EP0493280B1 - Kupferrohre mit verbesserter Korrosionsbeständigkeit sowie Verfahren zu ihrer Herstellung - Google Patents

Kupferrohre mit verbesserter Korrosionsbeständigkeit sowie Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0493280B1
EP0493280B1 EP19910420463 EP91420463A EP0493280B1 EP 0493280 B1 EP0493280 B1 EP 0493280B1 EP 19910420463 EP19910420463 EP 19910420463 EP 91420463 A EP91420463 A EP 91420463A EP 0493280 B1 EP0493280 B1 EP 0493280B1
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Prior art keywords
tube
treatment according
tubes
liquid mixture
hydrophobic
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English (en)
French (fr)
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EP0493280A1 (de
Inventor
Pascal Leterrible
Marcel Negrerie
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Trefimetaux SAS
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Trefimetaux SAS
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
    • F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1287—Process of deposition of the inorganic material with flow inducing means, e.g. ultrasonic

Definitions

  • the invention relates to the field of copper tubes used for sanitary, for domestic or industrial heat exchangers and more generally the fields of use of copper tubes, or copper alloys, which involve localized heating of said tubes either during their mounting, possibly during their final use.
  • the tube heating conditions are generally not good under control. Indeed, the instantaneous temperature is assessed by visual examination of the color of the tube, which itself depends very much on the ambient light.
  • abnormally exaggerated heating conditions can occur, for example to make up for a poorly made weld or to connect tubes of very different diameter. In all cases, this results in an aggravation of the risk of corrosion by "pitting", or pitting of the metal which can lead to a perforation of the metal, when the tube is brought into contact with water, even moderately aggressive for copper. Numerous tests have shown the relationship between the heating conditions and the density of pits which appear later on contact with water.
  • the subject of the invention is a method of treating the interior, and also optionally the exterior, of copper tubes during their industrial manufacture so as to provide the user with a tube of improved resistance to corrosion without this user does not have to take any special precautions for use, in particular during temporary localized heating necessary for the shaping of the tubes or their mounting, or to carry out specific treatments on these tubes after having carried out said temporary heating.
  • the tubes obtained according to the invention make it possible to improve the life of the tubes without introducing constraints for the user client, which is of great practical interest.
  • the treatment of copper or copper alloy tubes intended to improve their resistance to corrosion resulting from temporary heating of said tubes is characterized in that a hydrophobic thin layer is formed on the surface of said tube comprising a boron compound, inert with respect to copper and forming boric anhydride B2O3 during said heating temporary.
  • a boron compound inert with respect to copper can, according to the invention, be chosen from non-ionic inorganic boron derivatives, typically B2O3, organic derivatives of boric acid, precursors of B2O3, leading to the formation of B2O3 by heating, in particular under the conditions of said temporary heating.
  • non-ionic inorganic boron derivatives typically B2O3, organic derivatives of boric acid, precursors of B2O3, leading to the formation of B2O3 by heating, in particular under the conditions of said temporary heating.
  • the Applicant has observed that the risks of corrosion are linked to the presence of discontinuous films, either of carbon or of copper oxides obtained during said localized heating, the nature or the chemical composition of the latter (in particular , the CuO content) having a great influence on the thickness of the film, its morphology and finally its greater or lesser adhesion.
  • B2O3 is the active substance which improves the corrosion resistance of the tubes after temporary heating.
  • B2O que had to be both very divided and very finely and evenly distributed on the surface of the tube, and for that, formed from of B2O3 or a precursor of B2O3 in the very state divided (in solution or in the form of a fine dispersion), and that B2O3 or its precursor forms a thin hydrophobic layer on the surface of the tube to be protected, such a layer being obtained by application, on the tube surface to be treated, d '' a hydrophobic liquid mixture comprising B2O3 or its precursor and an easily removable organic solvent.
  • easily removable solvent is meant a solvent which can be removed between room temperature and 200 ° C.
  • the precursors of B2O3 according to the invention are esters of boric acid, but can also be mineral boron compounds inert with respect to copper.
  • boric esters of formula B (OR) 3 or, B (OR) 2OH, or B (OH) 2OR, with the radical R representing an aliphatic chain having from 1 to 24 carbon atoms, were particularly suitable.
  • boric esters of formula B (OR) 3 or, B (OR) 2OH, or B (OH) 2OR are generally obtained by total or partial reaction of alcohol ROH with boron trichloride BCl3 or boric anhydride B2O3 or l 'boric acid H3BO3.
