EP0579904B1 - Corrosion resistant copper alloy - Google Patents
Corrosion resistant copper alloy Download PDFInfo
- Publication number
- EP0579904B1 EP0579904B1 EP19930106094 EP93106094A EP0579904B1 EP 0579904 B1 EP0579904 B1 EP 0579904B1 EP 19930106094 EP19930106094 EP 19930106094 EP 93106094 A EP93106094 A EP 93106094A EP 0579904 B1 EP0579904 B1 EP 0579904B1
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- European Patent Office
- Prior art keywords
- copper
- alloy
- cover layer
- corrosion
- copper alloy
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- Expired - Lifetime
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- 230000007797 corrosion Effects 0.000 title claims description 20
- 238000005260 corrosion Methods 0.000 title claims description 20
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 11
- 239000010949 copper Substances 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 20
- 239000000956 alloy Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 150000004677 hydrates Chemical class 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 3
- 239000003651 drinking water Substances 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 6
- 150000001875 compounds Chemical class 0.000 claims 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 4
- 230000001464 adherent effect Effects 0.000 claims 3
- 229910017052 cobalt Inorganic materials 0.000 claims 3
- 239000010941 cobalt Substances 0.000 claims 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 3
- 229910052742 iron Inorganic materials 0.000 claims 3
- 238000002844 melting Methods 0.000 claims 3
- 230000008018 melting Effects 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229910052788 barium Inorganic materials 0.000 claims 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 2
- 229910052790 beryllium Inorganic materials 0.000 claims 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052793 cadmium Inorganic materials 0.000 claims 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- 239000011575 calcium Substances 0.000 claims 2
- 229910052732 germanium Inorganic materials 0.000 claims 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 2
- 229910052735 hafnium Inorganic materials 0.000 claims 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 229910052712 strontium Inorganic materials 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910017777 Cu—Al—Zn Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the invention relates to a corrosion-resistant copper alloy which consists of copper and at least two alloy elements which are less noble than copper in their electrochemical voltage potential and which, together with copper, form a firmly adhering, pore-free cover layer of oxides, oxide hydrates and / or hydroxides, the amount of each Elements lies within the limits within which the alloy lies in the mixed crystal range under technical cooling conditions.
- Such an alloy is known for example from DE-OS 3,605,796.
- DE-OS 3,605,796 because of the high concentrations of the additional elements, there is a risk of excretion and thus of additional processing difficulties.
- the majority of corrosion damage in copper water pipes is caused by even surface corrosion or pitting. Improper installation can also lead to corrosion attacks in the area of solder joints and connections.
- the corrosion resistance of copper can in principle be increased by producing a firmly adhering, coherent oxide cover layer. This is applied to the inner surface of the pipe using special manufacturing processes, but this is technically complicated and labor-intensive.
- the more advanced method is to use alloy additives to form a material that, when used, automatically forms an improved oxide coating.
- the invention is based on the object of specifying a corrosion-resistant material which is characterized in particular by an improved covering layer formation compared to oxygen-free copper and by reduced copper solubility and for which there is no risk of pitting.
- the mass loss should be reduced.
- Phosphorus improves the pourability and acts as a deoxidizer.
- the elements mentioned are added in an amount of at least 0.1% by weight.
- the alloy according to the invention is preferably used as a material for pipes in installation and sanitary technology and for drinking water pipes.
- Tubes measuring 18 x 1 mm were made of oxygen-free copper and three comparative alloys of the following composition.
- the polarization resistance R p or the reciprocal, the polarization conductance R p ⁇ 1 is a measure of the rate of corrosion. The lower the polarization conductance, the greater the resistance to uniform corrosion.
- Figures 2a to g compare the polarization conductance of the materials CuMg0.7Ti0.2, CuAl0.5, Zn0.5 and CuLi0.6Si0.1 in different states (soft / hard) with that of SF-Cu. Unalloyed Cu not only exhibits poorer behavior, but also considerable scatter.
