EP0579904A1 - Corrosion resistant copper alloy - Google Patents
Corrosion resistant copper alloy Download PDFInfo
- Publication number
- EP0579904A1 EP0579904A1 EP93106094A EP93106094A EP0579904A1 EP 0579904 A1 EP0579904 A1 EP 0579904A1 EP 93106094 A EP93106094 A EP 93106094A EP 93106094 A EP93106094 A EP 93106094A EP 0579904 A1 EP0579904 A1 EP 0579904A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- corrosion
- copper alloy
- elements
- positive ions
- resistant copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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, non-porous cover layer made 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.
- the copper alloy contains at least 99.0% by weight of copper, the melting point of the mixed crystal is above 400 ° C., at least two alloy elements of unequal valence form thermodynamically stable chemical compounds of the types mentioned in the top layer Form that the two alloy elements together assume an average valence between 2.5 and 3.0, the difference between the valences being a maximum of 3.
- Average valence should be understood to mean the arithmetic mean of the valences of the two alloy elements.
- Claims 2 to 4 relate to preferred embodiments of the invention: Thereafter, at least one element forms thermodynamically stable chemical compounds of oxides, oxide hydrates and / or hydroxides in the form of divalent positive ions in the cover layer, and at least one further element forms thermodynamically stable chemical compounds of the type mentioned in the form of trivalent positive ions in the cover layer, or that Another element forms thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions in the cover layer, or at least one element forms thermodynamically stable chemical compounds of the types mentioned in the form of monovalent positive ions in the cover layer, and at least one further element forms in the cover layer thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions.
- the elements lithium, sodium, potassium, rubidium or cesium are selected from the group of monovalent positive ions; from the group of divalent positive ions, the elements zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt or nickel; from the group of the trivalent ions boron, aluminum, gallium, indium, scandium, yttrium, lanthanum, cerium, mixed metal, chromium, iron or cobalt and from the group of the tetravalent ions silicon, germanium, tin, titanium, zircon or hafnium.
- 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.
- Fig. 1 the current density-potential curves of the alloys CuMg0.7Ti0.2, CuAl0.5Zn0.5, CuLi0.6Si0.1 and SF-Cu are shown 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.
- 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.
Landscapes
- 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)
Abstract
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, non-porous cover layer made 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 folgende Merkmale gelöst: die Kupferlegierung enthält mindestens 99,0 Gew.-% Kupfer, der Schmelzpunkt des Mischkristalls liegt oberhalb 400° C, mindestens zwei Legierungselemente ungleicher Valenz bilden in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in der Form, daß die beiden Legierungselemente zusammen eine mittlere Valenz zwischen 2,5 und 3,0 annehmen, wobei die Differenz der Valenzen maximal 3 beträgt.The object is achieved according to the invention by the following features: the copper alloy contains at least 99.0% by weight of copper, the melting point of the mixed crystal is above 400 ° C., at least two alloy elements of unequal valence form thermodynamically stable chemical compounds of the types mentioned in the top layer Form that the two alloy elements together assume an average valence between 2.5 and 3.0, the difference between the valences being a maximum of 3.
(Unter "mittlerer Valenz" soll dabei das arithmetische Mittel der Valenzen der beiden Legierungselemente verstanden werden).("Average valence" should be understood to mean the arithmetic mean of the valences of the two alloy elements).
Die Ansprüche 2 bis 4 betreffen bevorzugte Ausführungsformen der Erfindung:
Danach bildet mindestens ein Element in der Deckschicht thermodynamisch stabile chemische Verbindungen aus Oxiden, Oxidhydraten und/oder Hydroxiden in Form zweiwertiger positiver Ionen, und mindestens ein weiteres Element bildet in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Art in Form dreiwertiger positiver Ionen, oder das weitere Element bildet in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form vierwertiger positiver Ionen, bzw. mindestens ein Element bildet in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form einwertiger positiver Ionen, und mindestens ein weiteres Element bildet in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form vierwertiger positiver Ionen.
Thereafter, at least one element forms thermodynamically stable chemical compounds of oxides, oxide hydrates and / or hydroxides in the form of divalent positive ions in the cover layer, and at least one further element forms thermodynamically stable chemical compounds of the type mentioned in the form of trivalent positive ions in the cover layer, or that Another element forms thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions in the cover layer, or at least one element forms thermodynamically stable chemical compounds of the types mentioned in the form of monovalent positive ions in the cover layer, and at least one further element forms in the cover layer thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions.
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 choice of 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.
