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EP1273671B1 - Alliage cuivre-zinc résistant à la dezincification et son procédé de fabrication - Google Patents

Alliage cuivre-zinc résistant à la dezincification et son procédé de fabrication Download PDF

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Publication number
EP1273671B1
EP1273671B1 EP20020015027 EP02015027A EP1273671B1 EP 1273671 B1 EP1273671 B1 EP 1273671B1 EP 20020015027 EP20020015027 EP 20020015027 EP 02015027 A EP02015027 A EP 02015027A EP 1273671 B1 EP1273671 B1 EP 1273671B1
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EP
European Patent Office
Prior art keywords
rest
weight
alloy
copper
dezincification
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EP20020015027
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German (de)
English (en)
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EP1273671A1 (fr
Inventor
Norbert Dr. Gaag
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Diehl Metall Stiftung and Co KG
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Diehl Metall Stiftung and Co KG
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    • 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
    • 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 invention relates to a dezincification-resistant copper-zinc alloy, which is particularly suitable for sanitary applications, e.g. suitable for drinking water fittings, drinking water pipes or pipe binders.
  • the invention further relates to a manufacturing method for such a copper-zinc alloy.
  • Common copper-zinc alloys can occur in two different metallic phases.
  • the brass alloy has an fcc (Face-Centered-Cubic) structure, while in the ⁇ -phase it has a Bcc (Body-Centered-Cubic) structure.
  • the pure ⁇ -phase occurs at a copper content of more than 62% by weight.
  • the brass alloy is present with portions of both the ⁇ and the ⁇ phase. In the presence of additional metallic components, the above-mentioned phase boundaries shift.
  • a brass alloy For sanitary applications, a brass alloy must have high corrosion resistance due to the constant water contact. Brass, and also copper, forms cover layers of copper oxide in aqueous, slightly acidic to alkaline electrolyte solutions, which generally provide some protection against general corrosion. In soft, chloride-containing waters, brass alloys may experience a special form of corrosion called dezincification. The zinc is dissolved out of the brass alloy and a porous copper sponge remains behind. Furthermore, the ⁇ -phase is attacked more as the ⁇ -phase, since the former is less electropositive to the latter. To improve the corrosion resistance of a brass alloy, it is therefore known to prevent the formation of a ⁇ -phase as much as possible by means of a heat treatment during production.
  • the addition of a single further metallic component can drastically change other characteristics of the brass alloy.
  • the additive arsenic although the corrosion protection for the ⁇ -phase, but deteriorates in the presence of ⁇ and ⁇ phase, the corrosion resistance to sulphate waters. Since the composition of drinking water, ie, the type and concentration of ions dissolved therein, is highly dependent on its geographical origin, lengthy research is needed to assemble a brass alloy that will not corrode even after decades of use and contact with water.
  • As dezincification and corrosion resistant brass alloy is from the WO 89/08725 a copper-zinc alloy containing up to 0.8% by weight of nickel, between 0.5 and 3% by weight of lead, between 0.3 and 1% by weight of silicon and between 0.07 and 0 , 8 wt .-% iron.
  • Arsenic is considered to be in principle disturbing because it promotes intergranular corrosion, which is why its content should be less than 0.02% by weight.
  • the object of the invention is to provide a copper-zinc alloy which has a particularly high resistance to dezincification and intercrystalline corrosion, and is particularly suitable for sanitary applications. It is another object of the invention to provide a manufacturing method for such a copper-zinc alloy.
  • the first-mentioned object is achieved for a copper-zinc alloy according to the invention in that it contains 50 to 80% by weight of copper, 0 to 5% by weight of lead, 0.01 to 0.1% by weight of arsenic, 0, 03 to less than 0.3% by weight of silicon, 0 to 0.3% by weight of iron, 0 to 0.04% by weight of manganese, the balance being zinc and unavoidable impurities, and that the effective copper Equivalent to 60 to 70 wt .-% is.
  • a copper-zinc alloy with the said composition both has a high dezincification resistance and also a very low intergranular corrosion, referred to below as IK shows.
  • the invention is based on the recognition that a certain content of arsenic is crucial for the avoidance of intercrystalline corrosion. Furthermore, the invention assumes that iron is not required for the corrosion resistance of the brass alloy, but has a disturbing effect. However, the disturbing influence of iron can be avoided to a limited extent by the addition of silicon.
  • the object of the production method for a copper-zinc alloy wherein the starting materials are mixed, melted and cast according to the desired composition into a metallic alloy, and wherein the metallic alloy for forming the ⁇ -phase at 500-650 Is annealed ° C, is inventively achieved in that the annealed metallic alloy is actively cooled by means of coolants.
