EP0683243B1 - Corrosion resistant tube with internal oxide layer - Google Patents

Corrosion resistant tube with internal oxide layer Download PDF

Info

Publication number
EP0683243B1
EP0683243B1 EP95107208A EP95107208A EP0683243B1 EP 0683243 B1 EP0683243 B1 EP 0683243B1 EP 95107208 A EP95107208 A EP 95107208A EP 95107208 A EP95107208 A EP 95107208A EP 0683243 B1 EP0683243 B1 EP 0683243B1
Authority
EP
European Patent Office
Prior art keywords
tube
corrosion
annealed
resistant
oxide layer
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.)
Expired - Lifetime
Application number
EP95107208A
Other languages
German (de)
French (fr)
Other versions
EP0683243A2 (en
EP0683243A3 (en
Inventor
Monika Dr. Dipl.-Ing. Breu
Klaus Dr.-Ing. Ohla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wieland Werke AG
Original Assignee
Wieland Werke AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Publication of EP0683243A2 publication Critical patent/EP0683243A2/en
Publication of EP0683243A3 publication Critical patent/EP0683243A3/en
Application granted granted Critical
Publication of EP0683243B1 publication Critical patent/EP0683243B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising

Definitions

  • the invention relates to a corrosion-resistant tube a copper alloy covered by at least one oxide layer is protected.
  • a known method for increasing corrosion resistance is the modification of the starting material by Alloy formation. This option is used for special Applications such as heavily polluted service water or also sea water used. Depending on the type and amount of alloying elements - usually more concentrated Alloys used - but that is expensive and the Material is inevitably more difficult to form than pure Copper, which also increases production costs.
  • the invention is therefore based on the object of a tube to provide a copper alloy, the Copper permeability through the formation of special oxide layers is reduced.
  • the object is achieved in that that a copper alloy with 0.01 to 1.0% of an alloyed Elements from the group aluminum, tin, zinc or silicon existing pipe under the inner and outer pipe surface located inner oxide layers, each consist exclusively of the oxide of the alloyed element.
  • the process for producing the corrosion-resistant pipes according to the invention is characterized in that the pipe is annealed for at least one hour before or at the final dimension in a gas atmosphere with a low oxygen partial pressure at annealing temperatures above 600 ° C, with the formation of mixed oxides avoid and to form only pure oxides, the oxygen partial pressure in the annealing atmosphere must be chosen as low as possible. In any case, the oxygen partial pressure must be lower than the equilibrium pressure of the following reaction: Cu 2 O ⁇ 2 Cu + 1/2 O 2 .
  • Annealing in hydrogen, nitrogen, forming gas (90% N 2 , 10% H 2 ) or other gas mixtures is expedient.
  • the residual oxygen contents present at the usual levels of purity (eg 99.9%) are sufficient for the desired oxide formation. It is particularly advisable to carry out the annealing at 800 to 900 ° C for 6 to 12 hours.
  • the material Due to the necessary annealing, the material is initially in the recrystallized state. Because the inner oxide layers however a cold deformation of the base material up to one endure a certain degree without damage, the soft pipes then with at least one pull, possibly several trains are further consolidated, so that a tough state results. The inner layers remain in the forming in the material, are therefore in themselves even against mechanical damage and chipping protected. They are even compressed by the forming and thus improved in their protective effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Heat Treatment Of Articles (AREA)

Description

Die Erfindung betrifft ein korrosionsbeständiges Rohr aus einer Kupferlegierung, das durch mindestens eine Oxidschicht geschützt ist.The invention relates to a corrosion-resistant tube a copper alloy covered by at least one oxide layer is protected.

Bringt man Kupfer in Kontakt mit wäßrigen Medien, löst sich ein Teil des Kupfers im Wasser. Dieser vom wäßrigen Medium (z. B. pH-Wert und Wasserhärte), dem Werkstoff (Legierungszusammensetzung, Gefüge und Oberflächenzustand) und den Betriebsbedingungen (Stagnationsphasen, Fließgeschwindigkeit, Rohrquerschnitt) abhängige Vorgang verläuft ohne äußeren Eingriff solange, bis sich ein Gleichgewicht zwischen den in Lösung befindlichen Ionen und dem festen Metall eingestellt hat. Unter ungünstigen Umständen führt der Prozeß zu einer irreparablen Materialschädigung.If copper is brought into contact with aqueous media, it dissolves part of the copper in the water. This from the aqueous medium (e.g. pH value and water hardness), the material (alloy composition, Structure and surface condition) and the Operating conditions (stagnation phases, flow speed, Pipe cross section) dependent process runs without external intervention until there is a balance between the ions in solution and the solid metal has stopped. Under unfavorable circumstances, the Process of irreparable material damage.