- the alloys according to the invention show significantly better behavior than SF-Cu. Not only is the quality of the covering layer improved, but also the rate of formation is influenced and, above all, the potential range of corrosion resistance is expanded. This formation of the passive layer significantly reduces the Cu solubility.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Powder Metallurgy (AREA)
- Laminated Bodies (AREA)
Description
Die Erfindung betrifft eine korrosionsbeständige Kupferlegierung, die aus Kupfer und mindestens zwei Legierungselementen besteht, die in ihrem elektrochemischen Spannungspotential unedler als Kupfer sind und die zusammen mit Kupfer eine festhaftende, porenfreie Deckschicht aus Oxiden, Oxidhydraten und/oder Hydroxiden bilden, wobei die Menge der einzelnen Elemente innerhalb derjenigen Grenzen liegt, innerhalb derer die Legierung unter technischen Abkühlbedingungen im Mischkristallbereich liegt.The invention relates to a corrosion-resistant copper alloy which consists of copper and at least two alloy elements which are less noble than copper in their electrochemical voltage potential and which, together with copper, form a firmly adhering, pore-free cover layer of oxides, oxide hydrates and / or hydroxides, the amount of each Elements lies within the limits within which the alloy lies in the mixed crystal range under technical cooling conditions.
Eine derartige Legierung ist beispielsweise bekannt durch die DE-OS 3.605.796. Wegen der hohen Konzentrationen der Zusatzelemente besteht dort jedoch die Gefahr der Ausscheidungsbildung und damit die Gefahr zusätzlicher Verarbeitungsschwierigkeiten.Such an alloy is known for example from DE-OS 3,605,796. However, because of the high concentrations of the additional elements, there is a risk of excretion and thus of additional processing difficulties.
Die Mehrzahl der Korrosionsschadensfälle in Wasserleitungsrohren aus Kupfer wird durch gleichmäßige Flächenkorrosion oder Lochfraß ausgelöst. Durch unsachgemäße Montage kann es außerdem zu Korrosionsangriffen im Bereich von Lötstellen und Verbindungen kommen. Die Korrosionsbeständigkeit von Kupfer kann zwar grundsätzlich dadurch erhöht werden, daß eine festhaftende, zusammenhängende oxidische Deckschicht erzeugt wird. Diese wird durch spezielle Herstellungsverfahren auf der Rohrinnenfläche aufgebracht, was jedoch technisch umständlich und arbeitsintensiv ist. Die fortschrittlichere Methode ist, durch Legierungszusätze einen Werkstoff zu bilden, bei dem sich im Gebrauch von selbst eine verbesserte oxidische Deckschicht bildet.The majority of corrosion damage in copper water pipes is caused by even surface corrosion or pitting. Improper installation can also lead to corrosion attacks in the area of solder joints and connections. The corrosion resistance of copper can in principle be increased by producing a firmly adhering, coherent oxide cover layer. This is applied to the inner surface of the pipe using special manufacturing processes, but this is technically complicated and labor-intensive. The more advanced method is to use alloy additives to form a material that, when used, automatically forms an improved oxide coating.
Der Erfindung liegt die Aufgabe zugrunde, einen korrosionsbeständigen Werkstoff anzugeben, der sich durch eine insbes. gegenüber sauerstofffreiem Kupfer verbesserte Deckschichtbildung und durch reduzierte Kupferlöslichkeit auszeichnet und für den keine Lochfraßgefährdung besteht. Der Massenabtrag soll dabei herabgesetzt werden.The invention is based on the object of specifying a corrosion-resistant material which is characterized in particular by an improved covering layer formation compared to oxygen-free copper and by reduced copper solubility and for which there is no risk of pitting. The mass loss should be reduced.
