EP0306810B2 - Method of producing pitting-resistant hard drawn tubes made of copper or copper-based alloys - Google Patents

Method of producing pitting-resistant hard drawn tubes made of copper or copper-based alloys Download PDF

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Publication number
EP0306810B2
EP0306810B2 EP88114157A EP88114157A EP0306810B2 EP 0306810 B2 EP0306810 B2 EP 0306810B2 EP 88114157 A EP88114157 A EP 88114157A EP 88114157 A EP88114157 A EP 88114157A EP 0306810 B2 EP0306810 B2 EP 0306810B2
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EP
European Patent Office
Prior art keywords
copper
tubes
pitting
films
treated
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
EP88114157A
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German (de)
French (fr)
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EP0306810A3 (en
EP0306810B1 (en
EP0306810A2 (en
Inventor
Achim Dr. Baukloh
Ulrich Dr. Reiter
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.)
KM Kabelmetal AG
Original Assignee
KM Europa Metal AG
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Filing date
Publication date
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Application filed by KM Europa Metal AG filed Critical KM Europa Metal AG
Priority to AT88114157T priority Critical patent/ATE103225T1/en
Publication of EP0306810A2 publication Critical patent/EP0306810A2/en
Publication of EP0306810A3 publication Critical patent/EP0306810A3/en
Application granted granted Critical
Publication of EP0306810B1 publication Critical patent/EP0306810B1/en
Publication of EP0306810B2 publication Critical patent/EP0306810B2/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C3/00—Abrasive blasting machines or devices; Plants
    • B24C3/32—Abrasive blasting machines or devices; Plants designed for abrasive blasting of particular work, e.g. the internal surfaces of cylinder blocks
    • B24C3/325—Abrasive blasting machines or devices; Plants designed for abrasive blasting of particular work, e.g. the internal surfaces of cylinder blocks for internal surfaces, e.g. of tubes
    • B24C3/327—Abrasive blasting machines or devices; Plants designed for abrasive blasting of particular work, e.g. the internal surfaces of cylinder blocks for internal surfaces, e.g. of tubes by an axially-moving flow of abrasive particles without passing a blast gun, impeller or the like along the internal surface

Definitions

  • the invention relates to a method for the treatment of hard-drawn Pipes made of copper or a copper alloy for use in the sanitary area.
  • a multi-stage cleaning process where the inside of the pipe first with steam degreased, dried, treated with an abrasive and then blow with medically clean air becomes.
  • Another type of treatment is that Perform annealing in a reducing atmosphere and the resulting carbon film to be removed by an abrasive.
  • an abrasive either by pressurized water or compressed air.
  • the invention lies based on the state of the art the task is based on a method for the treatment of hard drawn copper or copper pipes to create a copper alloy for use in the sanitary area in which the Formation of carbon and / or oxide films in the Brazing or hot bending prevented and thus the pitting resistance of this Pipes is improved.
  • the method according to the teaching of the invention differs from the previously known in relevant soft annealed copper pipes Process by a combination of chemical and mechanical treatment stages.
  • the process succeeds in a surprising way Way, the formation of harmful films, e.g. B. carbon-containing pastures or oxide films, on the inner surface of hard-drawn Avoid copper pipes.
  • films acting as bipolar electrodes are formed usually in the case of brazing or Hot bending of copper pipes usual temperatures.
  • the invention is based on Embodiments explained in more detail.
  • tubes measuring 22 x 1 mm were used.
  • the tubes were treated with corundum for 10 s.
  • the mean roughness value R a was 1.0 am after the blasting agent treatment.
  • the residual carbon or lubricant content was again below the detection limit.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metal Extraction Processes (AREA)
  • Heat Treatment Of Articles (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Meat, Egg Or Seafood Products (AREA)
  • Processing Of Meat And Fish (AREA)
  • Saccharide Compounds (AREA)
  • Control Of Steam Boilers And Waste-Gas Boilers (AREA)
  • ing And Chemical Polishing (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning In General (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

The corrosion damage, particularly that due to local pitting, which occurs on hard-drawn copper tubes used in the sanitary sector is generally caused by carbon-containing films but also by oxide films. A carbon film on the inside of the tube is formed, for example, if the drawing compound added when drawing the tube is subjected to excessive heat. To avoid these damaging films and to improve the pitting resistance of hard tubes made of copper or copper-based alloys, the tubes are first of all degreased. In a further process step, the inner surface of the tubes is then treated with a blasting abrasive in order to establish a minimum roughness. A mean roughness of 0.8 to 1.0 mu m has proven particularly advantageous. The hard-drawn tubes treated by the method according to the invention have none of the films which promote pitting, even after brazing and/or hot bending.

