EP3050983B1 - Laiton ayant une coulabilité améliorée et une résistance à la corrosion - Google Patents

Laiton ayant une coulabilité améliorée et une résistance à la corrosion Download PDF

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EP3050983B1
EP3050983B1 EP16152304.8A EP16152304A EP3050983B1 EP 3050983 B1 EP3050983 B1 EP 3050983B1 EP 16152304 A EP16152304 A EP 16152304A EP 3050983 B1 EP3050983 B1 EP 3050983B1
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mass
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brass
range
present
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EP3050983A1 (fr
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Toru Uchida
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Toto Ltd
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Toto 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/002—Castings of light metals
    • B22D21/005—Castings of light metals with high melting point, e.g. Be 1280 degrees C, Ti 1725 degrees C
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
    • E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
    • E03C1/02—Plumbing installations for fresh water

Definitions

  • the present invention relates to a brass having reduced amounts of lead and nickel or not containing them; more specifically, the present invention relates to a brass for casting possessing having improved castability and corrosion resistance, which can be advantageously used, for example, for a water faucet metal fitting containing only minute amounts of lead and nickel, or not containing them.
  • a water faucet metal fitting is in general made of a brass or a bronze. From the viewpoint of improving the processability and corrosion resistance of the material, lead (Pb) and nickel (Ni) are added. In recent years, however, the influences of Pb and Ni on the human body and environment have become a concern, and regulations related to Pb and Ni have been actively established in various countries. For example, in California, U.S.A., a regulation of the content of Pb in a water-contacting member of a water tap faucet which should be in the range of 0.25% or less by mass in weighted average has come into effect from January, 2010. In addition, in the U.S.A.
  • JP H08 (1996)-337831 A proposes a copper alloy for metal mold casting which comprises 0.05 to 0.2% by weight of Sn, 0.05 to 0.3% by weight of at least one or more elements selected from the group consisting of Sb, As, and P, 0.1 to 0.5% by weight of Al, 33.0 to 37.0% by weight of Zn, 0.5 to 3.0% by weight of Pb, and the balance Cu, with 35.7 to 41.0% by weight of a zinc equivalent, 15% or less of the area occupation rate of the ⁇ phase, and 17°C or lower as the solidification temperature range thereof.
  • 0.5 to 3.0% by weight of Pb is added thereto.
  • Ni is not disclosed as the element contained in the copper alloy.
  • WO 2014/135181 A1 discloses a brass alloy comprising ⁇ 0.3% Sn, preferably ⁇ 0.2% Sn, for a water faucet metal fitting / plumbing fitting.
  • the present invention has an object to provide a brass having reduced amounts of lead and nickel or not containing them, and also having improved castability, corrosion resistance, and the like.
  • the brass according to the present invention is defined by claim 1.
  • Fig. 1 is a diagram showing the shape of mold 1 used in a both end restriction test method for evaluating casting cracking resistance.
  • the term "unavoidable impurities" as used herein means elements present in an amount of less than 0.1% by mass unless otherwise specified.
  • elements such as manganese (Mn) and chromium (Cr) are included in the unavoidable impurities.
  • the amount of the unavoidable impurities is preferably less than 0.05% by mass.
  • the brass according to the present invention contains Bi (bismuth) and optionally Pb with the total amount thereof in the range of 0.005% or more by mass to 0.25% or less by mass.
  • amount of Pb can be made very small as mentioned above.
  • the addition amount of the at least one or more elements selected from the group consisting of Pb and Bi is made in the range of 0.15% or more by mass to 0.25% or less by mass as the total amount of them.
  • the addition amount of Pb is made in the range of 0.13% or more by mass to 0.23% or less by mass.
  • the addition amount of Bi is in the range of 0.13% or more by mass to 0.23% or less by mass.
  • Ni The brass according to the present invention contains Ni with the amount of 0.2% or less by mass.
  • amount of Ni can be made very small as mentioned above.
  • the addition amount of Ni is made 0.1% or less by mass.
