable impurities is preferably less than 0.4% by mass, more preferably, less than 0.2% by mass, and still more preferably, less than the detection limit.
  • impurities include Fe, Mn, Cr, Zr, Mg, Ti, Te, Se, and Cd.
  • the contents of Se, Cd, and Te, which are known to be toxic are each preferably less than 0.1% by mass, and more preferably, less than the detection limit.
  • the content of Zr which increases the occurrence of shrinkage cavity defects, is preferably less than 0.1% by mass, and still more preferably, less than the detection limit.
  • the dezincification corrosion resistance is significantly improved. This is because the presence of B causes the crystal grains to be refined and to be formed into shapes less susceptible to dezincification corrosion.
  • the content of B is preferably 0.0007% by mass or more, because the dezincification corrosion resistance is further improved.
  • the B content exceeds 0.015% by mass, a large amount of hard compounds is formed within the texture of the alloy, potentially causing adverse effects on machinability or elongation.
  • the above mentioned brass alloy contains Ni as an intentionally included element. Since the Ni content is 0.1% by mass or more, the surface area of ⁇ -phase, which has an excellent corrosion resistance, is increased, thereby improving the dezincification corrosion resistance of the brass alloy. It is possible to adjust the composition such that the alloy benefits from both the effect provided by containing B, and the effect provided by containing Ni. At the same time, the Ni content is 0.5% by mass or less. The addition of an excessive amount of Ni increases the amount of a phase having a high Sn content, and the resulting alloy tends to have a reduced elongation and/or machinability.
  • the above mentioned brass alloy may contain both B and Ni as intentionally included elements, within the above described ranges.
  • the values of the contents of elements as used in the present invention indicate the contents thereof in the resulting alloy produced by casting or forging, not the contents in the raw materials.
  • the brass alloy according to the present invention will now be described with reference to Examples in which the brass alloys were actually produced. First, test methods carried out for the brass alloys will be described.
  • a sample prepared by casting in a metal mold having a size of 28 mm diameter ⁇ 200 mm length was processed into a type 14A test specimen defined in JIS Z2241.
  • the specific shape of the test specimen is as shown in FIG. 1 .
  • the diameter d 0 of the rod-like portion was 4 mm
  • the original gauge length L 0 was 20 mm
  • the length L c of the parallel portion which was cylindrical 30 mm
  • the radius R of the shoulder portions was 15 mm.
  • the test specimen was subjected to a tensile test according to JIS Z2241 and the tensile strength (MPa), the 0.2% proof stress (MPa) and the elongation (%) were evaluated as follows.
  • the tensile strength was defined as the maximum test force Fm, which was the force the test specimen withstood during the test until it exhibited discontinuous yielding.
  • the 0.2% proof stress is the value of the stress when the plastic elongation expressed in percentage relative to the original gauge length L 0 equals to 0.2%.
  • the elongation is the value of the permanent elongation of the test specimen after the test, obtained by continuing the test until it ruptures, expressed in percentage relative to the original gauge length L o .
  • a sample prepared by casting in a metal mold having a size of 20 mm diameter ⁇ 120 mm length was cut into a cylinder having a diameter of 16 mm as shown in FIG. 2 , to be used as a test specimen 12.
  • a nozzle 11 having a bore diameter of 1.6 mm was disposed at a position 0.4 mm spaced apart from the test specimen 12, and a 1% aqueous solution of CuCl 2 13 was allowed to continuously flow from the nozzle 11 toward the sample at a flow rate of 0.4 L/min for 5 hours. Then the amount of the weight lost (abrasion weight loss), which is the difference in weight of the sample before and after the test, and the maximum erosion-corrosion depth in the sample were measured.
  • Each of the alloys was subjected to a drilling test using a drilling machine.
  • the drilling test was carried out using the samples each formed by machining to a size of 18 mm diameter ⁇ 20 mm height, and using a drilling machine, under the drilling conditions shown in Table 1.
  • the evaluation was carried out as follows. The time required to drill a 5 mm hole in each of the samples was measured, and those with the results of 20 seconds or less were evaluated as "Good” (G), those with the results of more than 20 seconds and 25 seconds or less were evaluated as "Fair” (F), those with the results of more than 25 seconds were evaluated as "Insufficient” (I).
  • machining chips were categorized based on their shapes as shown in FIG. 3 .
  • the evaluation was carried out as follows: those having favorable shapes were evaluated as "Good” (G), and those having unfavorable shapes were evaluated as "Insufficient” (I).
  • a sample prepared by casting in a metal mold having a size of 28 mm diameter ⁇ 200 mm length was cut out into a cubic test specimen of 10 mm ⁇ 10 mm ⁇ 10 mm, and the test was performed according to ISO 6509. Specifically, the surroundings of the test specimen was covered with an epoxy resin having a thickness of 15 mm or more such that only one surface of the test specimen was exposed from the resin. After 100 mm 2 of this exposed surface was polished with wet abrasive paper, the exposed surface was finished with No. 1200 abrasive paper, and washed with ethanol immediately before the test.
  • This sample embedded in the epoxy resin with only one surface exposed was immersed in 250 mL of a 12.7 g/L aqueous solution of cupric chloride at 75 ⁇ 5°C for 24 hours. After the completion of the test, the sample was washed with water, rinsed with ethanol, and the dezincification depth in its cross section was immediately measured using a light microscope. Specifically, an arbitrary line of 10mm on cross-section of the exposed surface was divided into 5 visual fields and the dezincification depths of the points having the minimum and the maximum depths in each of the visual fields were measured. The mean value of the total 10 points was taken as the average dezincification corrosion depth, and the depth of the deepest point of all these 10 points was taken as the maximum dezincification corrosion depth. The average and maximum dezincification corrosion depths were evaluated as follows, and those having evaluations other than "insufficient" for both the dezincification depths were defined as "pass".
  • FIG. 4 shows line graphs obtained by plotting the data of the above obtained results, categorized in 3 groups based on the concentration of Al, with the values the maximum erosion-corrosion depth on the vertical axis against the values of the Sn content on the horizontal axis.
  • Test Examples 1 to 4 are alloys having an Al content of 0.6% by mass
  • Test Examples 5 to 8 are alloys having an Al content of 1.0% by mass
  • Test Examples 9 to 12 are alloys having an Al content of 1.7% by mass.
  • the alloy of Test Example 2 with a Sn content 0.2% higher than that of Test Example 1, and the alloy of Test Example 5 with an Al content 0.4% higher than that of Test Example 1, have the same level of reduction in the maximum erosion-corrosion depth relative to the alloy of Test Example 1. Consequently, it is assumed that, in the improvement in the erosion-corrosion resistance, which is observed as the reduction in the maximum erosion-corrosion depth associated with an increase in the Sn or Al content, an increase in the Sn content has twice as large an effect as an increase in the Al content does, when the Sn content is within the range of less than 1.0% by mass.
  • the value T represented by the following Equation (4) can be used as an index for the erosion-corrosion resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Domestic Plumbing Installations (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (2)

