EP0792941A1 - Use of a copper-aluminium-(zinc) alloy as a corrosion-resistant material - Google Patents
Use of a copper-aluminium-(zinc) alloy as a corrosion-resistant material Download PDFInfo
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- EP0792941A1 EP0792941A1 EP97102019A EP97102019A EP0792941A1 EP 0792941 A1 EP0792941 A1 EP 0792941A1 EP 97102019 A EP97102019 A EP 97102019A EP 97102019 A EP97102019 A EP 97102019A EP 0792941 A1 EP0792941 A1 EP 0792941A1
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- copper
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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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
Definitions
- the invention relates to the use of a copper-aluminum (zinc) alloy as a corrosion-resistant material for pipes in installation and sanitary engineering and in the drinking water sector.
- a copper-aluminum (zinc) alloy as a corrosion-resistant material for pipes in installation and sanitary engineering and in the drinking water sector.
- Pipes for the purpose mentioned are widely made from oxygen-free copper (SF-Cu).
- SF-Cu oxygen-free copper
- a special manufacturing process can be used to create an oxidic protective layer on the inside of the pipe.
- An alternative is an alloyed material, in which an oxidic, protective cover layer automatically forms under operating conditions.
- a copper-magnesium-aluminum / silicon alloy (DE-PS 3,043,833), for example, has also been proposed for the purpose mentioned, but this could only partially meet the requirements.
- the invention is therefore based on the object of specifying a corrosion-resistant material for which none There is a risk of pitting and in which the copper solubility and the mass removal are reduced.
- the object is achieved by the use of a copper-aluminum (zinc) alloy, which consists of 1.01 to 8.8% aluminum; optionally up to a maximum of 38% zinc; The rest is copper and usual impurities (the percentages relate to the weight).
- a copper-aluminum (zinc) alloy which consists of 1.01 to 8.8% aluminum; optionally up to a maximum of 38% zinc; The rest is copper and usual impurities (the percentages relate to the weight).
- composition of a copper alloy of the type mentioned is known, for example, from DE-OS 2,429,754, but there is no reference to the claimed use.
- DE-OS 4,423,635 describes an aluminum-zinc-based copper alloy.
- the compulsory components nickel and / or chromium are prescribed there, which increase the strength but in return also significantly impair the formability.
- the solubility of chromium in copper is very low. At the specified levels, the solubility limit is exceeded and excretion particles form. With such structural inhomogeneities, which can result in potential differences in the smallest areas, the risk of local corrosion attacks cannot be excluded.
- a copper alloy with 1.01 to 5% aluminum; optionally up to a maximum of 5% zinc is used.
- a copper alloy that additionally contains one or more of the elements silicon, tin, niobium in an amount that corresponds at most to that of the respective solubility limit of the mixed crystal.
- the solubility limit should not be exceeded in order to avoid precipitates, which can be preferred points of attack for corrosion as inhomogeneities. It must be taken into account here that the precipitation behavior can be influenced within certain limits by the corresponding cooling rate, i.e.
- Copper alloys having the compositions according to claims 3 to 7 are preferably used.
- Phosphorus improves the pourability and acts as a deoxidizer.
- FIG. 1 current density-potential curves (FIG. 1) and the electrochemical polarization resistance (R p ) or polarization conductance (R p -1 ) according to FIGS. 2a to d were measured on the tube samples, and the Cu non-conductivity ( Fig. 3) determined.
- 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. 2a to d compare the polarization conductance of the materials CuAl0.3Zn0.3, CuAl3Zn2 and CuAl5 with that of SF-Cu. Unalloyed Cu not only exhibits poorer behavior, but also considerable scatter.
- the Cu nonchalance is considerably reduced compared to SF-Cu according to FIG. 3.
- the Cu-Al (Zn) alloy used according to the invention shows a 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.
- Al is capable of forming reaction products in acidic media and thus contributing to the formation of an effective protective layer, the same applies to Zn in alkaline media.
- Both additives stabilize each other and are able to cover a relatively wide pH range together in the Cu-Al-Zn system.
- the materials to be used according to the invention cannot only be used in neutral waters. Certain pH fluctuations do not have a negative effect on the corrosion behavior.