Nach weiteren bevorzugten Ausführungsformen der Erfindung werden aus der Gruppe der einwertigen positiven Ionen die Elemente Lithium, Natrium, Kalium, Rubidium oder Cäsium ausgewählt;
aus der Gruppe der zweiwertigen positiven Ionen die Elemente Zink, Cadmium, Beryllium, Magnesium, Calcium, Strontium, Barium, Mangan, Eisen, Kobalt oder Nickel;
aus der Gruppe der dreiwertigen Ionen Bor, Aluminium, Gallium, Indium, Scandium, Yttrium, Lanthan, Cer, Mischmetall, Chrom, Eisen oder Kobalt und
aus der Gruppe der vierwertigen Ionen Silizium, Germanium, Zinn, Titan, Zirkon oder Hafnium.According to further preferred embodiments of the invention, the elements lithium, sodium, potassium, rubidium or cesium are selected from the group of monovalent positive ions;
from the group of divalent positive ions, the elements zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt or nickel;
from the group of the trivalent ions boron, aluminum, gallium, indium, scandium, yttrium, lanthanum, cerium, mixed metal, chromium, iron or cobalt and
from the group of the tetravalent ions silicon, germanium, tin, titanium, zircon or hafnium.
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.In Fig. 1, the current density-potential curves of the alloys CuMg0.7Ti0.2, CuAl0.5Zn0.5, CuLi0.6Si0.1 and SF-Cu are shown 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 (11)
gekennzeichnet durch folgende Merkmale:
die Kupferlegierung enthält mindestens 99,0 Gew.-% Kupfer, der Schmelzpunkt des Mischkristalls liegt oberhalb 400° C, mindestens zwei Legierungselemente ungleicher Valenz bilden in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in der Form, daß die beiden Legierungselemente zusammen eine mittlere Valenz zwischen 2,5 und 3,0 annehmen, wobei die Differenz der Valenzen maximal 3 beträgt.Corrosion-resistant copper alloy, consisting of copper and at least two alloy elements, whose electrochemical voltage potential is less noble than copper and which, together with copper, form a firmly adhering, non-porous cover layer made of oxides, oxide hydrates and / or hydroxides, the amount of the individual elements being within those limits , within which the alloy lies in the mixed crystal range under technical cooling conditions,
characterized by the following features:
the copper alloy contains at least 99.0% by weight of copper, the melting point of the mixed crystal is above 400 ° C, at least two alloy elements of unequal valence form thermodynamically stable chemical compounds of the types mentioned in the top layer in such a way that the two alloy elements together form a medium one Assume valence between 2.5 and 3.0, the difference between the valences being a maximum of 3.
dadurch gekennzeichnet,
daß mindestens ein Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form zweiwertiger positiver Ionen bildet
und
daß mindestens ein weiteres Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form dreiwertiger positiver Ionen bildet.Corrosion-resistant copper alloy according to claim 1,
characterized,
that at least one element in the cover layer forms thermodynamically stable chemical compounds of the types mentioned in the form of divalent positive ions
and
that at least one further element in the top layer forms thermodynamically stable chemical compounds of the types mentioned in the form of trivalent positive ions.
dadurch gekennzeichnet,
daß mindestens ein Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form zweiwertiger positiver Ionen bildet
und
daß mindestens ein weiteres Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form vierwertiger positiver Ionen bildet.Corrosion-resistant copper alloy according to claim 1,
characterized,
that at least one element in the cover layer forms thermodynamically stable chemical compounds of the types mentioned in the form of divalent positive ions
and
that at least one further element in the cover layer forms thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions.
dadurch gekennzeichnet,
daß mindestens ein Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form einwertiger positiver Ionen bildet
und
daß mindestens ein weiteres Element in der Deckschicht thermodynamisch stabile chemische Verbindungen der genannten Arten in Form vierwertiger positiver Ionen bildet.Corrosion-resistant copper alloy according to claim 1,
characterized,
that at least one element in the top layer forms thermodynamically stable chemical compounds of the types mentioned in the form of monovalent positive ions
and
that at least one further element in the cover layer forms thermodynamically stable chemical compounds of the types mentioned in the form of tetravalent positive ions.
dadurch gekennzeichnet,
daß die Elemente aus der Gruppe der einwertigen positiven Ionen aus Lithium, Natrium, Kalium, Rubidium oder Cäsium bestehen.Corrosion-resistant copper alloy according to claim 4,
characterized,
that the elements from the group of monovalent positive ions consist of lithium, sodium, potassium, rubidium or cesium.