  1. Alliage de laiton à faible teneur en plomb destiné à être utilisé dans un élément pour ouvrage hydraulique, l'alliage de laiton étant constitué de :
    27 % en masse ou plus et 34 % en masse ou moins de Zn ;
    0,5 % en masse ou plus et 1,7 % en masse ou moins de Sn ;
    0,4 % en masse ou plus et 1,8 % en masse ou moins d'Al ;
    0,005 % en masse ou plus et 0,2 % en masse ou moins de P ; et
    0,01 % en masse ou plus et 0,25 % en masse ou moins de Pb ;
    0,1 % en masse ou plus et 0,5 % en masse ou moins de Ni ; et
    éventuellement 0,0005 % en masse ou plus et 0,015 % en masse ou moins de B ;
    le reste étant du cuivre et des impuretés inévitables ;
    où, lorsque l'alliage de laiton a une teneur en Sn inférieure à 1,0 % en masse, les teneurs en Al et Sn en % en masse satisfont à l'inégalité (1) suivante : Al + 2 × Sn ≥ 2,8
    Figure imgb0010
     et
    où lesdites impuretés inévitables contiennent moins de 0,2 % en masse de Si et moins de 0,3 % en masse de Bi.
  2. Alliage de laiton à faible teneur en plomb selon la revendication 1, dans lequel la teneur en Sn est supérieure ou égale à 1,0 % en masse.
EP15772552.4A 2014-03-31 2015-03-06 Alliage de laiton à faible teneur en plomb pour élément de plomberie Active EP3128020B1 (fr)

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JP2014059499 2014-03-31
PCT/JP2015/056671 WO2015151720A1 (fr) 2014-03-31 2015-03-06 Alliage de laiton à faible teneur en plomb pour élément de plomberie

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US (1) US20170121791A1 (fr)
EP (1) EP3128020B1 (fr)
JP (1) JP6482530B2 (fr)
KR (1) KR102314457B1 (fr)
CN (1) CN106103755A (fr)
WO (1) WO2015151720A1 (fr)

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CN106103755A (zh) 2016-11-09
KR20160140821A (ko) 2016-12-07
JPWO2015151720A1 (ja) 2017-04-13
JP6482530B2 (ja) 2019-03-13
WO2015151720A1 (fr) 2015-10-08
EP3128020A1 (fr) 2017-02-08
US20170121791A1 (en) 2017-05-04
KR102314457B1 (ko) 2021-10-19
EP3128020A4 (fr) 2017-04-12

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