EP1439238B1 - Corrosion resistant brass alloy for parts suitable for use in drinking water service - Google Patents

Corrosion resistant brass alloy for parts suitable for use in drinking water service Download PDF

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EP1439238B1
EP1439238B1 EP04000423A EP04000423A EP1439238B1 EP 1439238 B1 EP1439238 B1 EP 1439238B1 EP 04000423 A EP04000423 A EP 04000423A EP 04000423 A EP04000423 A EP 04000423A EP 1439238 B1 EP1439238 B1 EP 1439238B1
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Prior art keywords
drinking water
brass alloy
corrosion
brass
moldings
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German (de)
French (fr)
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EP1439238A1 (en
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Claus Büttner
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Rehau Automotive SE and Co KG
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Rehau AG and Co
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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

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  • the invention relates to a corrosion-resistant brass alloy for drinking water moldings for use in drinking water and / or sanitary installations.
  • brass alloys with different copper contents of between 57 and 63% and zinc contents between 36 and 40% are used, which are used in domestic connection systems for drinking water or sanitary installations.
  • the addition of certain alloying constituents gives brass alloys whose properties are adjusted in different ways by these alloying constituents.
  • DIN 50930-6 determines the limits of brass alloys used today for drinking water or sanitary installations and currently defines the maximum values of the alloying components in question and their accompanying elements. It is known that alloying the element lead in weight percentages from 3 to a maximum of 4% improves the machinability.
  • Corrosion-resistant brass alloys with an alloy composition according to DIN EN 12163 to 12168, group D for drinking-water molded parts are known from the prior art, which in addition to the dezincification resistance, have good cutting and cold forming properties. These are brass alloys with 61 to 63% copper, 32.9 to 37% zinc, 1.7 to 2.8% lead, and 0.02 to 0.15% arsenic and residual alloying shares such as aluminum, Manganese and tin, each accounting for up to 0.1% by weight.
  • alloying ingredients such as those in DE 44 38 485 C2 and EP 0 506 995 A1 consist of thermally stable dispersoids such as Cr 2 Ta, Dy 2 O 3 , Er 2 O 3 , ZrC, WSi 2 , Yb 2 O 3 , Sm 2 O 3 in the total content of 0.1 to 5%, which is a chipbreaking
  • dispersoids such as Cr 2 Ta, Dy 2 O 3 , Er 2 O 3 , ZrC, WSi 2 , Yb 2 O 3 , Sm 2 O 3 in the total content of 0.1 to 5%
  • the invention is based, starting from the prior art, the object to provide an improved corrosion-resistant brass alloy for drinking water moldings available that has corrosion resistance to corrosion processes on the water-bearing surfaces of the drinking water moldings and future quality requirements for drinking water with respect to the limits of entry of corrosion products Fulfills.
  • This object is achieved by the use of a brass alloy with the composition mentioned in claim 1.
  • advantageous embodiments of the brass alloy used in the invention are given.
  • the brass alloy used according to the invention according to claim 1 is resistant to corrosion and has with respect to the crystalline and intergranular stress corrosion cracking and - even planar - Entzinkungsbe pretechnik no and with regard to Loch- / Muldenfrives on the water-bearing inner surfaces of drinking water moldings only smallest / isolated corrosion attack.
  • the copper content was varied within a range of 60 to 69%.
  • arsenic and simultaneous reduction of the iron content / content the corrosion resistance under the condition that the ratio of iron and arsenic within the limits specified in claim 1 according to the invention has been improved.
  • Another advantage of the invention is that under practical test conditions, compared to the known brass alloys, no selective corrosion could be determined experimentally in drinking water moldings consisting of the brass alloy according to the invention.
  • the corrosion characteristics of the brass alloy according to the invention are thus consistently more advantageous than previously known from the prior art and used brass alloys for use in drinking water or sanitary installations.
  • brass rods are made of brass alloy and drinking water moldings, such as coupling, angle, elbow, T-piece, distributor parts and fittings, manufactured with known and customary manufacturing and processing methods.
  • dezincification depth Hole / trough depth of cut Intercrystalline or crystalline corrosion or stress corrosion cracking depth 1 10-263 16-40 6-34, in places to 53 2 8-22 15-53 none 3 none isolated ⁇ 9 none 4 none isolated ⁇ 6 none 5 8-12 up to 32 9-31
  • Fig. 1 shows by way of example the drinking water moldings used in the test series, referred to below as fittings, consisting of the brass alloy used in accordance with the invention.
  • Fig. 2 shows in 200x magnification a microscope image of a fitting, consisting of a known brass alloy (CW602N), on the water-bearing inner surface, after 3 months of testing in different waters / drinking waters with different pH values and temperature load in the range of 5 to 20 ° C. ,
  • CW602N known brass alloy
  • Fig. 3 shows in 400-fold magnification a micrograph of a fitting made from the brass alloy used according to the invention fitting on a water-bearing inner surface after 3 months of testing in different waters / drinking waters with different pH values and temperature in the range of 5 to 20 ° C. It can be seen that only occasional hole / trough (marked A) occurs, which is significantly lower than in comparison to known brass alloys tested (see Fig. 2 ) and not spatially distributed.
  • Fig. 4 shows a microscope photograph of the inside surface of a fitting, prepared by a known dezincification resistant brass alloy (CW 602N) and after the ammonia test (DIN 50916). Significantly, this indicates progressive grain breakup (marked C) along the surface at a depth of up to 65 ⁇ m.
  • Fig. 5a, b show microscope images on the inside surface of a fitting, prepared according to the brass alloy used in the invention and after the ammonia test (DIN 50916).
  • Fig. 4 shows the use of the brass alloy according to claim 1 only minor corrosion attack and the first grain layer is still obtained as a whole, ie an intercrystalline and / or crystalline corrosion, especially stress corrosion cracking does not occur and a grain disintegration, as in Fig. 4 (C marked) is not recognizable.
  • Fig. 6 shows a 600-fold magnified microscope image of a known brass alloy after testing for Entzinkungsbe pretechnik according to ISO 6509. A corrosive attack of 3 grain layers and more is clearly recognizable, corresponding to a Entzinkungstiefe of up to 93 microns.
  • Fig. 7 shows a 600-fold magnified microscope image of the brass alloy used in the invention and tested for Entzinkungsbe pretechnik according to ISO 6509. Compared to Fig. 6 no dezincification was detected / observed along the inner surface.
  • the brass alloy used in the invention shows overall, compared to known brass alloys (s. Fig. 2 . 4 and 6 ), a significantly reduced corrosion attack, in particular no crystalline and / or intergranular corrosion / stress corrosion cracking and only partially occurring hole / Muldenfrrust on the water-bearing inside of drinking water moldings produced therefrom.