dadurch gekennzeichnet,
daß die Elemente aus der Gruppe der zweiwertigen positiven Ionen aus Zink, Cadmium, Beryllium, Magnesium, Calcium, Strontium, Barium, Mangan, Eisen, Kobalt oder Nickel bestehen.Corrosion-resistant copper alloy according to claim 2 or 3,
characterized,
that the elements from the group of divalent positive ions consist of zinc, cadmium, beryllium, magnesium, calcium, strontium, barium, manganese, iron, cobalt or nickel.
dadurch gekennzeichnet,
daß die Elemente aus der Gruppe der dreiwertigen positiven Ionen aus Bor, Aluminium, Gallium, Indium, Scandium, Yttrium, Lanthan, Cer, Mischmetall, Chrom, Eisen oder Kobalt bestehen.Corrosion-resistant copper alloy according to claim 2,
characterized,
that the elements from the group of trivalent positive ions consist of boron, aluminum, gallium, indium, scandium, yttrium, lanthanum, cerium, mixed metal, chromium, iron or cobalt.
dadurch gekennzeichnet,
daß die Elemente aus der Gruppe der vierwertigen Ionen aus Silizium, Germanium, Zinn, Titan, Zirkon oder Hafnium bestehen.Corrosion-resistant copper alloy according to claim 3,
characterized,
that the elements from the group of tetravalent ions consist of silicon, germanium, tin, titanium, zircon or hafnium.
dadurch gekennzeichnet,
daß sie bis zu 0,04 Gew.- % Phosphor enthält.Corrosion-resistant copper alloy according to one or more of claims 1 to 8,
characterized,
that it contains up to 0.04% by weight of phosphorus.
dadurch gekennzeichnet,
daß die Elemente mindestens 0,1 Gew.- % betragen.Corrosion-resistant copper alloy according to one or more of claims 1 to 9,
characterized,
that the elements are at least 0.1% by weight.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924213488 DE4213488C2 (en) | 1992-04-24 | 1992-04-24 | Corrosion resistant copper alloy |
DE4213488 | 1992-04-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0579904A1 true EP0579904A1 (en) | 1994-01-26 |
EP0579904B1 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) | FI102908B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0695810A1 (en) * | 1994-07-06 | 1996-02-07 | William Prym GmbH & Co. KG | Corrosion resistant copper alloy |
Families Citing this family (4)
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 |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2065166A (en) * | 1979-11-22 | 1981-06-24 | Sumitomo Light Metal Ind | Copper-base-alloy tube for carrying potable water and for a heat exchanger |
EP0238859A2 (en) * | 1986-02-22 | 1987-09-30 | William Prym GmbH & Co. KG | Corrosion-resistant copper alloy for pipings, tanks or the like for flowing liquids, particularly for cold and/or hot water pipes |
US4872048A (en) * | 1985-09-13 | 1989-10-03 | Mitsubishi Kinzoku Kabushiki Kaisha | Semiconductor device having copper alloy leads |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4047978A (en) * | 1975-04-17 | 1977-09-13 | Olin Corporation | Processing copper base alloys |
-
1992
- 1992-04-24 DE DE19924213488 patent/DE4213488C2/en not_active Expired - Fee Related
-
1993
- 1993-04-15 EP EP19930106094 patent/EP0579904B1/en not_active Expired - Lifetime
- 1993-04-15 DE DE59300844T patent/DE59300844D1/en not_active Expired - Lifetime
- 1993-04-15 ES ES93106094T patent/ES2081653T3/en not_active Expired - Lifetime
- 1993-04-15 DK DK93106094T patent/DK0579904T3/en active
- 1993-04-23 FI FI931830A patent/FI102908B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2065166A (en) * | 1979-11-22 | 1981-06-24 | Sumitomo Light Metal Ind | Copper-base-alloy tube for carrying potable water and for a heat exchanger |
US4872048A (en) * | 1985-09-13 | 1989-10-03 | Mitsubishi Kinzoku Kabushiki Kaisha | Semiconductor device having copper alloy leads |
EP0238859A2 (en) * | 1986-02-22 | 1987-09-30 | William Prym GmbH & Co. KG | Corrosion-resistant copper alloy for pipings, tanks or the like for flowing liquids, particularly for cold and/or hot water pipes |
Non-Patent Citations (4)
Title |
---|
Week 8229, Derwent Publications Ltd., London, GB; AN 82-60405E & JP-A-57 094 539 (FURUKAWA ELECTRIC CO) 12. Juni 1982 * |
Week 8608, Derwent Publications Ltd., London, GB; AN 86-051352 & JP-A-61 003 876 (NIPPON MINING KK) 9. Januar 1986 * |
Week 8648, Derwent Publications Ltd., London, GB; AN 86-314306 & JP-A-61 231 131 (KOBE STEEL KK) 15. Oktober 1986 * |
