EP0281641A1 - Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes - Google Patents

Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes Download PDF

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Publication number
EP0281641A1
EP0281641A1 EP87103276A EP87103276A EP0281641A1 EP 0281641 A1 EP0281641 A1 EP 0281641A1 EP 87103276 A EP87103276 A EP 87103276A EP 87103276 A EP87103276 A EP 87103276A EP 0281641 A1 EP0281641 A1 EP 0281641A1
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Prior art keywords
hard
tubes
pipes
heated
corrosion resistance
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EP87103276A
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German (de)
French (fr)
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EP0281641B1 (en
Inventor
Martin Dr. Bauser
Edmund Klingler
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Wieland Werke AG
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Wieland Werke AG
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Application filed by Wieland Werke AG filed Critical Wieland Werke AG
Priority to DE8787103276T priority Critical patent/DE3760510D1/en
Priority to EP87103276A priority patent/EP0281641B1/en
Priority to AT87103276T priority patent/ATE45993T1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents

Definitions

  • the invention relates to a method according to the preamble of claim 1.
  • Seamless drawn tubes made of phosphorus-deoxidized copper are produced as hard tube tubes and as soft-annealed tubes, especially coils, and are used extensively for the production of cold and hot water pipes in building construction.
  • the invention is therefore based on the object of specifying a method for improving the corrosion resistance of hard or semi-hard pipes.
  • the object is achieved in that the tubes for burning the lubricant residues are heated to a temperature which is below the lower limit of the recrystallization range for the tubes, an oxidizing atmosphere being present inside the tube.
  • the temperature for the heating is selected in accordance with the softening curve for copper.
  • the illustration shows the basic course of a softening curve (hardness as a function of temperature).
  • the course of the curve is particularly dependent on the degree of drawing of the pipes and the duration of the heating. For example, as the degree of drawing increases, the start of recrystallization begins at lower temperatures.
  • the pipes can be heated at higher temperatures if the pipes contain, according to the invention, additions of a maximum of 0.1% iron, cobalt, nickel, zinc, aluminum, lead, chromium, cadmium, magnesium, manganese, titanium, tin and / or zirconium (Specification in percent by weight).
  • the tubes are heated at a take-off speed of 40 to 80 m / min.
  • an oxygen-containing gas is preferably supplied to the interior of the tube in such an amount that it is sufficient for complete combustion of the lubricant residues. It is recommended to introduce air or oxygen-enriched air into the inside of the pipe.
  • Table II shows the strength values (Brinell hardness HB) and residue values measured on the pipes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Treatment Of Articles (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Metal Extraction Processes (AREA)

Abstract

1. Method to improve the corrosion resistance of hard or half-hard phosphorus-deoxidized copper tubes, drawn to size, by removal of residual lubricant from the tubes inside surface, wherein the tube is heated to a temperature below the range of recristallisation of the tubes, and wherein an oxidizing atmosphere prevails inside the tubes.

Description

Die Erfindung betrifft ein Verfahren nach dem Oberbegriff des Anspruchs 1.The invention relates to a method according to the preamble of claim 1.

Nahtlos gezogene Rohre aus phosphordesoxidiertem Kupfer werden als harte Stangenrohre und als weichgeglühte, ins­besondere zu Ringen, gewickelte Rohre produziert und in großem Umfang für die Herstellung von Kalt- und Warmwasser­leitungen im Hochbau verwendet.Seamless drawn tubes made of phosphorus-deoxidized copper are produced as hard tube tubes and as soft-annealed tubes, especially coils, and are used extensively for the production of cold and hot water pipes in building construction.

Die Erfahrung hat gezeigt, daß die Korrosionsbeständigkeit der Rohre wesentlich verbessert wird, wenn die vom Rohr­ziehen stammenden Schmiermittelrückstände weitgehend entfernt werden.Experience has shown that the corrosion resistance of the pipes is significantly improved if the lubricant residues from pipe drawing are largely removed.

Bei weichgeglühten Rohren sind hierfür eine Reihe von Ver­fahren bekanntgeworden (vgl. beispielsweise DE-PS 3.003.228).In the case of soft annealed tubes, a number of methods have become known for this (see, for example, DE-PS 3,003,228).