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Abstract

Use of a brass alloy for corrosion resistant drinking water molded parts is new. The alloy contains (in wt.%) 63.1-63.9 Cu, 0.5-1.1 Pb, 0.01-0.06 Fe, 0.01-0.1 Mn, 0.01-0.1 Ni, 0.001-0.02 Si, 0.001-0.005 Cr, 0.001-0.05 Al, 0.006-0.08 As, 0.005-0.08 Bi, 0.001-0.005 P, 0.001-0.05 Sb, 0.001-0.005 S, 0.001-0.01 Te, 0.001-0.02 Cd, 0.001-0.02 Se, 0.001-0.02 Ag, 0.05-0.3 Sn, 0-0.1 Be, B, Co, Mg, Ti and Zr, and a balance of Zn.

Description

Die Erfindung betrifft eine korrosionsbeständige Messinglegierung für Trinkwasserformteile für den Einsatz in Trinkwasser- und/oder Sanitärinstallationen.The invention relates to a corrosion-resistant brass alloy for drinking water moldings for use in drinking water and / or sanitary installations.

Zur Herstellung der Trinkwasserformteile werden bevorzugt Messinglegierungen mit unterschiedlichen Kupfergehalten zwischen 57 und 63% und Zinkgehalten zwischen 36 und 40% eingesetzt, die in Hausanschlusssystemen für Trinkwasser- oder Sanitärinstallationen zur Anwendung kommen. Durch den Zusatz bestimmter Legierungsbestandteile werden Messinglegierungen erhalten, deren Eigenschaften in unterschiedlicher Weise durch diese Legierungsbestandteile eingestellt werden. Die DIN 50930-6 bestimmt hierzu die Grenzwerte heute angewendeter Messinglegierungen für Trinkwasser- oder Sanitärinstallationen und legt zurzeit die Maximalwerte der in Frage kommenden Legierungsbestandteile und deren Begleitelemente fest. Es ist bekannt, dass das Zulegieren des Elements Blei in Gewichtsprozenten von 3 bis maximal 4% die spangebende Bearbeitbarkeit verbessert. Zur Herstellung von Trinkwasserformteilen für Trinkwasser- oder Sanitärinstallation werden bleihaltige Messingsorten mit 57 bis 63 % Kupfer, 1,6 bis 3,5% Blei, Legierungselemente wie Zinn, Eisen und Nickel im Bereich von 0,9 % unter Zugabe von Restgewichtsanteilen Zink verwendet. Diese Messinglegierungen besitzen den Nachteil, dass sie nicht entzinkungsbeständig sind, d.h. bei bestimmten pH-Werten von Trinkwässern löst sich Zink aus der Oberflächenmatrix an der Grenzfläche Trinkwasserformteilinnenseite einer Trinkwasser- oder Sanitärinstallation in das durchfließende oder stehende Wasser heraus; dies gilt insbesondere an den oberflächennahen Korngrenzbereichen und -schichten, die im ständigen Kontakt mit dem Wasser/Trinkwasser stehen.To produce the drinking water moldings preferably brass alloys with different copper contents of between 57 and 63% and zinc contents between 36 and 40% are used, which are used in domestic connection systems for drinking water or sanitary installations. The addition of certain alloying constituents gives brass alloys whose properties are adjusted in different ways by these alloying constituents. For this purpose, DIN 50930-6 determines the limits of brass alloys used today for drinking water or sanitary installations and currently defines the maximum values of the alloying components in question and their accompanying elements. It is known that alloying the element lead in weight percentages from 3 to a maximum of 4% improves the machinability. For the production of drinking water fittings for drinking water or sanitary installation leaded brass types with 57 to 63% copper, 1.6 to 3.5% lead, alloying elements such as tin, iron and nickel in the range of 0.9% with the addition of residual weight fractions of zinc are used. These brass alloys have the disadvantage that they are not resistant to dezincification, ie at certain pH values of drinking water, zinc dissolves out of the surface matrix at the interface of drinking water inside a drinking water or sanitary installation into the water flowing or standing; This applies in particular to the near-surface grain boundary areas and layers, which are in constant contact with the water / drinking water.