Die Aufgabe wird erfindungsgemäß durch die Merkmale von Ansprüche 1 bis 3 gelöst.The object is achieved by the features of
Durch die Wertigkeitspaarung von zweiwertigen zu dreiwertigen positiven Ionen, von zweiwertigen zu vierwertigen Ionen oder von einwertigen zu vierwertigen Ionen wird eine festhaftende und weitgehend porenfreie Deckschicht erzeugt. Es hat sich überraschenderweise gezeigt, daß durch die Auswahl der Wertigkeitspaarungen die Struktur der Cu₂O-Phase dahingehend beeinflußt wird, daß sich sowohl schneller eine Deckschicht bildet, als auch, daß die Schutzwirkung der entstehenden Deckschicht wirksamer ist.Through the valence pairing of divalent to trivalent positive ions, from divalent to tetravalent ions or from monovalent to tetravalent ions a firmly adhering and largely pore-free cover layer is generated. It has surprisingly been found that the structure of the Cu₂O phase is influenced by the selection of the valence pairs in such a way that a cover layer is formed more quickly, and that the protective effect of the resulting cover layer is more effective.
Es ist vorteilhaft, der Legierung bis zu 0,04 Gew.-% Phosphor zuzusetzen. Phosphor verbessert die Gießbarkeit und wirkt als Desoxidationsmittel.It is advantageous to add up to 0.04% by weight of phosphorus to the alloy. Phosphorus improves the pourability and acts as a deoxidizer.
Nach einer bevorzugten Ausführungsform der Erfindung werden die genannten Elemente in einer Menge von mindestens 0,1 Gew.-% zugesetzt.According to a preferred embodiment of the invention, the elements mentioned are added in an amount of at least 0.1% by weight.
Bevorzugt wird die erfindungsgemäße Legierung als Werkstoff für Rohre in der Installations- und Sanitärtechnik sowie für Trinkwasserleitungen verwendet.The alloy according to the invention is preferably used as a material for pipes in installation and sanitary technology and for drinking water pipes.
Die Erfindung wird anhand der folgenden Ausführungsbeispiele näher erläutert:
Es wurden Rohre der Abmessung 18 x 1 mm aus sauerstofffreiem Kupfer und aus drei Vergleichslegierungen der folgenden Zusammensetzung hergestellt.
Tubes measuring 18 x 1 mm were made of oxygen-free copper and three comparative alloys of the following composition.
Zur Beurteilung des Korrosionsverhaltens wurden an den Rohrmustern Stromdichte-Potential-Kurven (Fig.1) und der elektrochemische Polarisationswiderstand (Rp) bzw. Polarisationsleitwert (Rp⁻¹) gemäß Fig. 2a - 2g gemessen sowie der Massenabtrag (Fig.3) ermittelt.To assess the corrosion behavior, current density-potential curves (Fig. 1) and the electrochemical polarization resistance (R p ) or polarization conductance (R p ⁻¹) according to Figs. 2a - 2g were measured and the mass removal (Fig. 3) determined.
Es zeigen im einzelnen:
- Fig.1:
- die Stromdichte-Potential-Kurven der Legierungssysteme Cu-Mg-Ti, Cu-Al-Zn und Cu-Li-Si im Vergleich zu SF-Cu.
Bezugselektrode: gesättigte Kalomelektrode. - Fig.2a bis 2g:
- den Polarisationsleitwert Rp⁻¹ als Funktion der Versuchsdauer.
- (a) SF-Cu, Zustand weich, 50-70 HB bzw. hart, 100-120 HB
- (b) CuMg0,7Ti0,2, Zustand weich, 50-70 HB
- (c) CuMg0,7Ti0,2, Zustand hart, 100-120 HB
- (d) CuAl0,5Zn0,5, Zustand weich, 50-70 HB
- (e) CuAl0,5Zn0,5, Zustand hart, 100-120 HB
- (f) CuLi0,6Si0,1, Zustand weich, 50-70 HB
- (g) CuLi0,6Si0,1, Zustand hart, 100-120HB
- Fig.3:
- den auf die Fläche bezogenen Gewichtsverlust nach einer Zeit von 1000 h.
- Fig.1:
- the current density-potential curves of the alloy systems Cu-Mg-Ti, Cu-Al-Zn and Cu-Li-Si compared to SF-Cu.
Reference electrode: saturated calom electrode. - Fig.2a to 2g:
- the polarization conductance R p ⁻¹ as a function of the test duration.