Description

Die Erfindung bezieht sich auf ein Verfahren zur Behandlung von hartgezogenen Rohren aus Kupfer oder einer Kupferlegierung zur Verwendung im Sanitärbereich.The invention relates to a method for the treatment of hard-drawn Pipes made of copper or a copper alloy for use in the sanitary area.

Es ist bekannt, daß nach dem letzten Ziehvorgang weichgeglühte Kupferrohre in aggressiven Leitungswässern korrosionsanfällig sind. Eine besonders charakteristische Erscheinungsform der Korrosionsschäden wird durch die Lochkorrosion verursacht, bei der es auf der Rohrinnenseite zu örtlichen Lochfraßstellen kommt. Die Entstehung derartiger Korrosionsschäden wird kohlenstoffhaltigen Rückständen zugeschrieben, die beispielsweise durch thermische Zersetzung des beim Rohrziehen verwendeten Ziehmittels auftreten.It is known that after the last pull annealed copper tubes in aggressive Tap water is susceptible to corrosion. A special one characteristic manifestation of the Corrosion damage is caused by pitting caused at the inside of the pipe local pitting. The genesis such corrosion damage becomes carbonaceous Arrears attributed to, for example due to thermal decomposition during tube drawing pulling agent used occur.

Aber auch bei hartgezogenen Kupferrohren, die keinem Glühvorgang unterzogen werden, kann ein mehr oder weniger zusammenhängender Kohlenstoffilm auf der Rohrinnenseite entstehen, wenn die Rohre beispielsweise durch Hartlöten miteinander verbunden oder zur Erleichterung des Biegens erwärmt werden.But also for hard-drawn copper pipes that can not be subjected to an annealing process more or less coherent carbon film arise on the inside of the pipe when the For example, pipes are brazed together connected or heated to facilitate bending become.

Es hat sich herausgestellt, daß der beim Erwärmen entstehende Kohlenstoffilm dann nahezu unschädlich ist wenn sich weniger als 0,1 mg/dm2 Ziehöl auf der Innenoberfläche des Kupferrohres befindet.It has been found that the carbon film formed on heating is almost harmless if less than 0.1 mg / dm 2 of drawing oil is on the inner surface of the copper tube.

Kupferrohre für den klinischen Bereich, inbesondere Rohre zum Transport medizinischer Gase, müssen zur Vermeidung jeglichen Risikos eine absolut saubere und fettfreie Innenoberfläche aufweisen. Um diese hohen Anforderungen erfüllen zu können, schreibt das Dokument "British Hospital Technical Memorandum" 22, Ausgabe Mai 1972, ein mehrstufiges Reinigungsverfahren vor, wobei das Rohrinnere zunächst mit Wasserdampf entfettet, getrocknet, mit einem Strahlmittel behandelt und anschließend mit medizinisch reiner Luft durchblasen wird.Copper tubes for the clinical area, in particular Pipes for transporting medical gases, must absolutely avoid any risk have a clean and grease-free inner surface. To meet these high demands can, writes the document "British Hospital Technical Memorandum "22, May 1972 edition, a multi-stage cleaning process, where the inside of the pipe first with steam degreased, dried, treated with an abrasive and then blow with medically clean air becomes.

Zur Entfernung des Ziehölfilms bei Kupferrohres ist es auch bereits bekannt, Entfettungsmittel einzusetzen, beispielsweise organische Lösungsmittel, wie Per- oder Trichlorethylen. Noch ein anderes Verfahren sieht vor, das Ziehöl zu verdampfen und die Ziehöldämpfe abzusaugen.To remove the oil film with copper pipe is it also known degreasing agent use, for example organic solvents, such as per or trichlorethylene. Yet another method provides for the drawing oil to be closed evaporate and suck out the drawing oil vapors.

Eine weitere Behandlungsart besteht darin, die Glühung in einer reduzierenden Atmosphäre durchzuführen und den entstandenen Kohlenstoffilm durch ein Strahlmittel zu entfernen. Hierbei wird in das Rohr ein Strahlmittel entweder durch Druckwasser oder Druckluft eingeführt.Another type of treatment is that Perform annealing in a reducing atmosphere and the resulting carbon film to be removed by an abrasive. Here, in the pipe is an abrasive either by pressurized water or compressed air.