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- Engineering & Computer Science (AREA)
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Abstract
Description
Die Erfindung betrifft die Verwendung einer Kupfer-Aluminium-(Zink)-Legierung als korrosionsbeständiger Werkstoff für Rohre in der Installations- und Sanitärtechnik und auf dem Trinkwassersektor.The invention relates to the use of a copper-aluminum (zinc) alloy as a corrosion-resistant material for pipes in installation and sanitary engineering and in the drinking water sector.
Werkstoffe, die für den obigen Verwendungszweck eingesetzt werden, müssen vielfachen Anforderungen hinsichtlich ihrer Korrosionsbeständigkeit genügen. Die Mehrzahl der Schadensfälle wird durch gleichmäßige Flächenkorrosion oder Lochfraß ausgelöst. Durch unsachgemäße Montage kann es außerdem zu Korrosionsangriffen im Bereich von Lötstellen und Verbindungen kommen.Materials that are used for the above purpose have to meet multiple requirements with regard to their corrosion resistance. The majority of damage cases are caused by even surface corrosion or pitting. Improper installation can also lead to corrosion attacks in the area of solder joints and connections.
Rohre für den genannten Einsatzzweck werden verbreitet aus sauerstofffreiem Kupfer (SF-Cu) hergestellt. Durch spezielle Herstellungsverfahren kann auf der Rohrinnenfläche eine oxidische Schutzschicht erzeugt werden. Eine Alternative ist ein legierter Werkstoff, bei dem sich unter Einsatzbedingungen von selbst eine oxidische, schützende Deckschicht bildet.Pipes for the purpose mentioned are widely made from oxygen-free copper (SF-Cu). A special manufacturing process can be used to create an oxidic protective layer on the inside of the pipe. An alternative is an alloyed material, in which an oxidic, protective cover layer automatically forms under operating conditions.
Für den genannten Einsatzzweck ist weiterhin beispielsweise eine Kupfer-Magnesium-Aluminium/Silizium-Legierung (DE-PS 3.043.833) vorgeschlagen worden, welche jedoch die gestellten Anforderungen auch nur teilweise erfüllen konnte.A copper-magnesium-aluminum / silicon alloy (DE-PS 3,043,833), for example, has also been proposed for the purpose mentioned, but this could only partially meet the requirements.
Der Erfindung liegt daher die Aufgabe zugrunde, einen korrosionsbeständigen Werkstoff anzugeben, für den keine Lochfraßgefährdung besteht und bei dem die Kupfer-Löslichkeit und der Massenabtrag herabgesetzt werden.The invention is therefore based on the object of specifying a corrosion-resistant material for which none There is a risk of pitting and in which the copper solubility and the mass removal are reduced.
Die Aufgabe wird erfindungsgemäß durch die Verwendung einer Kupfer-Aluminium-(Zink)-Legierung gelöst, die aus 1,01 bis 8,8 % Aluminium; wahlweise bis maximal 38 % Zink; Rest Kupfer und üblichen Verunreinigungen besteht (die Prozentangaben beziehen sich dabei auf das Gewicht).The object is achieved by the use of a copper-aluminum (zinc) alloy, which consists of 1.01 to 8.8% aluminum; optionally up to a maximum of 38% zinc; The rest is copper and usual impurities (the percentages relate to the weight).
Die Zusammensetzung einer Kupfer-Legierung der genannten Art ist beispielsweise aus der DE-OS 2.429.754 bekannt, dort findet sich jedoch kein Hinweis auf den beanspruchten Verwendungszweck.The composition of a copper alloy of the type mentioned is known, for example, from DE-OS 2,429,754, but there is no reference to the claimed use.
In der DE-OS 4.423.635 wird eine Kupfer-Legierung auf Aluminium-Zink-Basis beschrieben. Allerdings sind dort die Zwangskomponenten Nickel und/oder Chrom vorgeschrieben, die zwar die Festigkeit steigern, aber im Gegenzug auch das Umformvermögen deutlich beeinträchtigen. Bekanntermaßen ist die Löslichkeit von Chrom in Kupfer sehr klein. Bei den angegebenen Gehalten wird die Löslichkeitsgrenze überschritten, und es bilden sich Ausscheidungspartikel. Mit derartigen Gefügeinhomogenitäten, wodurch sich Potentialunterschiede in kleinsten Bereichen ergeben können, ist die Gefahr von lokalen Korrosionsangriffen nicht auszuschließen.DE-OS 4,423,635 describes an aluminum-zinc-based copper alloy. However, the compulsory components nickel and / or chromium are prescribed there, which increase the strength but in return also significantly impair the formability. It is known that the solubility of chromium in copper is very low. At the specified levels, the solubility limit is exceeded and excretion particles form. With such structural inhomogeneities, which can result in potential differences in the smallest areas, the risk of local corrosion attacks cannot be excluded.