Weiterhin ist bekannt, dass mit zunehmender Standzeit eingebaute Trinkwasserformteile, bestehend aus bekannten Messinglegierungen, Materialveränderungen aufweisen, die Gefügestrukturen des Trinkwasserformteils verändern, so dass Undichtigkeiten, insbesondere an den Verbindungen der Trinkwasserformteile, entstehen können und somit deren Austausch erforderlich machen.Furthermore, it is known that built with increasing service life drinking water moldings consisting of known brass alloys, material changes, change the microstructures of the drinking water molding so that leaks, especially on the compounds of drinking water moldings, can arise and thus make their replacement required.

Zum Schutz des Trinkwassers sind die Werkstoffe der Trinkwasserformteile für Trinkwasseranwendungen in den Normen und Regelwerken der DIN 50930-1 bis 50930-6 und in DIN EN 806-2 ausführlich beschrieben und ergänzend in der Trinkwasserverordnung (TrinkwV) in der Fassung der Bekanntmachung vom November 2000 benannt. Für die Einhaltung und Unterschreitung der Grenzwerte der Werkstoffbestandteile für Trinkwasserformteile gelten die in der Trinkwasserverordnung festgelegten Parameterwerte und hinsichtlich der Werkstoffauswahl, die DIN 50930-6, Seite 7 und 8.For the protection of drinking water, the materials of drinking water fittings for drinking water applications in the standards and regulations of DIN 50930-1 to 50930-6 and DIN EN 806-2 are described in detail and in addition in the Drinking Water Ordinance (TrinkwV) as amended in November 2000 named. For adhering to and undercutting the limit values of the material components for drinking water fittings, the parameter values specified in the Drinking Water Ordinance and with regard to the selection of materials, the DIN 50930-6, page 7 and 8 apply.

Weiterhin ist bekannt, dass Trinkwasserformteile aus derzeit verwendeten Messinglegierungen bei bestimmten Wasserqualitäten und langen Wasserstandzeiten den Nachteil aufweisen, dass Kupferionen und/oder Zinkionen aus Trinkwasserformteilinnenoberflächen in fließendes oder stehendes Trinkwasser abgegeben werden. Nach der novellierten Trinkwasserverordnung auf Basis der EU-Richtlinie: 98/83/EG des Rates vom 3.11.1998 mit dem Titel "Über die Qualität von Wasser für den menschlichen Gebrauch" (Amtsblatt der Europäischen Gemeinschaft, L 330/32 DE vom 5.12.1998, Anhang I, Teil B) ist der Kupfereintrag von derzeitig 3 mg Cu/l auf 2 mg Cu/l abzusenken. In diesem Zusammenhang wird auch der Zinkeintrag zurzeit von der Europäischen Union behandelt.Furthermore, it is known that drinking water moldings made of currently used brass alloys have the disadvantage, with certain water qualities and long water lives, that copper ions and / or zinc ions are released from drinking-water molded part inner surfaces into flowing or standing drinking water. According to the amended Drinking Water Ordinance on the basis of EU Directive: Council Directive 98/83 / EC of 3.11.1998 entitled "On the quality of water intended for human consumption" (Official Journal of the European Union, L 330/32 DE of 5.12. 1998, Appendix I, Part B) is the copper input from currently 3 mg Cu / l to 2 mg Cu / l lower. In this context, the zinc entry is currently being handled by the European Union.

Aus dem Stand der Technik sind korrosionsfeste Messinglegierungen mit einer Legierungszusammensetzung nach DIN EN 12163 bis 12168, Gruppe D für Trinkwasserformteile bekannt, die neben der Entzinkungsbeständigkeit, gute Zerspanungs- und Kaltumformeigenschaften aufweisen. Es handelt sich hierbei um Messinglegierungen mit 61 bis 63% Kupfer-, 32,9 bis 37 % Zink-, 1,7 bis 2,8% Blei-, und 0,02 bis 0,15 % Arsenanteil und restlichen Legierungsanteilen wie Aluminium, Mangan und Zinn, die jeweils einen Gewichtsanteil bis zu maximal 0, 1 % ausmachen.Corrosion-resistant brass alloys with an alloy composition according to DIN EN 12163 to 12168, group D for drinking-water molded parts are known from the prior art, which in addition to the dezincification resistance, have good cutting and cold forming properties. These are brass alloys with 61 to 63% copper, 32.9 to 37% zinc, 1.7 to 2.8% lead, and 0.02 to 0.15% arsenic and residual alloying shares such as aluminum, Manganese and tin, each accounting for up to 0.1% by weight.