Bei harten Rohren hat man bisher versucht, den Schmier­mittelfilm durch Lösungsmittelbehandlung zu entfernen. Diese Behandlung war allerdings nicht ausreichend; denn bei einer Wärmebehandlung der Rohre auf der Baustelle, insbesondere beim Hartlöten oder Warmbiegen, treten an den behandelten Stellen gelegentlich Korrosionserschei­nungen auf, wenn die Qualität des Wassers dementsprechend ist.So far, attempts have been made to remove the lubricant film by means of solvent treatment on hard pipes. However, this treatment was not sufficient; Because with heat treatment of the pipes on the construction site, especially when brazing or hot bending, the treated areas occasionally show signs of corrosion if the quality of the water is corresponding.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren zur Verbesserung der Korrosionsbeständigkeit von harten bzw. halbharten Rohren anzugeben.The invention is therefore based on the object of specifying a method for improving the corrosion resistance of hard or semi-hard pipes.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Rohre zur Verbrennung der Schmiermittelrückstände maximal auf eine Temperatur erwärmt werden, die unter­halb der unteren Grenze des Rekristallisationsbereichs für die Rohre liegt, wobei im Rohrinneren eine oxidie­rende Atmosphäre vorliegt.The object is achieved in that the tubes for burning the lubricant residues are heated to a temperature which is below the lower limit of the recrystallization range for the tubes, an oxidizing atmosphere being present inside the tube.

Es hat sich überraschend gezeigt, daß mit dieser Erwärmung der harten bzw. halbharten Rohre eine Verbrennung des Schmiermittelfilms möglich ist und gleichzeitig ein aus­reichender Kupferoxidfilm (Cu₂0) erzielt wird, der zur Verhinderung der Korrosion beiträgt. Die Rohre sind also auf eine Temperatur zu erwärmen, die mindestens so hoch ist, daß eine Verbrennung der Schmiermittelrückstände möglich ist, und die andererseits unterhalb der unteren Grenze des Rekristallisationsbereichs liegt.It has surprisingly been found that with this heating of the hard or semi-hard pipes, a combustion of the lubricant film is possible and at the same time a sufficient copper oxide film (Cu₂0) is achieved, which contributes to the prevention of corrosion. The pipes must therefore be heated to a temperature which is at least high enough to allow combustion of the lubricant residues and which, on the other hand, is below the lower limit of the recrystallization range.

Nach einer besonderen Ausführungsform der Erfindung wird die Temperatur für die Erwärmung entsprechend der Ent­festigungskurve für Kupfer gewählt. Zur Erläuterung ist in der Abbildung der prinzipielle Verlauf einer Entfesti­gungskurve (Härte als Funktion der Temperatur) dargestellt. Der Rekristallisationsbereich setzt - wie allgemein be­kannt - zu Beginn des Steilabfalls der Kurve ein (= untere Grenze des Rekristallisationsbereichs). Der Verlauf der Kurve ist insbesondere stark abhängig vom Ziehgrad der Rohre und von der Dauer der Erwärmung. So setzt bei­spielsweise bei zunehmendem Ziehgrad der Beginn der Rekristallisation bereits bei niedrigeren Temperaturen ein.According to a particular embodiment of the invention, the temperature for the heating is selected in accordance with the softening curve for copper. The illustration shows the basic course of a softening curve (hardness as a function of temperature). The recrystallization area begins - as is generally known - at the beginning of the steep decline of the curve (= lower limit of the recrystallization area). The course of the curve is particularly dependent on the degree of drawing of the pipes and the duration of the heating. For example, as the degree of drawing increases, the start of recrystallization begins at lower temperatures.

Durch die Wahl der Maximaltemperatur unterhalb der unteren Grenze des Rekristallisationsbereichs ist also sichergestellt, daß der harte bzw. halbharte Zustand der Rohre erhalten bleibt.The choice of the maximum temperature below the lower limit of the recrystallization range ensures that the hard or semi-hard condition of the tubes is maintained.