Bereits in der DE-PS 4.213.487 wurden niedriglegierte Werkstoffe auf Kupfer-Aluminium-Zink-Basis vorgeschlagen, die die genannten Eigenschaften aufweisen. Aus den seinerzeit durchgeführten elektrochemischen Messungen und dem hierbei erfolgten Massenabtrag ist eine klar verbesserte Korrosionsbeständigkeit gegenüber SF-Cu ersichtlich. Die höherkonzentrierten Legierungen schneiden im elektrochemischen Test ebenfalls besser ab als SF-Cu. Ein Vorteil gegenüber den niedriglegierten Werkstoffen ging aus diesen Messungen aber nicht hervor, so daß eine weitere Steigerung des Korrosionsschutzes zunächst nicht zu erwarten war. Vielmehr wurde eine Sättigung der Schutzwirkung angenommen. Erst ergänzende Untersuchungen der Kupfer-Lässigkeit im Trinkwasser zeigten den nicht unerheblichen Konzentrationseinfluß auf, der sich dadurch äußert, daß mit zunehmender Legierungskonzentration die Schutzwirkung erst unter Einsatzbedingungen deutlich verbessert wird und somit die Kupfer-Abgabe an das Wasser entsprechend stark reduziert wird. Entscheidend ist hierbei der Einsatz unter Praxisbedingungen, wodurch offensichtlich nicht nur die Bildungsgeschwindigkeit der Deckschicht, sondern auch durch den ständigen Kontakt mit dem Korrosionsmedium ein Weiterwachsen und eine Verdichtung der Schutzschicht erreicht werden.Low-alloy copper-aluminum-zinc-based materials which have the properties mentioned have already been proposed in DE-PS 4,213,487. From the electrochemical measurements carried out at the time and the mass removal that occurred, a clearly improved corrosion resistance compared to SF-Cu can be seen. The higher-concentration alloys also perform better in the electrochemical test than SF-Cu. However, these measurements gave an advantage over the low-alloy materials not apparent, so that a further increase in corrosion protection was not initially expected. Rather, the protective effect was assumed to be saturated. Only additional studies of the nonchalance of copper in drinking water showed the not inconsiderable influence of the concentration, which manifests itself in the fact that with increasing alloy concentration the protective effect is only significantly improved under operating conditions and thus the copper release to the water is correspondingly greatly reduced. The decisive factor here is the use under practical conditions, whereby obviously not only the rate of formation of the cover layer, but also the constant contact with the corrosion medium allows the protective layer to continue to grow and compact.