Durch das Zulegieren von Arsen wird eine Inhibierung der α-Phase des Messinggefüges erreicht. Bei diesen Messinglegierungen sind Entzinkungstiefen, die nach Prüfvorschrift ISO 6509 ermittelt werden, von 200 bis 400 µm in der Praxis bekannt und führen somit zu korrosionsbedingten Ausfällen von Trinkwasserformteilen.By alloying arsenic, an inhibition of the α-phase of the brass structure is achieved. With these brass alloys, dezincification depths, which are determined according to test specification ISO 6509, of 200 to 400 μm are known in practice and thus lead to corrosion-related failures of drinking water moldings.

Andere Legierungsbestandteile, wie sie in DE 44 38 485 C2 und EP 0 506 995 A1 beschrieben sind, bestehen aus thermisch stabilen Dispersoiden wie Cr2Ta, Dy2O3, Er2O3, ZrC, WSi2, Yb2O3, Sm2O3 im Gesamtgehalt von 0,1 bis 5%, die eine spanbrechende Wirkung und Verarbeitungsvorteile aufweisen. Der Eintrag von Dispersoiden als Ersatz von Blei erfolgt herstellungsbedingt in Form von Pulvern während des Gießprozesses. Hinsichtlich der physiologischen Wirkung dieser Zusätze von Seltenen Erden auf das Trinkwasser und die einhergehende Belastung für den Menschen, existieren bisher keine wissenschaftlich fundierten Ergebnisse.Other alloying ingredients, such as those in DE 44 38 485 C2 and EP 0 506 995 A1 consist of thermally stable dispersoids such as Cr 2 Ta, Dy 2 O 3 , Er 2 O 3 , ZrC, WSi 2 , Yb 2 O 3 , Sm 2 O 3 in the total content of 0.1 to 5%, which is a chipbreaking Have effect and processing advantages. The introduction of dispersoids as a replacement of lead takes place due to production in the form of powders during the casting process. With regard to the physiological effect of these rare earths additives on drinking water and the associated burden on humans, no scientifically sound results exist so far.

Neben diesen neuen Anforderungen an die Qualität von Trinkwassern, besteht auf Seiten der Hersteller von Messinglegierungen und bzgl. der zum Einsatz kommenden Trinkwasserformteile die Anforderung, dass das Korrosionsverhalten zu verbessern ist.In addition to these new requirements for the quality of drinking water, there is a requirement on the part of the manufacturers of brass alloys and with regard to the drinking water moldings used that the corrosion behavior is to be improved.

Der Erfindung liegt, ausgehend vom Stand der Technik, die Aufgabe zu Grunde, eine verbesserte korrosionsbeständige Messinglegierung für Trinkwasserformteile zur Verfügung zu stellen, die Korrosionsbeständigkeit gegen Korrosionsvorgänge an den wasserführenden Oberflächen der Trinkwasserformteile aufweist und zukünftigen Qualitätsanforderungen an das Trinkwasser hinsichtlich der Grenzwerte des Eintrages von Korrosionsprodukten erfüllt. Diese Aufgabe wird durch die Verwendung einer Messinglegierung mit der in Anspruch 1 genannten Zusammensetzung gelöst.
In Unteranspuch 2 sind vorteilhafte Ausführungsbeispiele der erfindungsgemäß verwendeten Messinglegierung angegeben.The invention is based, starting from the prior art, the object to provide an improved corrosion-resistant brass alloy for drinking water moldings available that has corrosion resistance to corrosion processes on the water-bearing surfaces of the drinking water moldings and future quality requirements for drinking water with respect to the limits of entry of corrosion products Fulfills. This object is achieved by the use of a brass alloy with the composition mentioned in claim 1.
In Subanspuch 2 advantageous embodiments of the brass alloy used in the invention are given.

Die erfindungsgemäß verwendete Messinglegierung nach Anspruch 1 ist korrosionsbeständig und weist hinsichtlich der kristallinen und interkristallinen Spannungsrisskorrosion und der - auch flächenhaften - Entzinkungsbeständigkeit keinen und hinsichtlich Loch-/Muldenfraß an den wasserführenden Innenoberflächen der Trinkwasserformteile nur geringsten/vereinzelten Korrosionsangriff auf.The brass alloy used according to the invention according to claim 1 is resistant to corrosion and has with respect to the crystalline and intergranular stress corrosion cracking and - even planar - Entzinkungsbeständigkeit no and with regard to Loch- / Muldenfraß on the water-bearing inner surfaces of drinking water moldings only smallest / isolated corrosion attack.