  • the brass according to the present invention contains at least one or more elements selected from the group consisting of Sb, As (arsenic), and P (phosphorous) with the total amount thereof in the range of 0.05% or more by mass to 0.32% or less by mass.
  • the addition amount of Ni is so small that there is a tendency that sufficient corrosion resistance cannot be obtained; however, by containing the at least one or more elements selected from the group consisting of Sb, As, and P with the total amount thereof in the range of 0.05% or more by mass to 0.32% or less by mass, the corrosion resistance thereof can be enhanced. This effect can be synergistically expressed by adding a prescribed amount of Sn (this will be mentioned later) as compared with the single addition thereof.
  • the total addition amount of these elements is more than 0.32% by mass, there is a tendency that the corrosion resistance of the brass is not improved so eminently; and therefore, in view of economy, the upper limit thereof is determined to be 0.32% by mass.
  • the total addition amount of the at least one or more elements selected from the group consisting of Sb, As, and P is made in the range of 0.056% or more by mass to 0.315% or less by mass.
  • addition amount of each of Sb, As, and P is made in the range of 0.01% or more by mass to 0.30% or less by mass, in the range of 0.001% or more by mass to 0.30% or less by mass, and in the range of 0.005% or more by mass to 0.30% or less by mass, respectively.
  • the brass according to the present invention contains Sn in the range of 0.05% or more by mass to 0.2% or less by mass.
  • the addition amount of Ni is so small that there is a tendency that sufficient corrosion resistance cannot be obtained; however, by containing Sn in the range of 0.05% or more by mass to 0.2% or less by mass, the corrosion resistance thereof can be enhanced.
  • This effect can be synergistically expressed by adding a prescribed amount of the at least one or more elements selected from the group consisting of Sb, As, and P, as compared with the single addition thereof.
  • the brass according to the present invention contains at least one or more elements selected from the group consisting of Fe and B with the total amount thereof in the range of 0.0001% or more by mass to 0.3% or less by mass.
  • the addition amounts of Pb and Ni, the containing amounts thereof or the leaching amounts thereof being regulated or intended to be regulated are controlled to be very small. And therefore, this is based on the finding that deterioration of the corrosion resistance due to these reductions can be compensated by addition of prescribed amount of Sn as well as each of the at least one or more elements selected from the group consisting of Sb, As, and P.
  • the brass according to the present invention is based on the simultaneous finding that the castability thereof can be remedied by containing the at least one or more elements selected from the group consisting of Fe and B within the range as mentioned above. That is, each of Fe and B facilitates refinement of crystals (especially proeutectic ⁇ phase) so that cracking during the time of casting can be effectively avoided. Further, the brass according to the present invention, by virtue of the refinement, can also be imparted with good mechanical properties.
  • B forms, together with Fe, Cr, and the like (these will be mentioned later), an intermetallic compound thereby forming hard spots which possibly pose problems in the surface processing of the molded product after casting. Accordingly, when a smooth and flat surface is wanted, it is preferable to lower the addition amount of B and/or the amounts of Fe, Cr, and the like.
  • the amount of B is preferably 0.005% or less by mass, more preferably 0.003% or less by mass, while still more preferably 0.002% or less by mass; and the amount of Fe is preferably 0.10% or less by mass; and the amount of Cr is preferably less than 0.1% by mass.
  • the brass according to the present invention contains Zn in the range of 33.0% or more by mass to 40.0% or less by mass.
  • Zn in the range of 33.0% or more by mass
  • the casting yield thereof can be made higher.
  • increase of the ⁇ -phase region, which is poor in the corrosion resistance can be suppressed so that deterioration of the dezincification corrosion resistance may be avoided.
  • the brass according to the present invention contains Al in the range of 0.1% or more by mass to 0.5% or less by mass.
  • the addition amount of Al in the range of 0.1% or more by mass, castability thereof can be improved.
  • the warm-water fluidity and casting surface texture thereof can be improved.
