EP0683243A2 - Corrosion resistant tube with internal oxide layer - Google Patents
Corrosion resistant tube with internal oxide layer Download PDFInfo
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- EP0683243A2 EP0683243A2 EP95107208A EP95107208A EP0683243A2 EP 0683243 A2 EP0683243 A2 EP 0683243A2 EP 95107208 A EP95107208 A EP 95107208A EP 95107208 A EP95107208 A EP 95107208A EP 0683243 A2 EP0683243 A2 EP 0683243A2
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- European Patent Office
- Prior art keywords
- tube
- corrosion
- annealed
- oxide layer
- pipe according
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- 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.)
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- 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 made of a copper alloy, which is protected by at least one oxide layer.
- a known method for increasing the 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 sea water. Depending on the type and amount of the alloying elements - usually more concentrated alloys are used - this is expensive and the material is inevitably more difficult to form than pure copper, which also increases the production costs.
- EPS 0.356.732 appropriate outer oxide layers are generated by appropriate annealing treatments.
- these layers are very thin and therefore susceptible to mechanical damage. Due to the annealing treatment to create the protective layer, the material is always in a soft state. Hard pipes cannot be manufactured in this way.
- the invention is therefore based on the object of providing a tube made of a copper alloy, the copper permeability of which is reduced by the formation of special oxide layers.
- the tube consisting of a copper alloy with 0.01 to 1.0% of an alloyed element from the group aluminum, tin, zinc or silicon has inner oxide layers located under the inner and outer tube surface, each of which consist exclusively of the oxide of the alloyed element.
- tubes made of low-alloy copper materials can be provided both in the hard and in the soft state.
- the method for producing the corrosion-resistant tubes according to the invention is characterized in that the tube 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.
- the oxygen partial pressure in the annealing atmosphere must be chosen to be as low as possible. In any case, the oxygen partial pressure must be lower than the equilibrium pressure of the following reaction: Cu2O ⁇ 2 Cu + 1/2 O2.
- Annealing in hydrogen, nitrogen, forming gas (90% N2, 10% H2) or other gas mixtures is advisable.
- 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. However, since the inner oxide layers can endure cold deformation of the base material to a certain extent without damage, the soft tubes can then be further consolidated with at least one pull, possibly several pulls, so that a hard state results. The inner layers remain in the material during forming, so they are protected against mechanical damage and chipping. They are even compressed by the forming and thus their protective effect is improved.
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- 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)
Abstract
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 made of a copper alloy, which is protected by at least one oxide layer.
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, some of the copper dissolves in the water. This process, which depends on 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), takes place without external intervention until there is a balance between the in Solution ions and the solid metal has set. Under unfavorable circumstances, the process leads to 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.In recent times, the discussion of copper solubility in drinking water installations has increased due to increased environmental awareness and due to poor water quality in certain areas.
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 a guideline of max. 3 mg Cu / l before. Due to the ongoing discussions, a lowering of this benchmark or the introduction of a lower limit is likely in the near future. The guideline value of 3 mg Cu / l and even lower limit values can at least temporarily be exceeded under certain circumstances (new installations, poor water quality).
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 the 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 sea water. Depending on the type and amount of the alloying elements - usually more concentrated alloys are used - this is expensive and the material is inevitably more difficult to form than pure copper, which also increases the 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-OS 4.110.584), 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. An internal tinning of pipes is described in the magazine "Tube & Pipe Technology", May / June 1989, pp. 19 to 21. Elsewhere a method is described (DE-OS 4.110.584) in which a plastic layer is applied to the inner surface of the tube during the drawing process by polymerization, polyaddition or polycondensation. Defined application of such layers with a uniform thickness is difficult and not practical for long pipe lengths. It is also to be feared that these layers will change adversely as a result of the introduction of heat, for example during soldering or hot bending. In the presence of small defects, infiltration of such layers with local corrosion attack cannot be ruled out.
Weiterhin werden durch entsprechende Glühbehandlungen künstliche äußere Oxidschichten erzeugt (EPS 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, appropriate outer oxide layers are generated by appropriate annealing treatments (EPS 0.356.732). However, these layers are very thin and therefore susceptible to mechanical damage. Due to the annealing treatment to create the protective layer, the material is always in a soft state. Hard pipes cannot be manufactured in this way.
Die Korrosionsbeständigkeit harter Rohre kann bisher nur durch gründliche Entfettung zwecks Entfernung schädlicher Schmiermittelrückstände bzw. durch aufwendige Innenbehandlung mit einem Strahlmittel (DE-OS 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 by complex internal treatment can be improved with an abrasive (DE-OS 3.730.367).
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 providing a tube made of a copper alloy, the copper permeability of which is reduced by the formation of special oxide layers.
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 the tube consisting of a copper alloy with 0.01 to 1.0% of an alloyed element from the group aluminum, tin, zinc or silicon has inner oxide layers located under the inner and outer tube surface, each of which 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 in the following, the production of the protective layer is achieved by simple, tried and tested treatments. With the invention, tubes made of low-alloy copper materials can be provided both in the hard and in the soft state.
Das Verfahren zur Herstellung der erfindungsgemäßen, korrosionsbeständigen Rohre 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.The method for producing the corrosion-resistant tubes according to the invention is characterized in that the tube 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.