Ausgehend von den bekannten herkömmlichen Messinglegierungen wurde der Kupfergehalt in einem Bereich von 60 bis 69 % variiert. Dies erforderte eine Zudotierung von erfindungsgemäßen Messinglegierungsbestandteilen wie Blei, Eisen, Mangan, Nickel, Silizium, Chrom, Aluminium, Arsen, Bismut, Phosphor, Antimon, Schwefel, Tellur, Cadmium, Selen, Silber, Zinn sowie Beryllium, Bor, Kobalt, Magnesium, Titan und Zirkon und Zink als Rest in den angegeben Gewichtsprozenten (Gew%) gemäß Anspruch 1, so dass die Gefügestruktur der Legierung und das damit verbundene gesamthafte Korrosionsverhalten vorteilhaft beeinflusst wird. Weiterhin zeigte sich überraschenderweise, dass durch die Zugabe von Arsen und gleichzeitige Reduktion des Eisengehaltes/-anteils, die Korrosionsbeständigkeit unter der Bedingung, dass das Verhältnis von Eisen und Arsen in den erfindungsgemäß angegebenen Grenzen nach Anspruch 1 liegt , verbessert wurde.Starting from the known conventional brass alloys, the copper content was varied within a range of 60 to 69%. This required the addition of brass alloy constituents of the invention such as lead, iron, manganese, nickel, silicon, chromium, aluminum, arsenic, bismuth, phosphorus, antimony, sulfur, tellurium, cadmium, selenium, silver, tin and beryllium, boron, cobalt, magnesium, Titanium and zirconium and zinc as balance in the indicated weight percentages (wt%) according to claim 1, so that the microstructure of the alloy and the associated overall corrosion behavior are advantageously influenced. Furthermore, it was surprisingly found that by the addition of arsenic and simultaneous reduction of the iron content / content, the corrosion resistance under the condition that the ratio of iron and arsenic within the limits specified in claim 1 according to the invention has been improved.

Ein weiterer Vorteil der Erfindung besteht darin, dass unter praxisnahen Testbedingungen, im Vergleich zu den bekannten Messinglegierungen, keine selektive Korrosion experimentell bei Trinkwasserformteilen, bestehend aus der erfindungsgemäßen Messinglegierung, bestimmt werden konnte.Another advantage of the invention is that under practical test conditions, compared to the known brass alloys, no selective corrosion could be determined experimentally in drinking water moldings consisting of the brass alloy according to the invention.

Die Korrosionskenndaten der erfindungsgemäßen Messinglegierung sind somit durchweg vorteilhafter gegenüber bisher aus dem Stand der Technik bekannten und verwendeten Messinglegierungen für den Einsatz in Trinkwasser- oder Sanitärinstallationen.
Insbesondere zeigte sich keine Spannungsrisskorrosion der erfindungsgemäßen Messinglegierung; dies auch nicht während oder nach Langzeituntersuchungen.The corrosion characteristics of the brass alloy according to the invention are thus consistently more advantageous than previously known from the prior art and used brass alloys for use in drinking water or sanitary installations.
In particular, there was no stress corrosion cracking of the brass alloy according to the invention; This also not during or after long-term investigations.

Metallografisch durchgeführte Schliffuntersuchungen an Trinkwasserformteilen, bestehend aus der erfindungsgemäßen Messinglegierung, zeigten überraschenderweise auf der wasserführenden Innenseite nur vergleichsweise geringen Korrosionsangriff, jedoch keine flächenhaft ausgeprägte Entzinkungskorrosion, wie dies bei bekannten Messinglegierungen nach Experimenten mit unterschiedlichen Trinkwässern, verschiedener pH-Werte und unterschiedlichen Wassertemperaturen der Fall ist.Surprisingly, metallographically conducted ground investigations on drinking-water moldings consisting of the brass alloy according to the invention showed only comparatively little corrosive attack on the water-bearing inside, but no extensive decalcification corrosion, as is the case with known brass alloys after experiments with different drinking waters, different pH values and different water temperatures ,

Die Erfindung wird im Folgenden näher beschrieben.The invention will be described in more detail below.

Es wurden Versuche mit einer erfindungsgemäß verwendeten Messinglegierung durchgeführt, die 63,1 % Kupfer, 1,1 % Blei, 0,01 % Eisen, 0,1 % Mangan, 0,1 % Nickel, 0,001 % Silizium, 0,001 % Chrom, 0,001 % Aluminium, 0,06 % Arsen, 0,04 % Bismut, 0,001 % Phosphor, 0,05 % Antimon, 0,001 % Schwefel, 0,001 % Tellur, 0,001 % Cadmium, 0,001 % Selen, 0,001 % Silber, 0,05 % Zinn, gesamthaft 0,01 % Beryllium, Bor, Kobalt, Magnesium, Titan, Zirkon und Zink als Rest enthalten. Hierzu sind Messingstangen aus der Messinglegierung hergestellt und Trinkwasserformteile, wie Kupplungs-, Winkel-, Winkelbogen-, T-Stück-, Verteilerteile und Fittinge, mit bekannten und üblichen Herstellungs- und Bearbeitungsverfahren gefertigt worden.Tests were carried out on a brass alloy used in accordance with the invention containing 63.1% copper, 1.1% lead, 0.01% iron, 0.1% manganese, 0.1% nickel, 0.001% silicon, 0.001% chromium, 0.001% % Aluminum, 0.06% arsenic, 0.04% bismuth, 0.001% phosphorus, 0.05% antimony, 0.001% sulfur, 0.001% tellurium, 0.001% cadmium, 0.001% selenium, 0.001% silver, 0.05% tin containing a total of 0.01% beryllium, boron, cobalt, magnesium, titanium, zirconium and zinc. For this purpose, brass rods are made of brass alloy and drinking water moldings, such as coupling, angle, elbow, T-piece, distributor parts and fittings, manufactured with known and customary manufacturing and processing methods.