In der letzten Zeit hat die Diskussion der Kupferlöslichkeit in Trinkwasserinstallationen sowohl aufgrund eines gesteigerten Umweltbewußtseins als auch mit Hinblick auf gebietsweise schlechte Wasserqualitäten zugenommen.Lately, the discussion of copper solubility in drinking water installations both due to an increased Environmental awareness as well as in terms of area bad water quality increased.

In Deutschland gibt die Trinkwasserverordnung derzeit einen Richtwert von max. 3 mg Cu/l vor. Aufgrund der anhaltenden Diskussionen ist eine Absenkung dieses Richtwertes oder auch die Einführung eines darunterliegenden Grenzwertes in nächster Zeit wahrscheinlich. Der Richtwert von 3 mg Cu/l und erst recht kleinere Grenzwerte können unter gewissen Umständen (Neuinstallationen, schlechte Wasserqualität) zumindest zeitweise überschritten werden. In Germany, the drinking water ordinance currently gives one Guide value of max. 3 mg Cu / l before. Because of the persistent Discussions is a lowering of this benchmark or too the introduction of an underlying limit in probably in the near future. The guide value of 3 mg Cu / l and even smaller limit values can under certain Circumstances (new installations, poor water quality) at least temporarily exceeded.

Ein bekanntes Verfahren zur Erhöhung der Korrosionsbeständigkeit ist die Modifizierung des Ausgangsmaterials durch Legierungsbildung. Diese Möglichkeit wird für spezielle Anwendungsfälle wie stark verschmutzte Brauchwässer oder auch Meerwasser genutzt. Je nach Art und Menge der Legierungselemente - in der Regel werden hier höher konzentrierte Legierungen eingesetzt - ist das jedoch teuer und der Werkstoff ist zwangsläufig schwieriger umformbar als reines Kupfer, was außerdem die Produktionskosten erhöht.A known method for increasing corrosion resistance is the modification of the starting material by Alloy formation. This option is used for special Applications such as heavily polluted service water or also sea water used. Depending on the type and amount of alloying elements - usually more concentrated Alloys used - but that is expensive and the Material is inevitably more difficult to form than pure Copper, which also increases production costs.

Andere Verfahren beschränken sich auf den Oberflächenschutz. In der Zeitschrift "Tube & Pipe Technology", Mai/Juni 1989, S.19 bis 21 wird eine Innenverzinnung von Rohren beschrieben. An anderer Stelle wird ein Verfahren beschrieben (DE-A4 110 584), bei dem während des Ziehvorgangs durch Polymerisation, Polyaddition oder Polykondensation eine Kunststoffschicht auf die Rohrinnenfläche aufgebracht wird. Eine definierte Aufbringung solcher Schichten mit gleichmäßiger Dicke ist schwierig und bei großen Rohrlängen nicht praktikabel. Außerdem ist zu befürchten, daß sich diese Schichten infolge Wärmeeinbringung, beispielsweise beim Löten oder Warmbiegen, nachteilig verändern. Beim Vorhandensein kleiner Fehlstellen ist eine Unterwanderung derartiger Schichten mit lokalem Korrosionsangriff nicht auszuschließen.Other methods are limited to surface protection. In the magazine "Tube & Pipe Technology", May / June 1989, P.19 to 21 describe an internal tinning of pipes. A procedure is described elsewhere (DE-A4 110 584), in which during the drawing process by polymerization, Polyaddition or polycondensation a plastic layer is applied to the inner surface of the pipe. A defined application of such layers with even Thickness is difficult and not practical for long pipe lengths. It is also feared that these layers due to the introduction of heat, for example when soldering or Hot bending, change disadvantageously. In the presence of smaller Defects are an infiltration of such layers local corrosion attack cannot be excluded.