  • Boric esters can also be used in which the radical R representing an aliphatic chain having from 1 to 22 carbon atoms substituted by an amine group (-NR′R ⁇ , R′ and R ⁇ representing H or an aliphatic chain unless 5 carbon atoms) and / or nitro (-NO2) and / or halogen.
  • the boric esters according to the invention are chosen according to different criteria such as their availability or the possibility of preparing them easily, their cost, their volatility and solubility in organic solvents, esters soluble in organic solvents being preferred . It is also possible according to the invention to use mixtures of these boric esters.
  • boric esters preferably used are those which are soluble in volatile organic solvents or which are easily removable.
  • boric esters are used which are soluble in organic solvents, in which the radical R represents an aliphatic chain having from 2 to 5 carbon atoms. It is important to note the non-toxicity of these boric esters.
  • a fine dispersion of B2O3 or of B2O3 precursor in the volatile solvent using known means of dispersion or grinding and using additives with dispersing action in an organic solvent medium to obtain a liquid mixture consisting of a stable dispersion of fine particles, and / or film-forming additives which make it possible to obtain, after elimination of the solvents, a thin hydrophobic layer having no discontinuity, such an additive coating the fine particles, in particular in the case of a dispersion of B2O3 in a solvent medium.
  • a liquid mixture is obtained in an organic solvent medium, consisting of a fine suspension of B2O3 or of an organic or mineral precursor of B2O3, making it possible to form a thin hydrophobic layer containing said organic or mineral boron derivative in the highly divided state, with a particle size typically less than a few »m.
  • This liquid mixture forms a stable dispersion which does not decant.
  • said liquid mixtures according to the invention comprise at least one volatile solvent and B2O3 or a B2O3 precursor with a content of borated derivative of between 1 and 40% and preferably between 10 and 30% by weight.
  • the surface of said tubes is brought into contact with said hydrophobic liquid mixture, possibly using a medium carrying said hydrophobic liquid mixture, so as to deposit and form a thin layer adhering to said surface, then the surface of the tube is removed. excess hydrophobic liquid mixture not adhering to the surface of the tube.
  • the deposition of thin layer can be carried out according to different methods of the process depending in particular on the nature of said carrier medium.
  • a gas is used as the carrier medium: said hydrophobic liquid mixture is nebulized under form of gaseous suspension, aerosol type, which is circulated inside the tubes, with deposition on the walls.
  • a fibrous pad, impregnated with said hydrophobic liquid mixture is used as the medium carrying said liquid mixture, which is circulated inside the tube and from one end to the other of the tube, thanks to a means of relative displacement of the tampon with respect to the tube, which can be a compressed gas, preferably compressed air.
  • said medium carrying said liquid mixture is the drawing lubricant used at the last drawing pass of the tube.
  • a boric ester miscible with the drawing lubricant is preferably chosen as the liquid mixture.
  • a pad loaded with lubricant and boric ester soluble in the lubricant is circulated inside the tube and from one end to the other of the tube, by means of a means of relative displacement of the buffer with respect to the tube, so as to simultaneously provide lubrication of the tube and the formation of a thin hydrophobic layer comprising a B2O3 precursor.
  • a fibrous buffer is used as a medium carrying borated derivative and possibly lubricant (last stretch pass)
  • a device comprising a mandrel metallic iron or iron alloy inside the tube to which is fixed the fibrous pad (s), and a fixed electromagnet outside the tube ensuring the immobility of the metal mandrel by its electromagnetic field, thanks electromagnetic forces exerted on the mandrel.
  • the method according to the invention can also include heating the tube during or after the formation of said hydrophobic thin layer.
  • this heating can facilitate the formation of a continuous layer of boron derivative, but it can also be used to remove the solvents or to reduce the organic matter content of the layer deposited on the interior surface of the tube by scanning with an oxidizing gas stream (formation of B2O3 from boric ester) during all or part of the heating.
  • this heating can consist of static or dynamic heating at a temperature between 150 and 950 ° C.
  • dynamic heating is used, for example an induction heater which allows heating of tubes in the process, with localized heating on a portion of tube for a time typically of a few seconds.
  • the presence on the surface of the borated derivative and preferably of organic borate causes during dynamic heating the formation either of a film of B2O3 (heating at low temperature) or of a continuous film of Cu2O (heating at high temperature), which in all cases provides better protection against corrosion of the copper tube.