Dabei zeigten sich im gesamten Fertigungsprozess keinerlei Bearbeitungsschwierigkeiten, so dass für die Oberflächenbearbeitung bei der erfindungsgemäßen Messinglegierung herkömmliche Fertigungsverfahrensparameter vorteilhafterweise beibehalten werden konnten.There were no machining difficulties during the entire production process, so that conventional production process parameters could advantageously be retained for the surface treatment in the brass alloy according to the invention.

An zahlreichen, aus einer Messinglegierung gemäß Anspruch 1 hergestellten Trinkwasserformteilen wurde festgestellt, dass der Korrosionsangriff, insbesondere die Spannungsrisskorrosion (kristalline und/oder interkristalline) und die selektive Korrosion entlang der wasserführenden Oberfläche der Trinkwasserformteile nicht auftritt.In numerous, made of a brass alloy according to claim 1 drinking water moldings was found that the corrosion attack, especially the stress corrosion cracking (crystalline and / or intergranular) and the selective corrosion along the water-bearing surface of drinking water moldings does not occur.

Weiterhin wurden standardisierte Entzinkungsbeständigkeitsuntersuchungen nach ISO 6509 durchgeführt und die Trinkwasserformteile anschließend mittels metallografischen Untersuchungsmethoden auf der wasserführenden Innenseite analysiert.
Für die Mikroskopaufnahmen wurden polierte Schliffe nach dem Aufschneiden der Trinkwasserformteile angefertigt. Die nach Anspruch 1 und 2 gefertigten Trinkwasserformteile zeigten keine Entzinkungstiefen und die erfindungsgemäße Legierung ist daher als entzinkungsbeständig einzustufen.Furthermore, standardized dezincification resistance tests according to ISO 6509 were carried out and the drinking water moldings were subsequently analyzed by metallographic examination methods on the water-bearing inside.
For the micrographs, polished sections were made after cutting the drinking water moldings. The manufactured according to claim 1 and 2 drinking water moldings showed no Entzinkungstiefen and the alloy of the invention is therefore classified as dezincification resistant.

Aus der Tabelle 1 geht hervor, dass die aus der erfindungsgemäß verwendeten Messinglegierung bestehenden Trinkwasserformteile (Probe-Nr. 3 und 4) keine interkristalline oder kristalline Korrosion/Spannungsrisskorrosion aufweisen, wie die Vergleichsproben (Probe-Nr. 1, 2 und 5), bestehend aus bekannten Messinglegierungen.It is apparent from Table 1 that the drinking water moldings (Sample Nos. 3 and 4) consisting of the brass alloy used in the present invention have no intergranular or crystalline corrosion / stress corrosion cracking as the comparative samples (Sample Nos. 1, 2 and 5) from known brass alloys.

Durchgeführte polarisationsmikroskopische Untersuchungen an den Innenoberflächen von Trinkwasserformteilen, hergestellt nach Anspruch 1, die 3 Monate zu Testzwecken in unterschiedlichen Trinkwässern mit verschiedenen pH-Werten von 6,5 bis 8 und/oder bei Temperaturen im Bereich von 5 bis 20 °C behandelt wurden, belegen, dass die flächenhafte Korrosion sich nur in einer Tiefe von kleiner 12 µm entlang der untersuchten Innenflächen der getesteten Trinkwasserformteile vereinzelt ausbreitet und damit gegenüber dem Stand der Technik ein besseres Flächenkorrosionsverhalten gesamthaft aufweist. Tabelle 1: Ergebnisse der metallografischen Untersuchung nach 3-monatigem Einsatz; alle Messwerte in µm Proben-Nr. Entzinkungstiefe Loch-/ Muldenfraßtiefe Interkristalline oder kristalline Korrosion bzw. Spannungsrisskorrosionstiefe 1 10-263 16-40 6-34, stellenweise bis 53 2 8-22 15-53 keine 3 keine vereinzelt <9 keine 4 keine vereinzelt <6 keine 5 8-12 bis zu 32 9-31 Polarized microscopic investigations on the inner surfaces of drinking water moldings, produced according to claim 1, which were treated for 3 months for test purposes in different drinking waters with different pH values of 6.5 to 8 and / or at temperatures in the range of 5 to 20 ° C, prove in that the areal corrosion spreads only occasionally at a depth of less than 12 μm along the examined inner surfaces of the tested drinking-water moldings and thus has a better overall surface corrosion behavior compared with the prior art. Table 1: Results of metallographic examination after 3 months of use; all measured values in μm Sample no. dezincification depth Hole / trough depth of cut Intercrystalline or crystalline corrosion or stress corrosion cracking depth 1 10-263 16-40 6-34, in places to 53 2 8-22 15-53 none 3 none isolated <9 none 4 none isolated <6 none 5 8-12 up to 32 9-31