Nach einer bevorzugten Ausführungsform der Erfindung wird eine Kupfer-Legierung mit 1,01 bis 5 % Aluminium; wahlweise bis maximal 5 % Zink verwendet. Weiterhin empfiehlt es sich, eine Kupfer-Legierung zu verwenden, die zusätzlich ein oder mehrere der Elemente Silizium, Zinn, Niob in einer Menge, die maximal derjenigen der jeweiligen Löslichkeitsgrenze des Mischkristalls entspricht, enthält. Die Löslichkeitsgrenze soll nicht überschritten werden, damit Ausscheidungen, die als Inhomogenitäten bevorzugte Angriffspunkte für Korrosion sein können, vermieden werden. Hierbei muß berücksichtigt werden, daß das Ausscheidungsverhalten durch entsprechende Abkühlgeschwindigkeit in gewissen Grenzen beeinflußt werden kann, d. h. Ausscheidungen können bei schneller Abkühlung unterdrückt werden, bzw. daß ein Überschreiten der Löslichkeitsgrenzen bei Temperaturen < 300 °C keine Rolle mehr spielt, da infolge der Diffusionsträgheit hier in den in Frage kommenden Systemen keine unerwünschten Ausscheidungsvorgänge mehr ablaufen. Vorzugsweise werden Kupfer-Legierungen mit den Zusammensetzungen nach den Ansprüchen 3 bis 7 verwendet.According to a preferred embodiment of the invention, a copper alloy with 1.01 to 5% aluminum; optionally up to a maximum of 5% zinc is used. Furthermore, it is advisable to use a copper alloy that additionally contains one or more of the elements silicon, tin, niobium in an amount that corresponds at most to that of the respective solubility limit of the mixed crystal. The solubility limit should not be exceeded in order to avoid precipitates, which can be preferred points of attack for corrosion as inhomogeneities. It must be taken into account here that the precipitation behavior can be influenced within certain limits by the corresponding cooling rate, i.e. precipitations can be suppressed during rapid cooling, or that exceeding the solubility limits at temperatures <300 ° C no longer plays a role, because of the diffusion inertia here In the systems in question, there are no longer any undesired elimination processes. Copper alloys having the compositions according to claims 3 to 7 are preferably used.
Weiterhin ist es vorteilhaft, der Legierung maximal 0,04 % Phosphor zuzusetzen. Phosphor verbessert dabei die Gießbarkeit und wirkt als Desoxidationsmittel.It is also advantageous to add a maximum of 0.04% phosphorus to the alloy. Phosphorus improves the pourability and acts as a deoxidizer.
Die Erfindung wird anhand der folgenden Ausführungsbeispiele näher erläutert:The invention is explained in more detail using the following exemplary embodiments:
Es wurden Rohre der Abmessung 15 x 1 mm aus SF-Cu, CuAl0,3Zn0,3 und zweier erfindungsgemäßer Legierungen mit der Zusammensetzung gemäß der folgenden Tabelle hergestellt:
- SF-Cu
- CuAl0,3Zn0,3
- CuAl3Zn2
- CuAl5
- SF-Cu
- CuAl0.3Zn0.3
- CuAl3Zn2
- CuAl5
Zur Beurteilung des Korrosionsverhaltens wurden an den Rohr-mustern Stromdichte-Potential-Kurven (Fig. 1) und der elektrochemische Polarisationswiderstand (Rp) bzw. Polarisationsleitwert (Rp -1) gemäß Fig. 2a bis d gemessen sowie die Cu-Lässigkeit (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 to d were measured on the tube samples, and the Cu non-conductivity ( Fig. 3) determined.
Es zeigen im einzelnen
Fig. 1 die Stromdichte-Potential-Kurve der Legierungen CuAl3Zn2 und CuAl5 im Vergleich zu CuAl0,3Zn0,3 und SF-Cu. Bezugselektrode: gesättigte Kalomelektrode;
Fig. 2a bis 2 d den Polarisationsleitwert Rp -1 als Funktion der Versuchsdauer.
- (a) SF-Cu
- (b) CuAl0,3Zn0,3
- (c) CuAl3Zn2
- (d) CuAl5
Fig. 3 die Cu-Lässigkeit im Stagnationstest in einem aggressiven Trinkwasser, wobei alle 24 h bzw. an Wochenenden alle 72 h ein Wasseraustausch mit Ermittlung der Cu-Gehalte im Stagnationswasser erfolgte und das Prüfwasser folgende mittlere Analysendaten aufwies:
Fig. 1 shows the current density-potential curve of the alloys CuAl3Zn2 and CuAl5 compared to CuAl0.3Zn0.3 and SF-Cu. Reference electrode: saturated calom electrode;
2a to 2 d the polarization conductance R p -1 as a function of the test duration.
- (a) SF-Cu
- (b) CuAl0.3Zn0.3
- (c) CuAl3Zn2
- (d) CuAl5
3 shows the Cu nonchalance in the stagnation test in an aggressive drinking water, with a water exchange with determination of the Cu contents in the stagnation water taking place every 24 h or on weekends and the test water having the following average analysis data:
In Fig. 1 sind die Stromdichte-Potentialkurven der Legierungen CuAl0,3Zn0,3, CuAl3Zn2, CuAl5 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 Potentialen hin verschoben.1 shows the current density-potential curves of the alloys CuAl0.3Zn0.3, CuAl3Zn2, CuAl5 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 potentials have shifted towards more positive potentials.