  • Table 1 lists the composition of these 44 experimental alloys in terms of copper, lead, arsenic, iron, silicon, manganese, aluminum and zinc.
  • the desired and the actual proportion in wt .-% is reproduced.
  • the trial alloys are each designated with four-digit numbers. This term is used below for the respective alloy.
  • the experimental alloys listed in Table 1 were prepared as follows: 1. Cast the molten alloy at a temperature of 1050 to 1100 ° C in a steel mold of the dimensions 110 mm x 40 mm 2. Milling the sample to a thickness of 14 mm 3. Rolling the sample to 5 mm, with intermediate annealing for 1 hour at temperatures of about 700 ° C. 4. ⁇ -anneal for 2 hours at a temperature of 550 degrees Celsius Table 1: ⁇ b> Nominal and actual compositions of the experimental alloys in% by weight ⁇ / b> Leg.-Nr.
  • a dezincification test was performed according to ISO 6509.
  • the degree of dezincification of the respective alloy becomes corroding after a predefined test procedure Liquids determined by measuring a maximum Entzinkungstiefe in microns.
  • the maximum depth of dezincification determined in this way is a measure of the susceptibility of the test alloy to be dezincified. The greater the maximum dezincification depth of the particular experimental alloy, the greater its susceptibility to dezincification.
  • the dezincification resistance test according to ISO 6509 uses a very aggressive electrolyte solution for dezincification, which is not suitable for detecting IK due to very fine potential differences between grain boundaries and grain area.
  • IK susceptibility compared to CuZn36Pb2As in% Maximum dezincification depth to ISO 6509 in ⁇ m 2088 19 13 2089 46 12 2090 100 15 2094 30 6 2102 8th 0 2106 24 12 2131 91 0 2132 25 0 2133 10 0 2134 10 0 2135 65 0 2136 27 0 2156 5 212 2157 7 18 2158 7 0 2159 100 0 2160 100 0 2161 17 0 2162 13 0 2163 10 0 2164 8th 0 2165 23 0 2166 15 0 2167 18 0 2168 18 0 2169 17 0 2170 48 0 2171 100 0 2172 10 0 2173 11 0 2174 10 0 2175 88 50 2176 96 46 2177 100 75 2178 100 45 2179 83 60 2180 42 80 2181 42 95 2182 33 40 2183 58 34 2184 42 38 2185 46 54 2186 21 62 2187 33 108
  • FIG. 1 the susceptibility to intergranular corrosion in% is shown in column 3 of Table 2 for test alloys Nos. 2088, 2089, 2090, 2131 and 2132. These alloys differ in otherwise substantially the same composition in their arsenic content. The respective arsenic content in wt .-% is on the abscissa in FIG. 1 applied.
  • the illustrated experimental alloys have only a negligible or no share of iron, silicon, manganese and aluminum.
  • FIG. 1 a necessary for arsenic content between 0.01 and 0.1 wt .-% for a dezincification and resistant to IK brass alloy. Above a proportion of arsenic of 0.1 wt .-% protection against IK is no longer guaranteed. If the arsenic content is reduced below 0.08 wt .-%, the susceptibility to intergranular corrosion is only less than 60%.
  • the experimental alloys Nos. 2180 and 2181 have a value of 0.05% by weight with respect to their arsenic content which is not critical with respect to the IC. In addition, however, these trial alloys show a small amount of iron of 0.03 wt% and 0.06 wt%, respectively.
  • a comparison with the non-ferrous experimental alloys Nos. 2088 and 2089 shows that the addition of iron obviously lowers the critical upper limit for the arsenic content.
  • susceptibility to intergranular corrosion increases.
  • the susceptibility to dezincification increases with the addition of iron.
  • the trial alloy No. 2159 having an iron content of 0.082% by weight is used, its susceptibility to intergranular corrosion becomes clear.
  • the trial alloy No. 2159 shows a susceptibility to IK of 100% according to Table 2, whereas the trial alloys No. 2088 and No. 2089 show a susceptibility of only 19% and 46%, respectively.
  • alloys Nos. 2094, 2102 and 2106. These alloys have iron contents at an arsenic content of 0.07 wt% of 0.14 wt .-%, 0.1 wt .-% and 0.2 wt .-% to.
  • these experimental alloys contain silicon in a proportion of 0.08% by weight and 0.2% by weight.
  • a look at Table 2 shows that silicon can neutralize the damaging effects of iron. Susceptibility to intergranular corrosion decreases.
  • these experimental alloys are generally dezincification.
  • alloys Nos. 2135 and 2136 which have a silicon content of about 2% by weight, that they again become susceptible to intergranular corrosion.
  • FIG. 2 the susceptibility to intergranular corrosion is shown according to the results of Table 2 for trial alloys Nos. 2168 to 2171. These alloys differ in their composition in terms of their manganese content, which increases from the test alloy No. 2168 to the test alloy 2171 of 0.006 wt .-% to 0.055 wt .-%. It turns out that manganese is a very critical element in intercrystalline corrosion, and can not be neutralized by a proportion of silicon. All trial alloys Nos. 2168 to 2171 have a silicon content of about 0.2% by weight.
  • the permissible tolerances for manganese must therefore remain low. At a level of 0.04 wt%, the susceptibility to intergranular corrosion is less than 50%.
  • FIG. 3 is for a trial alloy containing 64.05% copper, 2.7% lead, 0.1% iron, 0.3% aluminum, 0.2% silicon and 0.05% arsenic and the remainder zinc (* symbol) , a CuZn36Pb2.7As0.14 alloy (O symbol) and a CuZn36Pb2.7 alloy ( ⁇ symbol), the lead release to drinking water based on NSF Standard 61, 1994 shown.
  • the lead levy is shown in ⁇ g per liter over time.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (6)