Wie aus der Tabelle 1 weiterhin zu entnehmen ist, sind die Loch-/Muldenfraßtiefen der erfindungsgemäßen Messinglegierung mit der Proben-Nr. 3 und 4 deutlich kleiner gegenüber den Vergleichsproben 1, 2 und 5, die Ergebnisse für Trinkwasserformteile, bestehend aus bekannten Messinglegierungen (bspw. CW602N), zeigen. Insbesondere trat Loch-/Muldenfraß nur vereinzelt und mit maximalen Tiefen von 6 bis 9 µm entlang der untersuchten Trinkwasserformteilinnenoberfläche der Proben 3 und 4 auf.As can also be seen from Table 1, the hole / Muldenfraßtiefen the brass alloy according to the invention with the sample no. 3 and 4 significantly smaller compared to the comparative samples 1, 2 and 5, the results for drinking water moldings, consisting of known brass alloys (eg. CW602N) show. In particular, pit / trough feces occurred only sporadically and with maximum depths of 6 to 9 μm along the examined drinking water mold cavity inner surfaces of Samples 3 and 4.

Fig. 1 zeigt beispielhaft die bei den Versuchsreihen verwendeten Trinkwasserformteile, nachfolgend Fittinge genannt, bestehend aus der erfindungsgemäß verwendeten Messinglegierung. Fig. 1 shows by way of example the drinking water moldings used in the test series, referred to below as fittings, consisting of the brass alloy used in accordance with the invention.

Die Untersuchungen erfolgten nach dem Aufschneiden entlang der Längsachse der Fittinge auf der wasserführenden Innenoberfläche und unter den genannten Testbedingungen.The tests were carried out after cutting along the longitudinal axis of the fittings on the water-bearing inner surface and under the test conditions mentioned.

Fig. 2 zeigt in 200-facher Vergrößerung eine Mikroskopaufnahme eines Fitting, bestehend aus einer bekannten Messinglegierung (CW602N), an der wasserführenden Innenoberfläche, nach 3-monatigem Testeinsatz in verschiedenen Wässern/Trinkwässern mit unterschiedlichen pH-Werten und Temperaturbelastung im Bereich von 5 bis 20°C. Zu erkennen sind deutliche Loch-/Muldenfraßtiefen und eine davon ausgehende - auch flächenhafte - Entzinkung, die mit A bzw. B gekennzeichnet sind. Derartige Bereiche können über die Standzeit der Trinkwasserformteile betrachtet zu Leckagen und Undichtigkeiten führen, sofern sich diese Bereiche über die Gesamtmaterialstärke des Trinkwasserformteils erstrecken oder an Verbindungsbereichen auftreten. Fig. 2 shows in 200x magnification a microscope image of a fitting, consisting of a known brass alloy (CW602N), on the water-bearing inner surface, after 3 months of testing in different waters / drinking waters with different pH values and temperature load in the range of 5 to 20 ° C. , Evident are clear hole / Muldenfraßtiefen and one outgoing - even areal - Entzinkung, which are marked with A and B respectively. Such areas can be considered over the life of the drinking water moldings lead to leaks and leaks, provided that these areas extend beyond the total material thickness of the drinking water molding or occur at connection areas.

Fig. 3 zeigt in 400-facher Vergrößerung eine Mikroskopaufnahme eines aus der erfindungsgemäß verwendeten Messinglegierung hergestellten Fitting an einer wasserführenden Innenoberfläche, nach 3-monatigem Testeinsatz in verschiedenen Wässern/Trinkwässern mit unterschiedlichen pH-Werten und Temperaturbelastung im Bereich von 5 bis 20 °C. Zu erkennen ist, dass nur vereinzelter Loch-/Muldenfraß (mit A gekennzeichnet) auftritt, der deutlich geringer ausfällt, als im Vergleich zu bekannten getesteten Messinglegierungen (siehe Fig. 2) und nicht flächenhaft verteilt ist. Fig. 3 shows in 400-fold magnification a micrograph of a fitting made from the brass alloy used according to the invention fitting on a water-bearing inner surface after 3 months of testing in different waters / drinking waters with different pH values and temperature in the range of 5 to 20 ° C. It can be seen that only occasional hole / trough (marked A) occurs, which is significantly lower than in comparison to known brass alloys tested (see Fig. 2 ) and not spatially distributed.

Fig. 4 zeigt eine Mikroskopaufnahme an der innenseitigen Oberfläche eines Fittings, hergestellt nach einer bekannten entzinkungsbeständigen Messinglegierung (CW 602N) und nach erfolgtem Ammoniaktest (DIN 50916). Deutlich ist hieraus ein fortschreitender Kornzerfall (mit C gekennzeichnet) entlang der Oberfläche in einer Tiefenlage von bis zu 65 µm zu erkennen. Fig. 4 shows a microscope photograph of the inside surface of a fitting, prepared by a known dezincification resistant brass alloy (CW 602N) and after the ammonia test (DIN 50916). Significantly, this indicates progressive grain breakup (marked C) along the surface at a depth of up to 65 μm.