Weiterhin werden durch entsprechende Glühbehandlungen künstliche äußere Oxidschichten erzeugt (EP-A-0 356 732). Diese Schichten sind jedoch sehr dünn und somit anfällig gegenüber mechanischen Beschädigungen. Durch die Glühbehandlung zur Erzeugung der Schutzschicht liegt der Werkstoff stets im weichen Zustand vor. Harte Rohre können auf diese Art und Weise nicht hergestellt werden.Furthermore, through appropriate annealing treatments creates artificial outer oxide layers (EP-A-0 356 732). However, these layers are very thin and therefore vulnerable against mechanical damage. Through the annealing treatment the material is used to create the protective layer always in soft condition. Hard pipes can be on this Way not be manufactured.

Die Korrosionsbeständigkeit harter Rohre kann bisher nur durch gründliche Entfettung zwecks Entfernung schädlicher Schmiermittelrückstände bzw. durch aufwendige Innenbehandlung mit einem Strahlmittel (DE-A-3 730 367) verbessert werden.The corrosion resistance of hard pipes has so far only been possible by thorough degreasing to remove harmful Lubricant residues or through complex internal treatment improved with an abrasive (DE-A-3 730 367) will.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Rohr aus einer Kupferlegierung zur Verfügung zu stellen, dessen Kupferlässigkeit durch die Ausbildung spezieller Oxidschichten reduziert wird.The invention is therefore based on the object of a tube to provide a copper alloy, the Copper permeability through the formation of special oxide layers is reduced.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß das aus einer Kupferlegierung mit 0,01 bis 1,0 % eines zulegierten Elements aus der Gruppe Aluminium, Zinn, Zink oder Silizium bestehende Rohr unter der inneren und äußeren Rohroberfläche befindliche, innere Oxidschichten aufweist, die jeweils ausschließlich aus dem Oxid des zulegierten Elements bestehen.The object is achieved in that that a copper alloy with 0.01 to 1.0% of an alloyed Elements from the group aluminum, tin, zinc or silicon existing pipe under the inner and outer pipe surface located inner oxide layers, each consist exclusively of the oxide of the alloyed element.

Die Dicke der inneren Oxidschichten beträgt vorzugsweise D = 2 bis 20 µm.The thickness of the inner oxide layers is preferably D = 2 to 20 µm.

Durch die Auswahl bestimmter Legierungselemente wie Aluminium, Zinn, Zink oder Silizium, können damit, angepaßt an die Wasserqualität, spezielle Oxidschutzschichten erzeugt werden, die einen verstärkten Korrosionsschutz in sauren bzw. basischen Wässern bieten.
Das Basismaterial wird in seiner Zusammensetzung nur gering verändert, wodurch das Umformverhalten bei der Rohrherstellung nicht nennenswert beeinträchtigt wird.
Die gebildete Oxidschicht wird durch mechanische Einwirkung in gewissen Grenzen nicht zerstört, und somit sind eine Verarbeitung mit weiterer Querschnittsreduzierung oder Biegeoperationen unproblematisch.Through the selection of certain alloy elements such as aluminum, tin, zinc or silicon, adapted to the water quality, special oxide protection layers can be created that offer increased corrosion protection in acidic or basic water.
The composition of the base material is changed only slightly, which means that the forming behavior during pipe production is not significantly impaired.
The oxide layer formed is not destroyed by mechanical action within certain limits, and processing with a further reduction in cross-section or bending operations are therefore unproblematic.

Wie im folgenden noch gezeigt wird, wird die Herstellung der Schutzschicht durch einfache, in der Praxis bewährte Behandlungen erzielt. Mit der Erfindung können Rohre aus niedriglegierten Kupferwerkstoffen sowohl im harten als auch im weichen Zustand bereitgestellt werden. As will be shown below, the manufacture of the Protective layer through simple, tried and tested treatments achieved. With the invention, tubes made of low-alloy Copper materials both in hard and in soft condition.

Das Verfahren zur Herstellung der erfindungsgemäßen, korrosionsbeständigen Rohre gemäß Anspruch 5 ist dadurch gekennzeichnet, daß das Rohr vor oder an Endabmessung in einer Gasatmosphäre mit geringem Sauerstoffpartialdruck bei Glühtemperaturen oberhalb von 600 °C für mindestens eine Stunde geglüht wird, wobei um die Bildung von Mischoxiden zu vermeiden und um ausschließlich reine Oxide zu bilden, der Sauerstoffpartialdruck in der Glühatmosphäre möglichst gering gewählt werden muß. In jedem Fall muß der Sauerstoffpartialdruck geringer sein als der Gleichgewichtsdruck folgender Reaktion: Cu2O ⇄ 2 Cu + 1/2 O2. The process for producing the corrosion-resistant pipes according to the invention is characterized in that the pipe is annealed for at least one hour before or at the final dimension in a gas atmosphere with a low oxygen partial pressure at annealing temperatures above 600 ° C, with the formation of mixed oxides avoid and to form only pure oxides, the oxygen partial pressure in the annealing atmosphere must be chosen as low as possible. In any case, the oxygen partial pressure must be lower than the equilibrium pressure of the following reaction: Cu 2 O ⇄ 2 Cu + 1/2 O 2 .