  • the advantage of this process is to obtain a more adherent oxide than that obtained in a passage oven, especially in the case of large diameter tubes.
  • tests 1 to 3 a professional plumber, on the treated tubes (tests 1 to 3) and on the untreated tubes (control tubes) was made to solder at high temperature with a butane torch, under the same conditions, in using usual copper fittings and CuP7% brazing without using solid flux and without water quenching after heating.
  • the brazed tubes After opening the brazed tubes, it appears, on the interior surface, several zones having a surface variable in appearance (color, continuity and thickness of the film), the CuO content of the film, which corresponds to different heating zones .
  • zone A 750 ° C
  • zone B located 2 cm from the center
  • zone C located 5 cm from the center
  • zone D located 7 cm from the center
  • Zone A is black and flaking for the control test:
  • FIG. 2 reproduces a photograph of zone A in the control test which illustrates the flaking of the inner film (large CuO "plates", 100 to 150 " m, between which the metal is bare, unprotected).
  • Zone A is red (absence of CuO) and not flaking for test 2 according to the invention:
  • FIG. 4 reproduces a photograph of zone A of test 2 which shows the presence of a continuous film made up of cells contiguous, adherent to the underlying metal and of small dimensions, of the order of 5-15 ”m.
  • test 4 The Applicant has carried out a test (test 4) by applying the method described in document SU 1077 950 A.
  • test 4 it found that the electrolytic deposition process described in this document is not applicable on an industrial scale to protect the interior of very long copper tubes (problem of the electrodes inside the tube / necessity of a high current density taking into account the surface of the tube / expensive process).
  • test 5 which takes up the conditions of test 2: use of '' a solution of amyl borate at 10% by weight in Dilutin).
  • Test 4 (according to SU) Trial 5 - electrolytic process - dipping process - not applicable on hydrophobic surface - applicable on hydrophobic surface - non-compatibility of boric acid with lubricating oils (degreasing required) - compatibility of the liquid mixture with lubricating oils - formation of non-adherent pulverulent deposit consisting of hydrated Cu borate soluble in water - formation of a continuous thin film of amyl borate (500 ⁇ ) - poor adhesion, non-uniform deposit - excellent grip and continuity - does not prevent the formation of CuO during heating - prevents the formation of CuO during heating - leaves saline residues which reduce the weldability - leaves no residue (easy Sn soldering)
  • FIGS. 6 to 8 which clearly show the advantage brought by the invention (FIG. 6), that either with respect to the untreated tube (control test in FIG. 8) or with respect to the tube treated according to SU 1077-950-A (FIG. 7): the tube treated according to the invention is the only one to have a continuous surface Cu2O free of CuO, which gives this tube a remarkable resistance to pitting corrosion.
  • the tubes treated according to the invention can be stored for several months before being used, for example brazed, without there being any loss of effect of the borated derivative deposited on the surface of the tube. , which may be due to the hydrophobic nature of the thin layer deposited.
  • the Applicant has obtained a marked improvement in the corrosion resistance after temporary heating of copper or copper alloys treated according to the invention, having, on all or part of their surface, a thin layer comprising a boron derivative according to the invention.
  • This improvement is particularly advantageous in the case of temporary and localized heating required by strong brazing or hot bending operations, operations which, as already mentioned, are often carried out on construction sites in more or less conditions severe resulting in use significant pitting corrosion which may however vary with the severity of the soldering or bending conditions.
  • the significant progress made possible by the invention makes it possible to obtain installations, based on copper tubes, not very sensitive to pitting corrosion, and this practically independently of the operating conditions of usual implementation of these tubes, in particular on construction sites.
  • the invention also makes it possible to carry out, with little risk of corrosion, works under severe conditions which it would have been inadvisable to carry out with tubes of the prior art.
  • Figure 1 shows in section a tube (1), control tube or tube according to the invention, and a copper fitting (2) assembled by brazing, with a positioning, substantially at scale 1, of the different zones A to D of the tube (1) corresponding to different temperature ranges reached during temporary heating.
  • FIG. 2 is a representation of a photograph obtained with an electron microscope which illustrates the flaking of the interior surface of zone A of the control tube after brazing at high temperature and the formation of large (hatched) plates (1 cm represents 20 ⁇ m), non-contiguous which reveal the underlying metal locally without a protective layer.