Fig. 5a, b zeigen Mikroskopaufnahmen an der innenseitigen Oberfläche eines Fitting, hergestellt nach der erfindungsgemäß verwendeten Messinglegierung und nach erfolgtem Ammoniaktest (DIN 50916). Im Vergleich zur Fig. 4 zeigt die Verwendung der Messinglegierung nach Anspruch 1 nur geringfügigen Korrosionsangriff und die erste Kornlage ist noch gesamthaft erhalten, d.h. eine interkristalline und/oder kristalline Korrosion, insbesondere Spannungsrisskorrosion tritt nicht auf und ein Kornzerfall, wie in Fig. 4 (C gekennzeichnet) dargestellt, ist nicht erkennbar. Fig. 5a, b show microscope images on the inside surface of a fitting, prepared according to the brass alloy used in the invention and after the ammonia test (DIN 50916). In comparison to Fig. 4 shows the use of the brass alloy according to claim 1 only minor corrosion attack and the first grain layer is still obtained as a whole, ie an intercrystalline and / or crystalline corrosion, especially stress corrosion cracking does not occur and a grain disintegration, as in Fig. 4 (C marked) is not recognizable.

Fig. 6 zeigt eine 600-fach vergrößerte Mikroskopaufnahme einer bekannten Messinglegierung nach erfolgter Prüfung auf Entzinkungsbeständigkeit gemäß ISO 6509. Dabei ist ein Korrosionsangriff von 3 Kornlagen und mehr deutlich erkennbar, entsprechend einer Entzinkungstiefe von bis zu 93 µm. Fig. 6 shows a 600-fold magnified microscope image of a known brass alloy after testing for Entzinkungsbeständigkeit according to ISO 6509. A corrosive attack of 3 grain layers and more is clearly recognizable, corresponding to a Entzinkungstiefe of up to 93 microns.

Fig. 7 zeigt eine 600-fach vergrößerte Mikroskopaufnahme der erfindungsgemäß verwendeten Messinglegierung und erfolgter Prüfung auf Entzinkungsbeständigkeit gemäß ISO 6509. Im Vergleich zur Fig. 6 wurde keine Entzinkung entlang der Innenoberfläche ermittelt/beobachtet. Fig. 7 shows a 600-fold magnified microscope image of the brass alloy used in the invention and tested for Entzinkungsbeständigkeit according to ISO 6509. Compared to Fig. 6 no dezincification was detected / observed along the inner surface.

Bei keinem der Trinkwasserformteile, insbesondere Fittinge, die aus einer nach Anspruch 1 bis 3 verwendeten Messinglegierung bestehen, konnte eine Undichtigkeit beobachtet werden.In none of the drinking water moldings, in particular fittings, which consist of a brass alloy used according to claim 1 to 3, a leak could be observed.

Die erfindungsgemäß verwendete Messinglegierung (s. Fig. 3, 5a, b und 7) zeigt somit gesamthaft, im Vergleich zu bekannten Messinglegierungen (s. Fig. 2, 4 und 6), einen deutlich reduzierten Korrosionsangriff, insbesondere keine kristalline und/oder interkristalline Korrosion/Spannungsrisskorrosion und nur partiell auftretend Loch-/Muldenfraß an der wasserführenden Innenseite von daraus hergestellten Trinkwasserformteilen.The brass alloy used in the invention (s. Fig. 3 . 5a . b and 7 ) thus shows overall, compared to known brass alloys (s. Fig. 2 . 4 and 6 ), a significantly reduced corrosion attack, in particular no crystalline and / or intergranular corrosion / stress corrosion cracking and only partially occurring hole / Muldenfraß on the water-bearing inside of drinking water moldings produced therefrom.

Claims (2)

  1. Use of a brass alloy for production of corrosion-resistant mouldings which are in contact with drinking water, characterized by the following composition (% by weight) 63.1% copper, 1.1% lead, 0.01% iron, 0.1% manganese, 0.1% nickel, 0.001% silicon, 0.001% chromium, 0.001% aluminium, 0.06% arsenic, 0.04% bismuth, 0.001% phosphorus, 0.05% antimony, 0.001% sulphur 0.001% tellurium, 0.001% cadmium, 0.001% selenium, 0.001% silver, 0.05% tin,
    and a total of 0.01% beryllium, boron, cobalt, magnesium, titanium, zirconium, zinc as the remainder.
  2. Use of a brass alloy according to Claim 1 for production of mouldings, especially coupling parts, angle parts, curve parts, T-piece parts, distributor parts and fittings.
EP04000423A 2003-01-16 2004-01-12 Corrosion resistant brass alloy for parts suitable for use in drinking water service Expired - Lifetime EP1439238B1 (en)

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DE10301552 2003-01-16
DE10301552A DE10301552B3 (en) 2003-01-16 2003-01-16 Use of a brass alloy for corrosion resistant drinking water molded parts, especially coupling parts, angular parts, angular bent parts, T-pieces, distribution parts and fittings

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