Zweckmäßig ist eine Glühung in Wasserstoff, Stickstoff, Formiergas (90 % N2, 10 % H2) oder weiteren Gasgemischen. Die bei den üblichen Reinheitsgraden (z.B. 99,9 %) vorhandenen Restsauerstoffgehalte reichen für die gewünschte Oxidbildung aus.
Es empfiehlt sich insbesondere, die Glühung bei 800 bis 900 °C für 6 bis 12 Stunden durchzuführen.Annealing in hydrogen, nitrogen, forming gas (90% N 2 , 10% H 2 ) or other gas mixtures is expedient. The residual oxygen contents present at the usual levels of purity (eg 99.9%) are sufficient for the desired oxide formation.
It is particularly advisable to carry out the annealing at 800 to 900 ° C for 6 to 12 hours.

Durch die notwendige Glühung liegt das Material zunächst im rekristallisierten Zustand vor. Da die inneren Oxidschichten jedoch eine Kaltverformung des Grundmaterials bis zu einem gewissen Grad ohne Schädigung rißfrei ertragen, können die weichen Rohre anschließend noch mit mindestens einem Zug, ggf. mehreren Zügen weiterverfestigt werden, so daß ein ziehharter Zustand resultiert. Die inneren Schichten verbleiben bei der Umformung im Material, sind also in sich selbst gegen mechanische Beschädigungen und Abplatzen geschützt. Sie werden durch die Umformung sogar noch verdichtet und somit in ihrer Schutzwirkung verbessert.Due to the necessary annealing, the material is initially in the recrystallized state. Because the inner oxide layers however a cold deformation of the base material up to one endure a certain degree without damage, the soft pipes then with at least one pull, possibly several trains are further consolidated, so that a tough state results. The inner layers remain in the forming in the material, are therefore in themselves even against mechanical damage and chipping protected. They are even compressed by the forming and thus improved in their protective effect.

Die Erfindung wird an Hand der folgenden Beispiele näher erläutert: CuA10,5-Gußbolzen wurden zunächst zu Vorrohren verpreßt und anschließend ohne Zwischenglühung in mehreren Zügen an die gewünschte Abmessung gezogen.

  • a) Bei Endabmessung 15 x 1 mm wurde das Rohr für 24 Stunden bei 850 °C in H2-Atmosphäre geglüht. Fig. 1 zeigt die Rohroberfläche im Längsschliff in einer Vergrößerung 500:1. Dort hat sich unter der Rohroberfläche eine innere Oxidschicht von Aluminiumoxid bis zu einer Dicke D ≈ 10 µm ausgebildet.
  • b) Die Glühung 850 °C/24 Stunden/H2 erfolgte vor dem letzten Zug. Danach wurde das Rohr an Endabmessung 18 x 1 mm bzw. 15 x 1 mm gezogen und erhielt somit eine Schlußumformung von ca 20 bzw. 30 %. Fig. 2a/2b (Vergrößerung 500:1) zeigt die Verdichtung der inneren Oxidschicht durch diesen letzten Zug für ε = 20 % bzw. ε = 30 %.
  • c) Bei Endabmessung 18 x 1 mm wurde das Rohr für 3 Stunden bei 900 °C in Formiergas (N2:H2-Gemisch im Verhältnis 90:10) geglüht (Fig. 3/Vergrößerung ebenfalls 500:1). Die Oxidationstiefe beträgt D ≈ 6 µm.
    • The invention is explained in more detail with the aid of the following examples: CuA10.5 cast bolts were first pressed to preliminary tubes and then pulled to the desired dimension in several passes without intermediate annealing.
  • a) With a final dimension of 15 x 1 mm, the tube was annealed for 24 hours at 850 ° C in an H 2 atmosphere. Fig. 1 shows the pipe surface in longitudinal section in an enlargement 500: 1. There, an inner oxide layer of aluminum oxide up to a thickness D ≈ 10 µm has formed under the pipe surface.
  • b) The annealing 850 ° C / 24 hours / H 2 was carried out before the last train. The tube was then drawn to a final dimension of 18 x 1 mm or 15 x 1 mm and thus received a final shaping of approx. 20 or 30%. 2a / 2b (magnification 500: 1) shows the compression of the inner oxide layer by this last train for ε = 20% and ε = 30%.
  • c) With a final dimension of 18 × 1 mm, the tube was annealed for 3 hours at 900 ° C. in forming gas (N 2 : H 2 mixture in a ratio of 90:10) (FIG. 3 / magnification also 500: 1). The depth of oxidation is D ≈ 6 µm.