  • preferable addition amount of Al is 0.3% or more by mass. With this, the warm-water fluidity and casting surface texture thereof can be improved furthermore. Also by having the addition amount of Al in the range of 0.5% or less by mass, deterioration of elongation and impact resistance value can be suppressed.
  • the brass according to the present invention contains Si in the range of 0.5% or less by mass.
  • the Zn equivalent of Si proposed by Guillet is 10; and thus, it increases an apparent Zn content thereby leading to a possibility that heterogeneous phases such as ⁇ phase and ⁇ phase are crystallized out in the crystal texture.
  • the addition amount of Si is 0.5% or less by mass, a possibility that heterogeneous phases such as ⁇ phase and ⁇ phase are crystallized out in the crystal texture is low.
  • the addition amount of Si is 0.1% or less by mass.
  • the balance after the above-mentioned element components comprises substantially copper (Cu) and unavoidable impurities.
  • the brass according to the present invention contains Cu in the range of 55% or more by mass to 70% or less by mass.
  • the addition amount of Cu is made in the range of 70% or less by mass, cracking due to crystallization of dendrite of the proeutectic ⁇ phase can be suppressed.
  • the addition amount of Cu is 55% or more by mass, deterioration of the castability, corrosion resistance, and mechanical properties as the brass can be suppressed.
  • the lower limit of the addition amount of Cu is 58% by mass, and the upper limit thereof is 66% by mass.
  • the brass according to the present invention may contain various additives in order to improve properties of the brass. Also in the present invention, it is preferable that amounts of the unavoidable impurities be as small as possible, though presence of them is not excluded.
  • Cr forms, together with Fe, B, and the like, an intermetallic compound thereby forming hard spots which possibly pose problems in the surface processing of the molded product after casting. Therefore, when a smooth and flat surface is wanted, it is preferable to lower the amount of Cr. Specifically, the amount thereof is less than 0.1% by mass, while preferably less than 0.01% by mass.
  • Mn improves strength of the brass.
  • an intermetallic compound of Mn and Si is formed thereby forming hard spots which possibly pose problems in the surface processing of the molded product after casting. Therefore, in order to suppress the influence to the castability as mentioned above, it is preferable that amount of Mn be made as small as possible. Specifically, the amount thereof is preferably less than 0.1% by mass, while more preferably less than 0.01% by mass.
  • an apparent Zn content in the brass of the present invention is in the range of 36% or more to 41% or less.
  • the apparent Zn content means the amount calculated by the following equation proposed by Guillet. This equation is based on the concept that the addition of additive elements other than Zn exhibits the same tendency as the addition of Zn.
  • Apparent Zn content % B + tq / A + B + tq ⁇ 100
  • the Zn equivalent of Bi has not been clearly defined yet. In the present specification, however, the Zn equivalent of Bi is calculated to be 0.6 in view of reference documents and the like. For the other elements, the value is regarded as "1," because the addition amount of them is very small and thus the influence on the Zn equivalent value is small, too.
  • the ratio of the ⁇ phase in the crystal texture thereof is 15% or less.
  • the brass having improved corrosion resistance can be realized.
  • the ratio of the ⁇ phase is 8% or less.
  • the brass for metal mold casting having improved corrosion resistance useful for a water faucet metal fitting can be realized. This is especially suitable for a pressure-resistant part of a water faucet metal fitting.
  • the ratio of the ⁇ phase is based on the area ratio of the cross section of the crystals.
  • the ratio of the ⁇ phase may be determined as the area ratio of the ⁇ phase, for example, by subjecting a photograph of a crystal texture taken with an optical microscope to image processing.
  • the brass according to the present invention has the amounts of Pb and Ni reduced to very small, or does not contain these elements; but on the other hand, the castability and corrosion resistance thereof are equal to or higher than the brass which contains Pb and Ni.
  • the brass is preferably used in a water faucet metal fitting material.
  • the brass according to the present invention is preferably used as a material for a water supply metal fitting, a drainage metal fitting, a valve, and the like.