- (a) SF-Cu, soft state, 50-70 HB or hard, 100-120 HB
- (b) CuMg0.7Ti0.2, soft state, 50-70 HB
- (c) CuMg0.7Ti0.2, hard condition, 100-120 HB
- (d) CuAl0.5Zn0.5, soft state, 50-70 HB
- (e) CuAl0.5Zn0.5, hard condition, 100-120 HB
- (f) CuLi0.6Si0.1, soft state, 50-70 HB
- (g) CuLi0.6Si0.1, hard condition, 100-120HB
- Fig. 3:
- the weight loss related to the area after a period of 1000 h.
In Fig. 1 sind die Stromdichte-Potential-Kurven der Legierungen CuMg0,7Ti0,2, CuAl0,5Zn0,5, CuLi0,6Si0,1 und SF-Cu im Vergleich dargestellt. Es ist zu erkennen, daß die zulegierten Elemente den Bereich der Korrosionsbeständigkeit deutlich erweitern. Die Passivstromdichte ist gegenüber SF-Cu verringert, was für die bessere Deckschichtqualität spricht. Die Durchbruchpotentiale sind zu positiveren Werten hin verschoben.1 shows the current density-potential curves of the alloys CuMg0.7Ti0.2, CuAl0.5Zn0.5, CuLi0.6Si0.1 and SF-Cu in comparison. It can be seen that the alloyed elements significantly expand the range of corrosion resistance. The passive current density is reduced compared to SF-Cu, which speaks for the better cover layer quality. The breakthrough potential has shifted towards more positive values.
Der Polarisationswiderstand Rp bzw. der Kehrwert, der Polarisationsleitwert Rp⁻¹, ist ein Maß für die Korrosionsgeschwindigkeit. Je geringer der Polarisationsleitwert, desto größer ist die Beständigkeit gegen gleichmäßige Korrosion. Die Figuren 2a bis g vergleichen den Polarisationsleitwert der Werkstoffe CuMg0,7Ti0,2, CuAl0,5,Zn0,5 und CuLi0,6Si0,1 in verschiedenen Zuständen (weich/hart) mit demjenigen von SF-Cu. Unlegiertes Cu zeigt nicht nur ein schlechteres Verhalten, sondern auch eine beträchtliche Streuung.The polarization resistance R p or the reciprocal, the polarization conductance R p ⁻¹, is a measure of the rate of corrosion. The lower the polarization conductance, the greater the resistance to uniform corrosion. Figures 2a to g compare the polarization conductance of the materials CuMg0.7Ti0.2, CuAl0.5, Zn0.5 and CuLi0.6Si0.1 in different states (soft / hard) with that of SF-Cu. Unalloyed Cu not only exhibits poorer behavior, but also considerable scatter.
Bei allen untersuchten Werkstoffen war der Massenverlust gegenüber SF-Cu entsprechend Fig.3 erheblich reduziert.The mass loss compared to SF-Cu was significantly reduced in accordance with Fig. 3 for all investigated materials.
In allen Fällen zeigen die erfindungsgemäßen Legierungen ein deutlich besseres Verhalten als SF-Cu. Es wird nicht nur die Deckschichtqualität verbessert, sondern auch die Bildungsgeschwindigkeit beeinflußt und vor allem der Potentialbereich der Korrosionsbeständigkeit ausgedehnt. Durch diese Ausbildung der Passivschicht wird die Cu-Löslichkeit deutlich herabgesetzt.In all cases, the alloys according to the invention show significantly better behavior than SF-Cu. Not only is the quality of the covering layer improved, but also the rate of formation is influenced and, above all, the potential range of corrosion resistance is expanded. This formation of the passive layer significantly reduces the Cu solubility.