    • Claims (8)

    1. Corrosion-resistant copper-alloy tube, which is protected by at least one oxide layer, characterised in that the tube comprising a copper alloy having from 0.01 to 1.0% of an alloyed element from the group aluminium, tin, zinc or silicon has inner oxide layers which are arranged under the inner and outer tube surface and each of which consists exclusively of the oxide of the alloyed element.
    2. Corrosion-resistant tube according to claim 1, characterised in that the thickness of the inner oxide layers is D = 2 to 20 µm.
    3. Corrosion-resistant tube according to claim 1 or 2, characterised in that it is in the soft-annealed state.
    4. Corrosion-resistant tube according to claim 1 or 2, characterised in that it is in the hard-drawn state.
    5. Process for the manufacture of a corrosion-resistant tube according to any one of claims 1 to 4, characterised in that the tube is annealed, before or at the final dimension, at annealing temperatures above 600°C for at least one hour in a gas atmosphere with an oxygen partial pressure which is lower than the equilibrium pressure of the reaction CU2O ⇄ 2 Cu + 1/2 O2.
    6. Process according to claim 5, characterised in that the tube is annealed in hydrogen, nitrogen or forming gas.
    7. Process according to claim 5 or 6, characterised in that the tube is annealed at from 800 to 900°C.
    8. Process according to one or more of claims 5 to 7, characterised in that the tube is annealed for from 6 to 12 hours.
    EP95107208A 1994-05-19 1995-05-12 Corrosion resistant tube with internal oxide layer Expired - Lifetime EP0683243B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE4417455A DE4417455C2 (en) 1994-05-19 1994-05-19 Use of a corrosion-resistant tube with inner oxide layers
    DE4417455 1994-05-19

    Publications (3)

    Publication Number Publication Date
    EP0683243A2 EP0683243A2 (en) 1995-11-22
    EP0683243A3 EP0683243A3 (en) 1996-12-04
    EP0683243B1 true EP0683243B1 (en) 1998-09-16

    Family

    ID=6518417

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP95107208A Expired - Lifetime EP0683243B1 (en) 1994-05-19 1995-05-12 Corrosion resistant tube with internal oxide layer

    Country Status (3)

    Country Link
    EP (1) EP0683243B1 (en)
    DE (2) DE4417455C2 (en)
    ES (1) ES2123853T3 (en)

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10159949C1 (en) * 2001-12-06 2003-05-22 Wieland Werke Ag Use of a copper-aluminum alloy as bearing material in the manufacture of wear resistant sliding bearings used in the car industry

    Family Cites Families (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    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
    DE1173764B (en) * 1957-05-23 1964-07-09 Siemens Ag Process for the production of abrasion-resistant surface layers of great hardness and conductivity, in particular for electrical sliding and friction contacts
    GB1157658A (en) * 1966-10-14 1969-07-09 Imp Metal Ind Kynoch Ltd Heat Exchangers
    LU80891A1 (en) * 1979-02-07 1980-09-24 Liege Usines Cuivre Zinc SANITARY TUBES OF PHOSPHORUEX COPPER OR CORROSION-RESISTANT PHOSPHORUS COPPER ALLOYS AND PROCESS FOR THEIR PRODUCTION
    US4500605A (en) * 1983-02-17 1985-02-19 Olin Corporation Electrical component forming process
    DE3730367C2 (en) 1987-09-10 1997-10-09 Km Europa Metal Ag Process for the production of pitting-resistant hard drawn tubes made of copper or copper alloys
    DE3827353A1 (en) * 1988-08-12 1990-02-22 Kabelmetal Ag INTERNAL OXIDIZED TUBES
    DE3932865A1 (en) 1989-10-02 1991-04-11 Akin Okan METAL TUBE PROTECTED FROM CORROSION
    DE4213487C1 (en) * 1992-04-24 1993-11-18 Wieland Werke Ag Use of a copper-aluminum-zinc alloy as a corrosion-resistant material