Week 9006, Derwent Publications Ltd., London, GB; AN 90-040228 & JP-A-1 316 431 (FURUKAWA ELECTRIC CO) 21. Dezember 1989 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0695810A1 (en) * | 1994-07-06 | 1996-02-07 | William Prym GmbH & Co. KG | Corrosion resistant copper alloy |
Also Published As
Publication number | Publication date |
---|---|
DE4213488C2 (en) | 1995-05-24 |
FI931830A0 (en) | 1993-04-23 |
ES2081653T3 (en) | 1996-03-16 |
DE4213488A1 (en) | 1993-10-28 |
FI931830A (en) | 1993-10-25 |
FI102908B1 (en) | 1999-03-15 |
DE59300844D1 (en) | 1995-12-07 |
DK0579904T3 (en) | 1996-02-05 |
FI102908B (en) | 1999-03-15 |
EP0579904B1 (en) | 1995-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE19816671C2 (en) | Use of alloys as lead-free solder alloys | |
DE3634495C2 (en) | Process for producing a copper-tin alloy and its use as a conductor material | |
DE2942345C2 (en) | ||
DE102006010760B4 (en) | Copper alloy and method of making the same | |
DE2631628A1 (en) | USE OF COLLOIDAL VANADIUM PENTOXIDE SOLUTIONS FOR ANTISTATIC EQUIPMENT OF HYDROPHOBIC SURFACES | |
DE112009000731T5 (en) | Cu-Ni-Si-Co-Cr system alloy for electronic materials | |
DE4036096A1 (en) | SYNTHETIC SEALED SEMICONDUCTOR DEVICE | |
DE2701411A1 (en) | CERAMIC CONNECTIONS WITH HIGH DIELECTRICITY CONSTANTS | |
DE4108564C2 (en) | ||
DE2703636A1 (en) | REGENERATING ELECTRIC CAPACITOR AND METHOD FOR MANUFACTURING IT | |
EP0034391A1 (en) | Use of a lead alloy for the anodes in the electrolytic production of zinc | |
EP0579904A1 (en) | Corrosion resistant copper alloy | |
DE2626004C3 (en) | Galvanic solid state cell | |
DE3908513C2 (en) | ||
DE3530736C2 (en) | ||
DE2536896A1 (en) | PROCEDURE FOR SOLDERING ALUMINUM OR ALUMINUM ALLOYS USING FLUX-SOLVENT COMPOSITIONS AND FLUX-SOLDER COMPOSITIONS FOR USE IN THIS PROCESS | |
EP1273671A1 (en) | Dezincification resistant copper-zinc alloy and method for producing the same | |
DE3412463A1 (en) | ELECTRIC CAPACITOR WITH POLYETHYLENE TEREPHTHALATE AS A DIELECTRIC, ESPECIALLY FOR USE AS A SOLVABLE CHIP COMPONENT | |
AT393697B (en) | IMPROVED COPPER-BASED METAL ALLOY, IN PARTICULAR FOR THE CONSTRUCTION OF ELECTRONIC COMPONENTS | |
DE2349233C3 (en) | Matrix of photoconductive cells | |
EP0566978B1 (en) | Use of a copper-aluminium-zinc alloy as corrosion resistant material | |
EP0258670B1 (en) | Impregnated-layers component | |
EP0792941B1 (en) | Use of a copper-aluminium-(zinc) alloy as a corrosion-resistant material | |
DE3204794C2 (en) | ||
DE3717246A1 (en) | NICKEL-BASED MATERIAL FOR A SEMICONDUCTOR ARRANGEMENT |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19930415 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE DK ES FR IT NL SE |
|
17Q | First examination report despatched |
Effective date: 19940704 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE DK ES FR IT NL SE |
|
REF | Corresponds to: |
Ref document number: 59300844 Country of ref document: DE Date of ref document: 19951207 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2081653 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20100521 Year of fee payment: 18 Ref country code: ES Payment date: 20100505 Year of fee payment: 18 Ref country code: DK Payment date: 20100412 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20100402 Year of fee payment: 18 Ref country code: IT Payment date: 20100419 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20100423 Year of fee payment: 18 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20100409 Year of fee payment: 18 |
|
BERE | Be: lapsed |
Owner name: *WIELAND-WERKE A.G. Effective date: 20110430 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20111101 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20111230 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110430 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111101 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110502 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110415 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20120524 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110416 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20120430 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59300844 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110416 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130416 |