  • FIG. 3 illustrates in cross section a puncture at the level of zone A of the control tube, following the corrosion test.
  • the plane (3) represents the starting copper level.
  • Corrosion results in a "mountain” of malachite (4) of 150 ⁇ m in height, on a layer formed in particular of oxide crystals (5) forming a vault above a "bowl” (the sting) of 60 ”m deep, the bottom of which contains chlorides.
  • FIG. 4 is a representation of a photograph obtained with an electron microscope which illustrates the state of the internal surface of zone A of the tube of test 2 after brazing at high temperature and the presence of a continuous layer made up of cells adherent to the underlying metal, contiguous and small (1 cm represents 20 ⁇ m), so that the entire metal surface is protected.
  • Figure 5 is a cross-sectional view of the device comprising a metal mandrel (6) to which is bound a felt pad (7) loaded with a solution of borated derivative, kept immobile, relative to the tube (1) which scrolls, thanks to a fixed electromagnet (8) surrounding the tube (1).
  • FIG. 6 corresponds to the tube obtained according to the invention (test 5). In this case, it is observed that the tube is coated with a continuous film of red Cu2O (10), the B2O3 formed having been removed by vaporization during brazing.
  • Figure 7 corresponds to the tube obtained in test 4 (according to SU 1077-950-A).
  • a Cu2O film is sometimes found red (10) favorable to the protection of the tube, sometimes a black CuO film (11) discontinuous, detrimental to the resistance to pitting corrosion.
  • Figure 8 corresponds to the untreated control tube.
  • the major part of the heated zone is covered with a highly flaking black CuO film (11), with parts which are not adherent to the tube, very harmful for resistance to pitting corrosion.

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  • Chemical & Material Sciences (AREA)
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  • Mechanical Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Arc Welding In General (AREA)

Claims (24)

  1. Behandlung von Rohren aus Kupfer oder Kupferlegierung, zwecks Verbesserung ihrer Beständigkeit gegenüber der Korrosion aufgrund einer zeitweiligen Erhitzung der Rohre, durch Bildung einer dünnen, hydrophoben, eine gegenüber Kupfer inerte und bei der zeitweiligen Erhitzung Borsäureanhydrid bildende Borverbindung aufweisenden Schicht auf der Innenoberfläche des Rohres,
    dadurch gekennzeichnet,
    daß die Borverbindung unter den mineralischen nichtionischen borhaltigen Abkömmlingen, typisch B₂O₃, und den Borsäureestern als Vorläufer von B₂O₃ gewählt wird.
  2. Behandlung nach dem Anspruch 1,
    bei der der Borsäureester unter den Borsäureestern mit der Formel B(OR)₃ oder B(OR)₂OH oder B(OH)₂OR gewählt wird, wobei das Radikal R eine aliphatische Kette mit 1 bis 22 Kohlenstoffatomen darstellt.
  3. Behandlung nach dem Anspruch 2,
    bei der das Radikal R eine aliphatische Kette mit 1 bis 22 Kohlenstoffatomen darstellt, die durch eine Amingruppe (-NR'R'', wobei R' und R'' H oder eine aliphatische Kette mit weniger als 5 Kohlenstoffatomen darstellen) und/oder Nitrogruppe (-NO₂) und/oder eine Halogengruppe substituiert ist.
  4. Behandlung nach irgendeinem der Ansprüche 2 oder 3,
    bei der das Radikal R eine aliphatische Kette mit 2 bis 5 Kohlenstoffatomen darstellt.
  5. Behandlung nach irgendeinem der Ansprüche 1 bis 4,
    bei der der Vorläufer von B₂O₃ eine Mischung von wenigstens zwei Vorläufern von B₂O₃ ist.
  6. Behandlung nach irgendeinem der Ansprüche 1 bis 5,
    bei der die dünne hydrophobe Schicht durch Aufbringen einer flüssigen hydrophoben Mischung, mit B₂O₃ oder einen Vorläufer von B₂O₃ in organischem, leicht entfernbaren Lösungsmittelmedium auf die zu behandelnde Rohroberfläche erhalten wird.
  7. Behandlung nach dem Anspruch 6,
    bei der der Gehalt an B₂O₃ oder dem Vorläufer von B₂O₃ in der flüssigen Mischung im Bereich von 1 bis 40 Gew.-% und vorzugsweise von 10 bis 30 Gew.-% liegt.