Schließlich ist noch ein Verfahren bekannt, bei dem zur Reinigung der Innenoberfläche installierter Rohrleitungen von ölhaltigen Ablagerungen beispielsweise ein Strahlmittel aus Sandteilchen verwendet wird (EP-A-0 180 228).Finally, a method is known for the one installed to clean the inside surface Pipelines of oily deposits, for example an abrasive made of sand particles is used (EP-A-0 180 228).

Der Erfindung liegt ausgehend vom Stand der Technik die Aufgabe zugrunde, ein Verfahren zur Behandlung von hartgezogenen Rohren aus Kupfer oder einer Kupferlegierung zur Verwendung im Sanitärbereich zu schaffen bei dem die Bildung von Kohlenstoff- und/oder Oxidfilmen beim Hartlöten oder Warmbiegen verhindert und damit die Lochfraßbeständigkeit dieser Rohre verbessert wird.The invention lies based on the state of the art the task is based on a method for the treatment of hard drawn copper or copper pipes to create a copper alloy for use in the sanitary area in which the Formation of carbon and / or oxide films in the Brazing or hot bending prevented and thus the pitting resistance of this Pipes is improved.

Diese Aufgabe wird nach der Erfindung durch die im Anspruch 1 angegebenen Merkmale gelöst.This object is achieved by the invention in claim 1 specified features solved.

Vorteilhafte Weiterbildungen sind in den Unteransprüchen angegeben.Advantageous further developments are in the subclaims specified.

Das Verfahren gemäß der Lehre der Erfindung unterscheidet sich von den bisher bekannten im wesentlichen weichgeglühte Kupferrohre betreffenden Verfahren durch eine Kombination chemischer und mechanischer Behandlungsstufen. Mit dem erfindungsgemäßen Verfahren gelingt es in überraschender Weise, die Bildung von schädlichen Filmen, z. B. kohlenstoffhaltigen Almen oder Oxidfilmen, auf der Innenoberfläche von hartgezogenen Kupferrohren zu vermeiden. Diese nach der Theorie als bipolare Elektroden wirkenden Filme entstehen in der Regel bei den beim Hartlöten oder Warmbiegen von Kupferrohren üblichen Temperaturen.The method according to the teaching of the invention differs from the previously known in relevant soft annealed copper pipes Process by a combination of chemical and mechanical treatment stages. With the invention The process succeeds in a surprising way Way, the formation of harmful films, e.g. B. carbon-containing pastures or oxide films, on the inner surface of hard-drawn Avoid copper pipes. According to the theory films acting as bipolar electrodes are formed usually in the case of brazing or Hot bending of copper pipes usual temperatures.

Eingehende Untersuchungen haben gezeigt, daß die schädlichen Filme im wesentlichen dadurch vermieden werden können, daß die vom Ziehöl weitgehend befreite Innenoberfläche von Kupferrohren nach der zusätzlichen Strahlbehandlung eine gewisse Mindestrauhigkeit aufweist. Es kommt also darauf an, daß an der Innenoberfläche der Rohre eine bestimmte Oberflächenstruktur erzielt wird, die den bei einer Wärmebehandlung entstehenden Filmen nur eine sehr geringe Haftung ermöglicht. Stabile Korrosionselemente, die für das Entstehen der Lochfraßkorrosion ursächlich sind, können sich somit nicht ausbilden.In-depth investigations have shown that the harmful films essentially by can be avoided that the from Drawing oil largely freed of the inner surface of Copper pipes after the additional blasting treatment has a certain minimum roughness. It so it depends on the inner surface the pipes achieve a certain surface structure is the one with a heat treatment resulting films have very little liability enables. Stable corrosion elements, which for the Are the cause of pitting corrosion, can therefore not train.

Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen noch näher erläutert. The invention is based on Embodiments explained in more detail.