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 Fig. 2a bis d vergleichen den Polarisationsleitwert der Werkstoffe CuAl0,3Zn0,3, CuAl3Zn2 und CuAl5 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. 2a to d compare the polarization conductance of the materials CuAl0.3Zn0.3, CuAl3Zn2 and CuAl5 with that of SF-Cu. Unalloyed Cu not only exhibits poorer behavior, but also considerable scatter.
Die Cu-Lässigkeit ist gegenüber SF-Cu entsprechend Fig. 3 erheblich reduziert.The Cu nonchalance is considerably reduced compared to SF-Cu according to FIG. 3.
Im Vergleich der legierten Werkstoffe untereinander, d. h. der niedriglegierten und der höherlegierten Varianten, zeigt sich bei den Stromdichte-Potential-Kurven (Fig. 1) und im Verlauf des Polarisationsleitwertes (Fig. 2b bis d) kein signifikanter Unterschied. Erst bei der Cu-Abgabe im Trinkwasser (Fig. 3) tritt das unterschiedliche Verhalten, d. h. abnehmende Cu-Lässigkeit und somit bessere Schutzwirkung mit wachsenden Legierungsgehalten, zu Tage.Comparing the alloyed materials with each other, i. H. the low-alloy and the higher-alloy variants show no significant difference in the current density-potential curves (FIG. 1) and in the course of the polarization conductance (FIGS. 2b to d). The different behavior only occurs when Cu is released in the drinking water (FIG. 3); H. Decreasing Cu nonchalance and thus better protection with increasing alloy contents, by day.
In allen Fällen zeigt die erfindungsgemäß verwendete Cu-Al-(Zn)-Legierung 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 Cu-Al (Zn) alloy used according to the invention shows a 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 der Komponenten Al und Zn der pH-Wert-Bereich für die Bildung von Deckschichten erweitert wird. Während Al gemäß dem Pourbaix-Diagramm fähig ist, auch in sauren Medien Reaktionsprodukte zu bilden und somit zum Aufbau einer wirksamen Schutzschicht beizutragen, gilt entsprechendes für Zn in alkalischen Medien. Beide Zusätze stabilisieren sich wechselseitig und sind in der Lage, gemeinsam im System Cu-Al-Zn einen verhältnismäßig weiten pH-Wert-Bereich abzudecken. Somit sind die erfindungsgemäß zu verwendenden Werkstoffe nicht nur in neutralen Wässern einsetzbar. Gewisse pH-Wert-Schwankungen wirken sich nicht negativ auf das Korrosionsverhalten aus.It is also to be regarded as a decisive advantage that the combination of components Al and Zn extends the pH range for the formation of cover layers. According to the Pourbaix diagram, Al is capable of forming reaction products in acidic media and thus contributing to the formation of an effective protective layer, the same applies to Zn in alkaline media. Both additives stabilize each other and are able to cover a relatively wide pH range together in the Cu-Al-Zn system. Thus, the materials to be used according to the invention cannot 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 (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19606162A DE19606162C2 (en) | 1996-02-20 | 1996-02-20 | Use of a copper-aluminum-zinc alloy as a corrosion-resistant material |
DE19606162 | 1996-02-20 |
Publications (2)
Publication Number | Publication Date |
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EP0792941A1 true EP0792941A1 (en) | 1997-09-03 |
EP0792941B1 EP0792941B1 (en) | 2000-05-03 |
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EP97102019A Expired - Lifetime EP0792941B1 (en) | 1996-02-20 | 1997-02-08 | Use of a copper-aluminium-(zinc) alloy as a corrosion-resistant material |
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Country | Link |
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EP (1) | EP0792941B1 (en) |
DE (2) | DE19606162C2 (en) |
DK (1) | DK0792941T3 (en) |
ES (1) | ES2147950T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102534295A (en) * | 2011-11-21 | 2012-07-04 | 宁波三旺洁具有限公司 | Anticorrosion boron copper alloy |