  • the brass according to the present invention be produced by the method which comprises heat treatment after casting thereby decreasing the ratio of the ⁇ phase in the crystal texture thereof. Because the corrosion resistance thereof increases with decrease of the ratio of the ⁇ phase, the brass having improved corrosion resistance can be obtained.
  • the heat treatment is carried out in the temperature range of 450°C to 550°C and the time range of 30 minutes to 3 hours.
  • the brass having the ratio of the ⁇ phase in the range of 15% or less, preferably in the range of 8% or less can be obtained.
  • the brass obtained in this way has improved corrosion resistance.
  • the region of the ⁇ phase decreases and the concentrations of Sn and Sb in the ⁇ phase increase, so that the corrosion resistance in the ⁇ phase improves dramatically.
  • increase of the region of the ⁇ phase can be suppressed thereby suppressing deterioration of the corrosion resistance.
  • uneven distribution of elements in particular region of a grain boundary is resolved without requiring time, so that the region of the ⁇ phase can be decreased.
  • the effect that the ⁇ phase becomes smaller can be obtained.
  • this effect can be sufficiently obtained within 3 hours of the heat treatment.
  • the heat treatment longer than 3 hours does not give a significant effect of it; and thus, in view of economy, it is preferable that the upper limit of the time for the heat treatment be within 3 hours.
  • molded products using the brass according to the present invention as a material may be produced by any of mold casting and sand casting by virtue of good castability thereof.
  • the effect of the good castability can be more clearly enjoyed in the mold casting.
  • the brass according to the present invention has good machinability and thus can be machined after casting.
  • the brass according to the present invention may be extruded into a bar for machining and a bar for forging, or alternatively may be drawn into a wire rod.
  • the casting cracking resistance was evaluated by a both end restriction test method.
  • a mold 1 having a shape shown in Fig. 1 was used.
  • a heat insulating material 2 was arranged at the central part thereof so that the central part might be cooled later than both end restriction parts 3.
  • the restriction end distance (2L) was 100 mm, and the length (21) of the heat insulating material was 70 mm.
  • the casting cracking resistance was evaluated as ⁇ (Excellent) when cracking did not take place; as O(Good) when cracking partially took place but the cracking was not such a level that the test piece was broken; and as ⁇ (Bad) when cracking took place resulting in breaking of the test piece.
  • a cast ingot having a diameter of 35 mm and a length of 100 mm was produced by metal mold casting. This cast ingot was used as a test piece and was tested according to the technical standards JBMA T-303-2007 established by Japan Copper and Brass Association.
  • the corrosion resistance was evaluated as ⁇ (Excellent) when the maximum erosion depth was 100 ⁇ m or less; as ⁇ (Good) when the maximum erosion depth was 150 ⁇ m or less; and as ⁇ (Bad) when the maximum erosion depth was more than 150 ⁇ m.