Es empfiehlt sich, die Rohre auf 250 - 350 ° C zu erwärmen.It is advisable to heat the pipes to 250 - 350 ° C.

Die Erwärmung der Rohre kann bei höheren Temperaturen er­folgen, sofern die Rohre erfindungsgemäß Zusätze von ins­gesamt maximal 0,1 % Eisen, Kobalt, Nickel, Zink, Aluminium, Blei, Chrom, Kadmium, Magnesium, Mangan, Titan, Zinn und/­oder Zirkon enthalten (Angabe in Gewichtsprozent).The pipes can be heated at higher temperatures if the pipes contain, according to the invention, additions of a maximum of 0.1% iron, cobalt, nickel, zinc, aluminum, lead, chromium, cadmium, magnesium, manganese, titanium, tin and / or zirconium (Specification in percent by weight).

Durch diese Zusätze wird die untere Grenze des Rekristalli­sationsbereichs zu höheren Temperaturen verschoben, d.h., es ist eine beschleunigte Verbrennung des Schmiermittelfilms bei höheren Temperaturen möglich, ohne daß ein Härteverlust eintritt. Durch diese Zusätze werden Temperaturerhöhungen von etwa 30 - 40 ° C ermöglicht.These additives shift the lower limit of the recrystallization range to higher temperatures, i.e. accelerated combustion of the lubricant film at higher temperatures is possible without loss of hardness. These additives enable temperature increases of around 30 - 40 ° C.

Nach einer besonderen Ausführungsform der Erfindung werden die Rohre bei einer Abzugsgeschwindigkeit von 40 bis 80 m/min erwärmt.According to a special embodiment of the invention, the tubes are heated at a take-off speed of 40 to 80 m / min.

Sofern die Erwärmung bei ruhender Luft nicht ausreichend ist, wird dem Rohrinneren vorzugsweise ein sauerstoffhalti­ges Gas in einer solchen Menge zugeführt, daß sie zur vollständigen Verbrennung der Schmiermittelrückstände aus­reicht. Dabei empfiehlt es sich, Luft oder mit Sauerstoff angereicherte Luft in das Rohrinnere einzuleiten.If the heating is not sufficient when the air is still, an oxygen-containing gas is preferably supplied to the interior of the tube in such an amount that it is sufficient for complete combustion of the lubricant residues. It is recommended to introduce air or oxygen-enriched air into the inside of the pipe.

Die Erfindung wird anhand der folgenden Ausführungsbeispiele näher erläutert:The invention is explained in more detail using the following exemplary embodiments:

Zur Untersuchung standen sechs auf die Endabmessung 15 x 1 mm gezogene Rohre aus phosphordesoxidiertem Kupfer in Form von Großringen der Länge 650 m zur Verfügung. Die Rohre mit einem Rest-Schmiermittelgehalt von 0,06 bis 0,08 mg C/dm² wurden mit einer Abzugsgeschwindigkeit von 50 m/min durch eine Strecke zur Widerstandserwärmung geführt und auf die Temperaturen gemäß folgender Tabelle I erwärmt. Die Erwärmung erfolgte bei Luft bzw. nach der Auffüllung der Großringe mit einem Sauerstoff/Stickstoff-Gemisch 50 % 0₂/50 % N₂.

Figure imgb0001
For the investigation, six pipes made of phosphorus-deoxidized copper in the form of large rings with a length of 650 m were drawn to the final dimensions of 15 x 1 mm. The tubes with a residual lubricant content of 0.06 to 0.08 mg C / dm² were passed through a resistance heating section at a take-off speed of 50 m / min and heated to the temperatures according to Table I below. The heating took place in air or after filling the large rings with an oxygen / nitrogen mixture 50% 0₂ / 50% N₂.
Figure imgb0001

In der Tabelle II sind die an den Rohren gemessenen Festig­keitswerte (Brinell-Härte HB) und Rückstandswerte aufgeführt.