Beispiel 1example 1

Auf Endabmessung hartgezogene 5 m lange Rohre aus SF- Cu mit einem Durchmesser von 15 mm und einer Wanddicke von 1 mm wurden in einer ersten Behandlungsstufe zum Entfernen des Ziehöls in ein Lösungsmittelbad aus Trichlorethylen getaucht In einer weiteren Behandlungsstufe wurden die Kupferrohre an die Strahldüse einer Strahlanlage angeschlossen und 5 s lang mit Korund der Körnung 54 (entsprechend einem mittleren Teilchendurchmesser von 300 bis 350 µm) behandelt Der Strahlmitteldruck betrug etwa 0,55 MPa. Um die Innenoberfläche der Rohre je nach späterem Einsatzfall von Korundteilchen zu reinigen, kann beispielsweise ein den Rohrquerschnitt ausfüllender Filzstopfen eingebracht und der gegebenenfalls mit einem Reinigungsmittel getränkte Filzstopfen dann mittels Druck durch die Rohrlänge transportiert werden. Vielfach wird schon ein einfaches Ausblasen mit Preßluft völlig ausreichend sein, um an der Rohrinnenwand haftende Korundteilchen zu beseitigen. Der Mittenrauhwert Ra wurde mit 0,8 µm bestimmt. Der Restkohlenstoffgehalt lag mit < 0,03 mg/dm2 unterhalb der Nachweisgrenze. Langzeitversuche in verschiedenen korrosionsfördernden Haushaltswässern ergaben keine signifikante Ausbildung von Lochkorrosion. Ebenso traten nach dem Hartlöten und/oder Warmbiegen keine Korrosionsschäden auf.5 m long pipes made of SF-Cu with a diameter of 15 mm and a wall thickness of 1 mm, hard-drawn to their final dimensions, were immersed in a trichlorethylene solvent bath to remove the drawing oil in a further treatment step connected and treated with corundum with a grain size of 54 (corresponding to an average particle diameter of 300 to 350 μm) for 5 s. The abrasive pressure was about 0.55 MPa. In order to clean the inner surface of the pipes from corundum particles depending on the later application, a felt plug filling the pipe cross-section can be inserted, for example, and the felt plug, which may be soaked with a cleaning agent, can then be transported through the pipe length by means of pressure. In many cases, simply blowing it out with compressed air will be sufficient to remove corundum particles adhering to the inner wall of the pipe. The average roughness R a was found to be 0.8 µm. The residual carbon content was <0.03 mg / dm 2 below the detection limit. Long-term tests in various corrosion-promoting household waters did not show any significant formation of pitting corrosion. Likewise, no corrosion damage occurred after brazing and / or hot bending.

Beispiel 2Example 2

Entsprechend den in Beispiel 1 angegebenen Verfahrensbedingungen wurden auf Endmaß gezogene Rohre der Abmessung 22 x 1 mm verwendet. In Abänderung des Verfahrens wurden die Rohre 10 s lang mit Korund behandelt. Der Mittenrauhwert Ra betrug nach der Strahlmittelbehandlung 1,0 am. Der Restkohlenstoff- bzw. Restschmiermittelgehalt lag wiederum unterhalb der Nachweisgrenze.In accordance with the process conditions given in Example 1, tubes measuring 22 x 1 mm were used. In a modification of the process, the tubes were treated with corundum for 10 s. The mean roughness value R a was 1.0 am after the blasting agent treatment. The residual carbon or lubricant content was again below the detection limit.

Beispiel 3Example 3

In weiterer Abwandlung der bisher angegebenen Verfahrensbedingungen wurden auf Endabmessung 15 x 1 mm gezogene Rohre zunächst mit Trichlorethan entfettet, getrocknet und dann kurzzeitig in ein Salpetersäurebad getaucht. Die weiteren Verfahrensbedingungen für die Strahlmittelbehandlung entsprachen denen des Beispiels 1. Langzeitversuche von fünf in Gebieten mit lochfraßbegünstigenden Wässern praxisnah betriebenen Prüfständen ergaben keine Anzeichen von Lochfraßangriff. Die Innenoberfläche der Rohre hatte ein blankes metallisches Aussehen. Der Wasserdurchsatz betrug während der Durchflußzeiten etwa 1,5 l/min, der beim Prüfrohr einer mittleren Strömungsgeschwindigkeit von etwa 0,2 m/s entspricht.In a further modification of the previously given Process conditions were based on final dimensions 15 x 1 mm drawn tubes with Trichloroethane degreased, dried and then briefly dipped in a nitric acid bath. The others Process conditions for abrasive treatment corresponded to those of Example 1. Long-term trials of five in areas with pitting-promoting Water practically operated Test benches showed no signs of pitting attack. The inside surface of the pipes had one bare metallic appearance. The water flow was about 1.5 during flow times l / min, the average flow velocity for the test tube of approximately 0.2 m / s.