  • Brasses having chemical compositions shown in the following Tables were produced by casting. Specifically, electrolytic Cu, electrolytic Zn, virgin Bi metal, electrolytic Pb, virgin Sn metal, virgin Sb metal, Cu-30% Ni mother alloy, electrolytic Al, Cu-15% Si mother alloy, Cu-2% B mother alloy, Cu-30% Mn mother alloy, Cu-10% Cr mother alloy, Cu-15% P mother alloy, Cu-10% Fe, Cu-20% As mother alloy and the like were provided as raw materials; and then, they were melted in a high frequency melting furnace while regulating the composition thereof. Firstly, the melt was cast into a mold for a both end restriction test to evaluate the casting cracking resistance.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Claims (6)

  1. Laiton composé de :
    Sn avec une teneur supérieure ou égale à 0,05 % en masse et inférieure ou égale à 0,2 % en masse,
    au moins un ou plusieurs éléments sélectionnés à partir du groupe constitué par le Sb, l'As et le P, une quantité totale de ceux-ci étant supérieure ou égale à 0,05 % en masse et inférieure ou égale à 0,32 % en masse,
    Al avec une teneur supérieure ou égale à 0,1 % en masse et inférieure ou égale à 0,5 % en masse,
    Zn avec une teneur supérieure ou égale à 33,0 % en masse et inférieure ou égale à 40,0 % en masse,
    Bi et, en variante, Pb
    une quantité totale de ceux-ci étant supérieure ou égale à 0,005 % en masse et inférieure ou égale à 0,25 % en masse,
    dans lequel la teneur en Bi est supérieure ou égale à 0,13 % en masse et inférieure ou égale à 0,23 % en masse,
    Ni avec une teneur inférieure ou égale à 0,2 % en masse,
    Si avec une teneur inférieure ou égale à 0,5 % en masse,
    au moins un ou plusieurs éléments sélectionnés à partir du groupe constitué par Fe et B, une quantité totale de ceux-ci étant supérieure ou égale à 0,0001 % en masse et inférieure ou égale à 0,3 % en masse,
    en variante, Cr avec une teneur inférieure ou égale à 0,1 % en masse ;
    en variante, Mn avec une teneur inférieure ou égale à 0,1 % en masse ; et
    le complément se composant de Cu et d'impuretés inévitables ; et aussi
    une teneur apparente de Zn étant supérieure ou égale à 36% et inférieure ou égale à 41%, dans lequel la teneur apparente de Zn est calculée par l'équation : teneur apparente % de Zn = B + tq / A + B + tq x 100
    Figure imgb0011
     dans laquelle A représente le % en masse de Cu ; B représente le % en masse du Zn ; t représente l'équivalent en Zn de l'élément additif, et q représente le % en masse de la quantité ajoutée de l'élément additif, l'équivalent en Zn de chaque élément étant Si = 10, Al = 6, Sn = 2, Pb = 1, Fe = 0,9, Mn = 0,5, Ni = -1.3 et Bi = 0,6 et 1 pour les autres éléments.
  2. Procédé de production d'un produit en laiton, ledit procédé comprend :
    la fourniture du laiton selon la revendication 1 ; le moulage du laiton ; et la mise en oeuvre d'un traitement thermique dans une plage de température de 450°C à 550°C et une plage de temps de 30 minutes à 3 heures.
  3. Produit en laiton réalisé suivant le procédé selon la revendication 2, dans lequel la texture de cristal présente un rapport de phase β inférieur ou égal à 15% par rapport à la texture de cristal.
  4. Raccord métallique de robinet d'eau comprenant le laiton selon la revendication 1, ou le produit en laiton selon la revendication 3.
  5. Raccord métallique d'alimentation en eau comprenant le laiton selon la revendication 1, ou le produit en laiton selon la revendication 3.
  6. Raccord métallique de purge comprenant le laiton selon la revendication 1, ou le produit en laiton selon la revendication 3.
EP16152304.8A 2015-01-28 2016-01-21 Laiton ayant une coulabilité améliorée et une résistance à la corrosion Active EP3050983B1 (fr)

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JP2015014370 2015-01-28
JP2015239068A JP6056947B2 (ja) 2015-01-28 2015-12-08 鋳造性および耐食性に優れた黄銅

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US10351933B2 (en) * 2012-02-01 2019-07-16 Toto Ltd. Brass with excellent corrosion resistance
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MX2017001955A (es) * 2017-02-10 2018-08-09 Nac De Cobre S A De C V Aleaciones de cobre bajas en plomo.
CN107385273B (zh) * 2017-07-07 2019-03-01 路达(厦门)工业有限公司 一种铸造用环保黄铜合金及其制造方法
CN109038940A (zh) * 2018-08-08 2018-12-18 东莞市特姆优传动科技有限公司 一种高效大推力太阳能板电动推杆
US11512370B2 (en) 2019-06-25 2022-11-29 Mitsubishi Materials Corporation Free-cutting copper alloy and method for producing free-cutting copper alloy
DE102020128955A1 (de) * 2020-11-03 2022-05-05 Aurubis Stolberg Gmbh & Co. Kg Messinglegierung

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