Figure imgb0002
Table II shows the strength values (Brinell hardness HB) and residue values measured on the pipes.
Figure imgb0002

Es zeigt sich, daß bei der durchgeführten Erwärmung der Rohre nicht nur der harte bzw. halbharte Zustand der Rohre erhalten bleibt, sondern auch der Restkohlenstoffgehalt unter der üblicherweise geforderten Grenze von 0,06 mg C/dm² liegt. An den untersuchten Rohren wurden außerdem dünne Oxidfilme (Cu₂O) festgestellt, die ebenfalls für eine gute Korrosionsbeständigkeit verantwortlich sind.It turns out that when the pipes are heated, not only the hard or semi-hard condition of the pipes is preserved, but also the residual carbon content is below the limit of 0.06 mg C / dm 2 which is usually required. Thin oxide films (Cu₂O) were also found on the pipes examined, which are also responsible for good corrosion resistance.

Claims (8)

1. Verfahren zur Verbesserung der Korrosionsbeständigkeit von auf Endabmessung gezogenen harten bzw. halbharten Rohren aus phosphordesoxidiertem Kupfer durch Reinigung der Rohrinnenfläche von Schmiermittelrückständen, dadurch gekennzeichnet,
daß die Rohre zur Verbrennung der Schmiermittelrück­stände maximal auf eine Temperatur erwärmt werden, die unterhalb der unteren Grenze des Rekristallisations­bereichs für die Rohre liegt, wobei im Rohrinneren eine oxidierende Atmosphäre vorliegt.1. A method for improving the corrosion resistance of hard or semi-hard tubes made of phosphorus deoxidized copper drawn to the final dimension by cleaning the inner surface of the tube from lubricant residues, characterized in that
that the tubes for the combustion of the lubricant residues are heated to a temperature which is below the lower limit of the recrystallization range for the tubes, an oxidizing atmosphere being present inside the tube. 2. Verfahren nach Anspruch 1,
dadurch gekennzeichnet,
daß die Temperatur für die Erwärmung entsprechend der Entfestigungskurve für Kupfer gewählt wird.2. The method according to claim 1,
characterized,
that the temperature for the heating is chosen according to the softening curve for copper. 3. Verfahren nach Anspruch 1 oder 2,
dadurch gekennzeichnet,
daß die Rohre auf 250 - 350 ° C erwärmt werden.3. The method according to claim 1 or 2,
characterized,
that the pipes are heated to 250 - 350 ° C. 4. Verfahren nach den Ansprüchen 1 bis 3,
dadurch gekennzeichnet,
daß Rohre mit Zusätzen von insgesamt maximal 0,1 % Eisen, Kobalt, Nickel, Zink, Aluminium, Blei, Chrom, Kadmium, Magnesium, Mangan, Titan, Zinn und/oder Zirkon auf höhere Temperaturen erwärmt werden als Rohre ohne Zusätze.4. The method according to claims 1 to 3,
characterized,
that pipes with additives totaling a maximum of 0.1% iron, cobalt, nickel, zinc, aluminum, lead, chromium, cadmium, magnesium, manganese, titanium, tin and / or zircon are heated to higher temperatures than pipes without additives. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4,
dadurch gekennzeichnet,
daß die Rohre im kontinuierlichen Durchlauf bei einer Abzugsgeschwindigkeit von 40 bis 80 m/min erwärmt werden.5. The method according to one or more of claims 1 to 4,
characterized,
that the tubes are heated in a continuous pass at a take-off speed of 40 to 80 m / min. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5,
dadurch gekennzeichnet,
daß dem Rohrinneren ein sauerstoffhaltiges Gas in einer solchen Menge zugeführt wird, daß sie zur vollständigen Verbrennung der Schmiermittelrückstände ausreicht.6. The method according to one or more of claims 1 to 5,
characterized,
that an oxygen-containing gas is supplied to the interior of the pipe in such an amount that it is sufficient for complete combustion of the lubricant residues. 7. Verfahren nach Anspruch 6,
dadurch gekennzeichnet,
daß Luft in das Rohrinnere eingeleitet wird.7. The method according to claim 6,
characterized,
that air is introduced into the interior of the pipe. 8. Verfahren nach Anspruch 6,
dadurch gekennzeichnet,
daß mit Sauerstoff angereicherte Luft in das Rohrinnere eingeleitet wird.8. The method according to claim 6,
characterized,
that oxygen-enriched air is introduced into the interior of the pipe.
EP87103276A 1987-03-07 1987-03-07 Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes Expired EP0281641B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8787103276T DE3760510D1 (en) 1987-03-07 1987-03-07 Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes
EP87103276A EP0281641B1 (en) 1987-03-07 1987-03-07 Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes
AT87103276T ATE45993T1 (en) 1987-03-07 1987-03-07 METHOD OF IMPROVING THE CORROSION RESISTANCE OF HARD SEMI-HARD COPPER INSTALLATION TUBES.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87103276A EP0281641B1 (en) 1987-03-07 1987-03-07 Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes

Publications (2)

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EP0281641A1 true EP0281641A1 (en) 1988-09-14
EP0281641B1 EP0281641B1 (en) 1989-08-30

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AT (1) ATE45993T1 (en)
DE (1) DE3760510D1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356732A1 (en) * 1988-08-12 1990-03-07 KM-kabelmetal Aktiengesellschaft Internally oxidized tube
EP0647723A1 (en) * 1993-10-09 1995-04-12 KM Europa Metal Aktiengesellschaft Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes
EP0976845A1 (en) 1998-07-30 2000-02-02 Outokumpu Oyj Method for producing copper tubes
WO2004055230A1 (en) * 2002-12-18 2004-07-01 Outokumpu Oyj Method and arrangement for treating the inner surface of a copper or copper alloy pipe
DE102007055446A1 (en) * 2007-11-12 2009-05-14 Hansgrohe Ag Provision of water-bearing components from brass alloys with reduced metal ion release

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2236023A1 (en) * 1973-07-06 1975-01-31 Liege Usines Cuivre Zinc
FR2308436A1 (en) * 1975-04-25 1976-11-19 Cit Alcatel Avoiding carbon deposits during annealing, from lubricants - in the bore of drawn copper tubes, by sweeping with nitrogen
DE2928084A1 (en) * 1979-07-12 1981-01-29 Kabel Metallwerke Ghh Heat treatment of drawn copper tube - where air is drawn through bore of hot tube for removal of carbon formed by drawing lubricants
DE3003228B1 (en) 1980-01-30 1981-03-26 Wieland-Werke Ag, 89079 Ulm Process for improving the corrosion resistance of copper installation pipes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2236023A1 (en) * 1973-07-06 1975-01-31 Liege Usines Cuivre Zinc
FR2308436A1 (en) * 1975-04-25 1976-11-19 Cit Alcatel Avoiding carbon deposits during annealing, from lubricants - in the bore of drawn copper tubes, by sweeping with nitrogen
DE2928084A1 (en) * 1979-07-12 1981-01-29 Kabel Metallwerke Ghh Heat treatment of drawn copper tube - where air is drawn through bore of hot tube for removal of carbon formed by drawing lubricants
DE3003228B1 (en) 1980-01-30 1981-03-26 Wieland-Werke Ag, 89079 Ulm Process for improving the corrosion resistance of copper installation pipes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356732A1 (en) * 1988-08-12 1990-03-07 KM-kabelmetal Aktiengesellschaft Internally oxidized tube
EP0647723A1 (en) * 1993-10-09 1995-04-12 KM Europa Metal Aktiengesellschaft Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes
EP0976845A1 (en) 1998-07-30 2000-02-02 Outokumpu Oyj Method for producing copper tubes
WO2004055230A1 (en) * 2002-12-18 2004-07-01 Outokumpu Oyj Method and arrangement for treating the inner surface of a copper or copper alloy pipe
EA011199B1 (en) * 2002-12-18 2009-02-27 Отокумпу Оюй Method and arrangement for treating the inner surface of a copper or copper alloy pipe
DE102007055446A1 (en) * 2007-11-12 2009-05-14 Hansgrohe Ag Provision of water-bearing components from brass alloys with reduced metal ion release

Also Published As

Publication number Publication date
ATE45993T1 (en) 1989-09-15
EP0281641B1 (en) 1989-08-30
DE3760510D1 (en) 1989-10-05

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