FR3064280A1 (en) * | 2017-03-23 | 2018-09-28 | Favi - Le Laiton Injecte | COPPER-ZINC ALLOY FOR USE IN THE FOOD INDUSTRY |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR20010032007A (en) * | 1997-11-11 | 2001-04-16 | 시게후치 마사토시 | Metallic material, brass, and process for producing the same |
EP3045740B1 (en) * | 2015-01-19 | 2021-04-21 | BTS BauTechnischeSysteme GmbH & Co. KG | Fastening device for fastening a component to a thermal insulation composite system |
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JPH03229836A (en) * | 1990-02-01 | 1991-10-11 | Kobe Steel Ltd | Corrosion-resistant copper alloy tube |
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DE4213487C1 (en) | 1992-04-24 | 1993-11-18 | Wieland Werke Ag | Use of a copper-aluminum-zinc alloy as a corrosion-resistant material |
DE4423635A1 (en) | 1994-07-06 | 1996-01-11 | Prym William Gmbh & Co Kg | Corrosion-resistant copper alloy |
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US1938172A (en) * | 1933-03-24 | 1933-12-05 | Chase Companies Inc | Copper-base alloys |
US2224095A (en) * | 1940-02-15 | 1940-12-03 | Scovill Manufacturing Co | Tube for heat exchanging apparatus |
DE1127092B (en) * | 1953-04-13 | 1962-04-05 | Osnabruecker Kupfer Und Draht | Use of copper alloys for the manufacture of washing kettles or interior fittings for washing machines |
DK99834C (en) * | 1962-09-19 | 1964-09-21 | Aktieselkabet Nordiske Kabel T | Seawater resistant brass or aluminum brass alloy suitable for plastic deformation. |
LU81564A1 (en) * | 1979-07-31 | 1981-03-24 | Liege Usines Cuivre Zinc | METHOD FOR MANUFACTURING TUBES, TUBES OBTAINED BY THIS PROCESS AND THEIR USE IN CONDENSERS AND HEAT EXCHANGERS |
DE4324008C2 (en) * | 1993-07-17 | 2003-03-27 | Km Europa Metal Ag | Use of a corrosion-resistant copper-based alloy |
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1996
- 1996-02-20 DE DE19606162A patent/DE19606162C2/en not_active Expired - Fee Related
-
1997
- 1997-02-08 DE DE59701554T patent/DE59701554D1/en not_active Expired - Lifetime
- 1997-02-08 EP EP97102019A patent/EP0792941B1/en not_active Expired - Lifetime
- 1997-02-08 DK DK97102019T patent/DK0792941T3/en active
- 1997-02-08 ES ES97102019T patent/ES2147950T3/en not_active Expired - Lifetime
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DE2429754A1 (en) | 1974-06-21 | 1976-01-02 | Olin Corp | Copper alloy treatment - to improve creep strength and stress degradation resistance, by cold-working, deformation, heating and cooling |
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JPH03229836A (en) * | 1990-02-01 | 1991-10-11 | Kobe Steel Ltd | Corrosion-resistant copper alloy tube |
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---|
"Metals Handbook 9th Edition", 1979, AMERICAN SOCIETY FOR METALS, OHIO, USA, XP002031566 * |
DATABASE WPI Section Ch Week 9147, Derwent World Patents Index; Class M26, AN 91-343745, XP002031567 * |
DATABASE WPI Section Ch Week 9206, Derwent World Patents Index; Class M26, AN 92-046046, XP002031568 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102534295A (en) * | 2011-11-21 | 2012-07-04 | 宁波三旺洁具有限公司 | Anticorrosion boron copper alloy |
CN102534295B (en) * | 2011-11-21 | 2016-07-06 | 宁波三旺洁具有限公司 | A kind of anticorrosion boron copper alloy |
FR3064280A1 (en) * | 2017-03-23 | 2018-09-28 | Favi - Le Laiton Injecte | COPPER-ZINC ALLOY FOR USE IN THE FOOD INDUSTRY |
Also Published As
Publication number | Publication date |
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DE19606162A1 (en) | 1997-08-21 |
DE19606162C2 (en) | 2003-01-30 |
ES2147950T3 (en) | 2000-10-01 |
DE59701554D1 (en) | 2000-06-08 |
EP0792941B1 (en) | 2000-05-03 |
DK0792941T3 (en) | 2000-10-02 |
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