  1. Alliage cuivre-zinc résistant à la dézincification, notamment destiné à être utilisé dans le domaine sanitaire, caractérisé en ce qu'il comprend
    50 à 80 % en poids de Cu,
    0 à 5 % en poids de Pb,
    0,01 à 0,10 % en poids d'As,
    0,03 à moins de 0,3 % en poids de Si,
    0 à 0,3 % en poids de Fe,
    0 à 0,04 % en poids de Mn,
    et éventuellement 0,15 à 0,3 % en poids d'A1,
    le reste étant Zn et des impuretés inévitables, et en ce que l'équivalent de Cu effectif est de 60 à 70 % en poids.
  2. Alliage cuivre-zinc selon la revendication 1, caractérisé en ce que 0 à 0,02 % en poids de Mn sont contenus.
  3. Alliage cuivre-zinc selon l'une quelconque des revendications précédentes, caractérisé en ce que 0,02 à 0,08 % en poids d'As sont contenus.
  4. Alliage cuivre-zinc selon l'une quelconque des revendications précédentes, caractérisé en ce que jusqu'à 0,2 % en poids de Fe et 0,15 à 0,25 % en poids de Si sont contenus.
  5. Procédé de fabrication d'un alliage cuivre-zinc selon l'une quelconque des revendications précédentes, selon lequel les matériaux de départ sont mélangés en le rapport en poids donné, fondus et coulés en un alliage métallique, et selon lequel l'alliage métallique est recuit pour la formation de la phase α à une température de 500 à 650 °C, caractérisé en ce que l'alliage métallique recuit est refroidi activement par des agents de refroidissement.
  6. Procédé selon la revendication 5, caractérisé en ce que l'alliage métallique est soumis à un recuit avec détente à une température de 250 à 600 °C pendant entre 10 min et 2 h après un traitement supplémentaire par formage à froid.
EP20020015027 2001-07-05 2002-07-05 Alliage cuivre-zinc résistant à la dezincification et son procédé de fabrication Expired - Lifetime EP1273671B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001132055 DE10132055C2 (de) 2001-07-05 2001-07-05 Entzinkungsbeständige Kupfer-Zink-Legierung sowie Verfahren zu ihrer Herstellung
DE10132055 2001-07-05

Publications (2)

Publication Number Publication Date
EP1273671A1 EP1273671A1 (fr) 2003-01-08
EP1273671B1 true EP1273671B1 (fr) 2012-11-28