Es ist weiterhin als entscheidender Vorteil anzusehen, daß durch die Kombination bestimmter Zwangskomponenten der pH-Wert-Bereich für die Bildung von Deckschichten erweitert wird. Während einige Legierungselemente entsprechend ihrem Pourbaix-Diagramm fähig sind, auch in sauren Medien Reaktionsprodukte zu bilden und somit zum Aufbau einer wirksamen Schutzschicht beizutragen, gilt entsprechendes für andere Elemente in alkalischen Medien. Somit sind die die Erfindung betreffenden Werkstoffe nicht nur in neutralen Wässern einsetzbar. Gewisse pH-Wert-Schwankungen wirken sich nicht negativ auf das Korrosionsverhalten aus.It is also considered to be a decisive advantage that the combination of certain compulsory components extends the pH range for the formation of cover layers. While some alloy elements are capable of forming reaction products in acidic media according to their Pourbaix diagram and thus contribute to the formation of an effective protective layer, the same applies to other elements in alkaline media. The materials relating to the invention can thus not only be used in neutral waters. Certain pH fluctuations do not have a negative effect on the corrosion behavior.
Verschiebt sich das Durchbruchpotential außerdem so weit in positive Richtung, daß es sich nicht mehr im Bereich des freien Korrosionspotentials befindet, so liegt ein zusätzlicher Schutz gegen Elementbildung wie z. B. Kontakt- oder Belüftungselemente vor. Zudem konnte bei den überprüften Rohrmustern keine Lochfraßgefährdung festgestellt werden.If the breakthrough potential also shifts so far in the positive direction that it is no longer in the area of the free corrosion potential, additional protection against element formation such as e.g. B. contact or ventilation elements. In addition, no risk of pitting was found in the tube samples checked.
Claims (6)
- Corrosion-resistant copper alloy, consisting of copper and at least two alloy elements, whose electrochemical stress potentials are more base than copper and which together with copper form an adherent, nonporous cover layer of oxides, oxide hydrates and/or hydroxides, with the levels of the individual elements lying within those limits within which the alloy remains in the mixed-crystal range under technical cooling conditions, characterized by the following features:
the melting point of the mixed crystal is above 400°C, the copper alloy contains at least 99.0 percent by weight copper, the remains two or more alloy elements of unequal valence chosen from groups A and B, with at least one element from group A consisting of zinc, cadmium, beryllium, calcium, strontium, barium, manganese, iron, cobalt or nickel, forming thermodynamically stable chemical compounds of the stated type in the form of bivalent positive ions in the cover layer
and
at least one further element from group B consisting of boron, aluminium, gallium, indium, scandium, yttrium, lanthanum, cerium, mixed metal, chromium, iron or cobalt, forming thermodynamically stable chemical compounds of the stated type in the form of trivalent positive ions in the cover layer. - Corrosion-resistant copper alloy, consisting of copper and at least two alloy elements, whose electrochemical stress potentials are more base than copper and which together with copper form an adherent, nonporous cover layer of oxides, oxide hydrates and/or hydroxides, with the levels of the individual elements lying within those limits within which the alloy remains in the mixed-crystal range under technical cooling conditions, characterized by the following features:
the melting point of the mixed crystal is above 400°C, the copper alloy contains at least 99.0 percent by weight copper, the remains two or more alloy elements of unequal valence chosen from groups A and C, with at least one element from group A consisting of zinc, cadmium, beryllium, calcium, strontium, barium, manganese, iron, cobalt or nickel, forming thermodynamically stable chemical compounds of the stated type in the form of bivalent positive ions in the cover layer
and
at least one further element from group C consisting of silicon, germanium, titanium, zirconium or hafnium, forming thermodynamically stable chemical compounds of the stated type in the form of quadrivalent positive ions in the cover layer. - Corrosion-resistant copper alloy, consisting of copper and at least two alloy elements, whose electrochemical stress potentials are more base than copper and which together with copper form an adherent, nonporous cover layer of oxides, oxide hydrates and/or hydroxides, with the levels of the individual elements lying within those limits within which the alloy remains in the mixed-crystal range under technical cooling conditions, characterized by the following features:
the melting point of the mixed crystal is above 400°C, the copper alloy contains at least 99.0 percent by weight copper, the remains two or more alloy elements of unequal valence chosen from groups D and C, with at least one element from group D consisting of lithium, sodium, potassium, rubidium or cesium, forming thermodynamically stable chemical compounds of the stated type in the form of monovalent positive ions in the cover layer
and
at least one further element from group C consisting of silicon, germanium, titanium, zirconium or hafnium, forming thermodynamically stable chemical compounds of the stated type in the form of quadrivalent positive ions in the cover layer. - Corrosion-resistant copper alloy according to claim 1, 2 or 3,
characterized by the fact that it contains up to 0.04 percent by weight phosphorous. - Corrosion-resistant copper alloy according to one or several of the claims 1 to 4,
characterized by the fact that the elements amount to at least 0.1 percent by weight. - Use of a corrosion-resistant copper alloy according to one or several of the claims 1 to 5 as material for pipes in installation and sanitary engineering and for drinking water pipes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4213488 | 1992-04-24 | ||
| DE19924213488 DE4213488C2 (en) | 1992-04-24 | 1992-04-24 | Corrosion resistant copper alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0579904A1 EP0579904A1 (en) | 1994-01-26 |
| EP0579904B1 true EP0579904B1 (en) | 1995-11-02 |
Family
ID=6457381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19930106094 Expired - Lifetime EP0579904B1 (en) | 1992-04-24 | 1993-04-15 | Corrosion resistant copper alloy |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0579904B1 (en) |
| DE (2) | DE4213488C2 (en) |
| DK (1) | DK0579904T3 (en) |
| ES (1) | ES2081653T3 (en) |
| FI (1) | FI102908B1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4401997C2 (en) * | 1994-01-25 | 1999-02-25 | Okan Dipl Ing Dr Akin | Use of a copper alloy for components in flowing water |
| DE4423635A1 (en) * | 1994-07-06 | 1996-01-11 | Prym William Gmbh & Co Kg | Corrosion-resistant copper alloy |
| DE29916516U1 (en) | 1999-09-20 | 2000-04-20 | Reif, Peter, 87600 Kaufbeuren | Faucet with integrated soap dispenser |
| DE102007015442B4 (en) | 2007-03-30 | 2012-05-10 | Wieland-Werke Ag | Use of a corrosion-resistant copper alloy |
| DE102011016318A1 (en) * | 2011-04-07 | 2012-10-11 | Wieland-Werke Ag | Hard phase copper-tin multicomponent bronze, method of manufacture and use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4047978A (en) * | 1975-04-17 | 1977-09-13 | Olin Corporation | Processing copper base alloys |
| JPS5675541A (en) * | 1979-11-22 | 1981-06-22 | Sumitomo Light Metal Ind Ltd | Copper alloy for water or hot water supply piping material and heat exchanger tube material |
| DE3605796A1 (en) * | 1985-08-24 | 1987-03-26 | Prym Werke William | Corrosion-resistant copper material for pipes, receptacles or the like for flowing media, in particular cold and/or hot water pipes |
| US4749548A (en) * | 1985-09-13 | 1988-06-07 | Mitsubishi Kinzoku Kabushiki Kaisha | Copper alloy lead material for use in semiconductor device |
-
1992
- 1992-04-24 DE DE19924213488 patent/DE4213488C2/en not_active Expired - Fee Related
-
1993
- 1993-04-15 DE DE59300844T patent/DE59300844D1/en not_active Expired - Lifetime
- 1993-04-15 DK DK93106094T patent/DK0579904T3/en active
- 1993-04-15 EP EP19930106094 patent/EP0579904B1/en not_active Expired - Lifetime
- 1993-04-15 ES ES93106094T patent/ES2081653T3/en not_active Expired - Lifetime
- 1993-04-23 FI FI931830A patent/FI102908B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK0579904T3 (en) | 1996-02-05 |
| DE4213488A1 (en) | 1993-10-28 |
| DE59300844D1 (en) | 1995-12-07 |
| FI931830A0 (en) | 1993-04-23 |
| FI931830A (en) | 1993-10-25 |
| ES2081653T3 (en) | 1996-03-16 |
| FI102908B (en) | 1999-03-15 |
| DE4213488C2 (en) | 1995-05-24 |
| FI102908B1 (en) | 1999-03-15 |
| EP0579904A1 (en) | 1994-01-26 |
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