Um die Bildung von Mischoxiden zu vermeiden und um ausschließlich reine Oxide zu bilden, muß der Sauerstoffpartialdruck in der Glühatmosphäre möglichst gering gewählt werden. In jedem Fall muß der Sauerstoffpartialdruck geringer sein als der Gleichgewichtsdruck folgender Reaktion:
Cu₂O ⇄ 2 Cu + 1/2 O₂.
In order to avoid the formation of mixed oxides and to form only pure oxides, the oxygen partial pressure in the annealing atmosphere must be chosen to be as low as possible. In any case, the oxygen partial pressure must be lower than the equilibrium pressure of the following reaction:
Cu₂O ⇄ 2 Cu + 1/2 O₂.
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% N₂, 10% H₂) or other gas mixtures is advisable. 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. However, since the inner oxide layers can endure cold deformation of the base material to a certain extent without damage, the soft tubes can then be further consolidated with at least one pull, possibly several pulls, so that a hard state results. The inner layers remain in the material during forming, so they are protected against mechanical damage and chipping. They are even compressed by the forming and thus their protective effect is improved.
Die Erfindung wird an Hand der folgenden Beispiele näher erläutert:
CuAl0,5-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.
CuAl0.5 cast bolts were first pressed into downpipes and then pulled to the desired size 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 H₂ 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 / H₂ took place 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 x 1 mm, the tube was annealed for 3 hours at 900 ° C in forming gas (N₂: H₂ mixture in a ratio of 90:10) (Fig. 3 / magnification also 500: 1). The depth of oxidation is D ≈ 6 µm.
Claims (8)
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.Corrosion-resistant tube made of a copper alloy, which is protected by at least one oxide layer, characterized in that
that the tube consisting of a copper alloy with 0.01 to 1.0% of an alloyed element from the group aluminum, tin, zinc or silicon has inner oxide layers located under the inner and outer surface of the tube, each consisting exclusively of the oxide of the alloyed element consist.
daß die Dicke der inneren Oxidschichten D = 2 bis 20 µm beträgt.Corrosion-resistant pipe according to claim 1, characterized in that
that the thickness of the inner oxide layers is D = 2 to 20 µm.
daß es im weichgeglühten Zustand vorliegt.Corrosion-resistant pipe according to claim 1 or 2, characterized in that
that it is in the annealed condition.
daß es im ziehharten Zustand vorliegt.Corrosion-resistant pipe according to claim 1 or 2, characterized in that
that it is in the hard state.
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.A method for producing a corrosion-resistant pipe according to one of claims 1 to 4, characterized in that
that the tube is annealed for at least one hour in a gas atmosphere with a low oxygen partial pressure at annealing temperatures above 600 ° C.
daß das Rohr bei 800 bis 900 °C geglüht wird.A method according to claim 5 or 6, characterized in that
that the tube is annealed at 800 to 900 ° C.
daß das Rohr für 6 bis 12 Stunden geglüht wird.Method according to one or more of claims 5 to 7, characterized in that
that the tube is annealed for 6 to 12 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4417455 | 1994-05-19 | ||
| DE4417455A DE4417455C2 (en) | 1994-05-19 | 1994-05-19 | Use of a corrosion-resistant tube with inner oxide layers |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0683243A2 true EP0683243A2 (en) | 1995-11-22 |
| EP0683243A3 EP0683243A3 (en) | 1996-12-04 |
| EP0683243B1 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)
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730367A1 (en) | 1987-09-10 | 1989-03-23 | Kabel Metallwerke Ghh | METHOD FOR PRODUCING PUNCH-RESISTANT HARD-DRAWN TUBES FROM COPPER OR COPPER ALLOYS |
| DE4110584A1 (en) | 1989-10-02 | 1992-10-08 | Akin Okan | Protecting cold-drawn metal pipes against corrosion - by using lubricating substance which is then converted on pipes into permanent coating |
Family Cites Families (7)
| 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 |
| DE3827353A1 (en) * | 1988-08-12 | 1990-02-22 | Kabelmetal Ag | INTERNAL OXIDIZED TUBES |
| DE4213487C1 (en) * | 1992-04-24 | 1993-11-18 | Wieland Werke Ag | Use of a copper-aluminum-zinc alloy as a corrosion-resistant material |
-
1994
- 1994-05-19 DE DE4417455A patent/DE4417455C2/en not_active Expired - Fee Related
-
1995
- 1995-05-12 DE DE59503577T patent/DE59503577D1/en not_active Expired - Lifetime
- 1995-05-12 EP EP95107208A patent/EP0683243B1/en not_active Expired - Lifetime
- 1995-05-12 ES ES95107208T patent/ES2123853T3/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730367A1 (en) | 1987-09-10 | 1989-03-23 | Kabel Metallwerke Ghh | METHOD FOR PRODUCING PUNCH-RESISTANT HARD-DRAWN TUBES FROM COPPER OR COPPER ALLOYS |
| DE4110584A1 (en) | 1989-10-02 | 1992-10-08 | Akin Okan | Protecting cold-drawn metal pipes against corrosion - by using lubricating substance which is then converted on pipes into permanent coating |
Non-Patent Citations (1)
| Title |
|---|
| TUBE & PIPE TECHNOLOGY, May 1989 (1989-05-01), pages 19 - 21 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4417455A1 (en) | 1995-11-23 |
| DE4417455C2 (en) | 1997-09-25 |
| ES2123853T3 (en) | 1999-01-16 |
| DE59503577D1 (en) | 1998-10-22 |
| EP0683243A3 (en) | 1996-12-04 |
| EP0683243B1 (en) | 1998-09-16 |
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