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EP20020015027 Expired - Lifetime EP1273671B1 (fr) 2001-07-05 2002-07-05 Alliage cuivre-zinc résistant à la dezincification et son procédé de fabrication

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EP (1) EP1273671B1 (fr)
DE (1) DE10132055C2 (fr)
ES (1) ES2399234T3 (fr)
PT (1) PT1273671E (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3665312B1 (fr) * 2017-08-11 2024-03-06 LIXIL Corporation Alliage de cuivre, utilisation d'un alliage de cuivre, armature sanitaire et procédé de fabrication d'une robinetterie sanitaire

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10301552B3 (de) * 2003-01-16 2004-06-24 Rehau Ag + Co. Korrosionsbeständige Messinglegierung für Trinkwasserformteile
DE102007055446A1 (de) * 2007-11-12 2009-05-14 Hansgrohe Ag Bereitstellung von wasserführenden Bauteilen aus Messinglegierungen mit verringerter Metallionenfreisetzung
CN101451204B (zh) * 2008-12-15 2010-10-13 无锡吉泉五金机械有限公司 汽车空调用导向球及其制备方法
CN101440445B (zh) 2008-12-23 2010-07-07 路达(厦门)工业有限公司 无铅易切削铝黄铜合金及其制造方法
CL2010000655A1 (es) * 2010-06-18 2010-10-22 Com Kraviva Spa Herraduras de aleacion de cobre con propiedades bactericidas y fungicidas que comprenden cobre, zinc, aluminio, hierro y opcionalmente manganeso.
DE102013003817A1 (de) * 2013-03-07 2014-09-11 Grohe Ag Kupfer-Zink-Legierung für eine Sanitärarmatur sowie Verfahren zu deren Herstellung
DE102013004081B4 (de) * 2013-03-11 2023-06-07 Hansa Metallwerke Ag Sanitärer Armaturenkörper
DE102013004383B4 (de) * 2013-03-12 2015-06-03 Diehl Metall Stiftung & Co. Kg Verwendung einer Kupfer-Zink-Legierung
CN104087782A (zh) * 2013-04-01 2014-10-08 浙江艾迪西流体控制股份有限公司 一种低铅黄铜合金及其制备方法
SE1450094A1 (sv) * 2014-01-30 2015-07-31 Arsenikfri mässing med förbättrad avzinkningshärdighet och skärbarhet

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
BE757349A (fr) * 1969-10-10 1971-03-16 A H Andersson & Co A B Alliage de cuve et de zinc convenant specialement pour le formage a chaud par pression
US3963526A (en) * 1972-08-22 1976-06-15 Aktieselskabet Nordiske Kabel-Og Traadfabriker Method of imparting increased dezincification resistance to brass
FR2356733A1 (fr) * 1976-06-30 1978-01-27 Toyo Valve Co Ltd Alliages de cuivre
FR2506334B1 (fr) * 1981-05-21 1986-01-10 Champagne Ardennes Affinage Alliage de laiton biphase pour fonderie, contenant de l'arsenic, et presentant des proprietes ameliorees de mise en oeuvre et une tres bonne resistance des pieces coulees, a la dezincification
SE8800931D0 (sv) * 1988-03-16 1988-03-16 Tour & Andersson Ab Messingslegering och sett att framstella densamma
DE19722827A1 (de) * 1997-05-30 1998-12-03 Diehl Stiftung & Co Verwendung einer Messinglegierung für Sanitärrohre
SE511680C2 (sv) * 1998-03-06 1999-11-08 Tour & Andersson Hydronics Ab Avzinkningsbeständig mässingslegering
JP3917304B2 (ja) * 1998-10-09 2007-05-23 三宝伸銅工業株式会社 快削性銅合金
SE514752C2 (sv) * 1999-08-26 2001-04-09 Tour & Andersson Hydronics Ab Avzinkningsbeständig mässingslegering för pressgjutning

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3665312B1 (fr) * 2017-08-11 2024-03-06 LIXIL Corporation Alliage de cuivre, utilisation d'un alliage de cuivre, armature sanitaire et procédé de fabrication d'une robinetterie sanitaire

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Publication number Publication date
PT1273671E (pt) 2013-02-27
DE10132055C2 (de) 2003-12-11
ES2399234T3 (es) 2013-03-26
EP1273671A1 (fr) 2003-01-08
DE10132055A1 (de) 2003-01-23

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