    Also Published As

    Publication number Publication date
    DE59503577D1 (en) 1998-10-22
    EP0683243A2 (en) 1995-11-22
    EP0683243A3 (en) 1996-12-04
    DE4417455C2 (en) 1997-09-25
    DE4417455A1 (en) 1995-11-23
    ES2123853T3 (en) 1999-01-16

    Similar Documents

    Publication Publication Date Title
    EP2054536B1 (en) Process for coating a hot- or cold-rolled steel strip containing 6 - 30% by weight of mn with a metallic protective layer
    DE102005008410B3 (en) Coating steel bands comprises heating bands and applying liquid metal coating
    DE3221857A1 (en) ALLOY, ESPECIALLY FOR THE PRODUCTION OF HIGHLY RESILIENT PIPING OF DEEP HOLES OR THE LIKE
    DE2031495A1 (en) Process for the production of corrosion-resistant metal objects
    DE2150731A1 (en) Corrosion-resistant, especially stainless steel
    EP3374533B1 (en) High tensile brass alloy and high tensile brass alloy product
    EP0681114A2 (en) Plain bearing material
    DE2458213A1 (en) OXIDATION-RESISTANT AUSTENITIC STAINLESS STEEL
    EP2692524B2 (en) Composite material with a protective layer against corrosion and method for its manufacture
    DE1807906A1 (en) Process for the production of materials with high strength, high electrical conductivity and high heat resistance
    EP1273671B1 (en) Dezincification resistant copper-zinc alloy and method for producing the same
    DE1608171A1 (en) Nickel-chromium-molybdenum alloy
    DE3326890C2 (en)
    EP0683243B1 (en) Corrosion resistant tube with internal oxide layer
    EP4092142A1 (en) Method for manufacturing a sheet component from a flat steel product with an anti-corrosion coating
    DE3237604C2 (en) Use of an iron-nickel-chromium alloy as a material for the production of sealing material for soft glass
    EP0045416B1 (en) Process to produce a protective layer on metallic pieces
    EP0647723A1 (en) Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes
    EP0009266A1 (en) Brazable memory alloy and process for the brazing of said memory alloy
    DE4395519C2 (en) Pitting resistant copper@ alloy pipe containing yttrium and/or zirconium@
    DE102019106131A1 (en) Process for the production of components for media-carrying gas or water pipes and the component produced thereby
    WO2005010223A1 (en) Resistant alloy for heat exchangers
    DE102022001563B4 (en) Wrought alloy for a bearing material
    DE3241394A1 (en) CORROSION-RESISTANT COPPER ALLOY
    DE3145236A1 (en) "METHOD FOR PRODUCING DEFORM-RESISTANT, OXIDIC PROTECTIVE LAYERS"

    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: 19950512

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): BE DE ES FR GB IT NL

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): BE DE ES FR GB IT NL

    17Q First examination report despatched

    Effective date: 19970730

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): BE DE ES FR GB IT NL

    REF Corresponds to:

    Ref document number: 59503577

    Country of ref document: DE

    Date of ref document: 19981022

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19981217

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2123853

    Country of ref document: ES

    Kind code of ref document: T3

    ET Fr: translation filed
    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
    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20100329

    Year of fee payment: 16

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20100525

    Year of fee payment: 16

    Ref country code: ES

    Payment date: 20100611

    Year of fee payment: 16

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20100501

    Year of fee payment: 16

    Ref country code: IT

    Payment date: 20100525

    Year of fee payment: 16

    Ref country code: DE

    Payment date: 20100531

    Year of fee payment: 16

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20100518

    Year of fee payment: 16

    BERE Be: lapsed

    Owner name: *WIELAND-WERKE A.G.

    Effective date: 20110531

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 59503577

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 59503577

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: V1

    Effective date: 20111201

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20110512

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20111201

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20120131

    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: 20110512

    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: 20110531

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110531

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110512

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20120717

    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: 20110513

    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 NON-PAYMENT OF DUE FEES

    Effective date: 20111130