Claims (5)

  1. Method of treating hard-drawn tubes made of copper or a copper alloy for use in the sanitary sector, wherein the tubes drawn to their final dimensions during the cold forming are immersed in an organic solvent bath through which the inner surfaces are degreased, characterised in that then the inner surfaces of the tubes are treated with a jet of sand or corundum particles for a period of approximately 3 to 30 seconds such that a mean surface roughness of 0.4 to 1.0 µm is produced on the inner surfaces.
  2. Method according to claim 1, characterised in that the inner surfaces of the tubes are treated with a jet of sand or corundum particles for a period of 5 to 10 seconds.
  3. Method according to claim 1 or 2, characterised in that the inner surfaces of the tubes are treated with a jet of sand or corundum particles at a pressure of at least 0.5 MPa.
  4. Method according to one of claims 1 to 3, characterised in that sand or corundum particles with a mean particle diameter of approximately 200 to 350 µm are used.
  5. Method according to claim 1, characterised in that at least the inner surfaces of the tubes are pickled in addition to the degreasing.
EP88114157A 1987-09-10 1988-08-31 Method of producing pitting-resistant hard drawn tubes made of copper or copper-based alloys Expired - Lifetime EP0306810B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88114157T ATE103225T1 (en) 1987-09-10 1988-08-31 PROCESS FOR THE MANUFACTURE OF PITTING RESISTANT HARD DRAWN COPPER OR COPPER ALLOY PIPES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3730367 1987-09-10
DE3730367A DE3730367C2 (en) 1987-09-10 1987-09-10 Process for the production of pitting-resistant hard drawn tubes made of copper or copper alloys

Publications (4)

Publication Number Publication Date
EP0306810A2 EP0306810A2 (en) 1989-03-15
EP0306810A3 EP0306810A3 (en) 1990-05-30
EP0306810B1 EP0306810B1 (en) 1994-03-23
EP0306810B2 true EP0306810B2 (en) 2000-03-29

Family

ID=6335681

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88114157A Expired - Lifetime EP0306810B2 (en) 1987-09-10 1988-08-31 Method of producing pitting-resistant hard drawn tubes made of copper or copper-based alloys

Country Status (11)

Country Link
EP (1) EP0306810B2 (en)
AT (1) ATE103225T1 (en)
DE (2) DE3730367C2 (en)
DK (2) DK493288D0 (en)
ES (1) ES2050684T5 (en)
FI (1) FI94496B (en)
GR (1) GR3033568T3 (en)
IE (1) IE63028B1 (en)
PL (1) PL163146B1 (en)
PT (1) PT88473B (en)
YU (1) YU46572B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4417455C2 (en) 1994-05-19 1997-09-25 Wieland Werke Ag Use of a corrosion-resistant tube with inner oxide layers
FI107543B (en) 1998-07-30 2001-08-31 Outokumpu Oy A method for making a copper tube
FI20001467A (en) * 2000-06-20 2001-12-21 Outokumpu Oy Process for making internally coated copper or copper alloy tubes

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
DE3018036A1 (en) * 1980-05-10 1981-11-12 Kabel- und Metallwerke Gutehoffnungshütte AG, 3000 Hannover METHOD OF TREATING COPPER PIPES
IT1160196B (en) * 1983-02-24 1987-03-04 Dalmine Spa HOT DEOXIDATION PROCESS OF SEMI-FINISHED METAL TUBES
DE3415376A1 (en) * 1984-04-25 1985-11-07 Uhlmann, Otto, 3167 Burgdorf Method and apparatus for degreasing tubes
US4579596A (en) * 1984-11-01 1986-04-01 Union Carbide Corporation In-situ removal of oily deposits from the interior surfaces of conduits

Also Published As

Publication number Publication date
PL274547A1 (en) 1989-05-02
EP0306810A3 (en) 1990-05-30
ATE103225T1 (en) 1994-04-15
DK495488A (en) 1989-03-11
FI94496B (en) 1995-06-15
DK493288D0 (en) 1988-09-05
GR3033568T3 (en) 2000-09-29
DE3730367A1 (en) 1989-03-23
YU46572B (en) 1993-11-16
YU171088A (en) 1990-04-30
DK170250B1 (en) 1995-07-17
ES2050684T5 (en) 2000-07-01
DE3730367C2 (en) 1997-10-09
PT88473A (en) 1988-10-01
ES2050684T3 (en) 1994-06-01
IE882707L (en) 1989-03-10
EP0306810B1 (en) 1994-03-23
FI884071A0 (en) 1988-09-02
DE3888605D1 (en) 1994-04-28
EP0306810A2 (en) 1989-03-15
DK495488D0 (en) 1988-09-06
FI884071A (en) 1989-03-11
PL163146B1 (en) 1994-02-28
PT88473B (en) 1992-11-30
IE63028B1 (en) 1995-03-22

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