  8. Behandlung nach irgendeinem der Ansprüche 6 und 7,
    bei der man zur Aufbringung der flüssigen hydrophoben Mischung die Oberfläche der Rohre und die flüssige hydrophobe Mischung, eventuell dank einem Trägermedium der flüssigen hydrophoben Mischung, derart in Kontakt bringt, um eine an der Oberfläche haftende dünne Schicht abzuscheiden und zu bilden, und dann von der Oberfläche des Rohres den Überschuß der flüssigen hydrophoben Mischung, der nicht an der Oberfläche des Rohres haftet, entfernt.
  9. Behandlung nach dem Anspruch 8,
    bei der man auf der Oberfläche der Rohre eine Schicht der Mischung durch Eintauchen der Rohre in ein aus der flüssigen Mischung bestehendes Bad derart abscheidet, um die Oberfläche im Kontakt mit dem Bad völlig zu benetzen, dann die Rohre aus dem Bad entnimmt und sie trocknen läßt.
  10. Behandlung nach dem Anspruch 9,
    bei der das Bad mit einer Einrichtung versehen ist, die eine kontinuierliche Durchführung der Behandlung durch kontinuierlichen Durchlauf der Rohre im Bad ermöglicht.
  11. Behandlung nach dem Anspruch 8,
    bei der man die flüssige Mischung in den Rohren derart durchströmen läßt, um die Innenoberfläche des Rohres völlig zu benetzen, und man dann, nach Unterbrechung des Durchstroms der flüssigen Mischung, das Innere des Rohres trocknet.
  12. Behandlung nach dem Anspruch 8,
    bei der man ein Gas als Trägermedium verwendet, worin die hydrophobe Mischung zersprüht wird, und man es im Inneren des Rohres durchströmen läßt.
  13. Behandlung nach dem Anspruch 8,
    bei der man als Trägermedium einen mit der flüssigen hydrophoben Mischung imprägnierten Pfropfen verwendet, den man im Inneren des Rohres und von einem zum anderen Ende des Rohres mit Hilfe eines Mittels zur Relativverschiebung des Pfropfens bezüglich des Rohres durchlaufen läßt.
  14. Behandlung nach dem Anspruch 13,
    bei der das Relativverschiebungsmittel ein komprimiertes Gas, vorzugsweise komprimierte Luft ist.
  15. Behandlung nach dem Anspruch 8,
    bei der das Trägermedium der flüssigen Mischung das beim letzten Ziehstich verwendete Ziehschmiermittel ist, wobei die flüssige Mischung einen mit dem ziehschmiermittel mischbaren Borsäureester aufweist.
  16. Behandlung nach dem Ansprüchen 13 und 15,
    bei der man als Trägermedium der flüssigen Mischung einen mit Schmiermittel und mit löslichem Borsäureester beladenen Pfropfen verwendet, den man beim letzten Ziehstich im Inneren des Rohres und von einem zum anderen Ende des Rohres mit Hilfe eines Mittels zur Relativverschiebung des Pfropfens bezüglich des Rohres derart durchlaufen läßt, um gleichzeitig die Schmierung des Rohres und die Bildung einer dünnen, hydrophoben, einen Vorläufer von B₂O₃ aufweisenden Schicht zu sichern.
  17. Behandlung nach irgendeinem der Ansprüche 13, 14 und 16,
    bei der mit dem das Trägermedium der flüssigen Mischung bildenden faserigen Pfropfen ein zweiter faseriger Pfropfen verbunden wird, der zur Absorption des Überschusses der flüssigen Mischung bestimmt ist, der eventuell an der Innenoberfläche des Rohres vom ersten faserigen Pfropfen als Träger der flüssigen Mischung hinterlassen wurde.
  18. Behandlung nach irgendeinem der Ansprüche 13, 14, 16 und 17,
    bei der die Relativverschiebung des faserigen Pfropfens durch Verschiebung des Rohres bei Unbeweglichhaltung des faserigen Pfropfens im Inneren des Rohres mit Hilfe einer Einrichtung, die im Inneren des Rohres einen metallischen Dorn aufweist, an dem der faserige Stopfen befestigt ist, und eines feststehenden Elektromagneten außerhalb des Rohres gesichert wird, der die Unbeweglichkeit des metallischen Dorns durch sein elektromagnetisches Feld sichert.
  19. Behandlung nach irgendeinem der Ansprüche 1 bis 18,
    bei der man das Rohr entweder während oder nach der Bildung der dünnen Schicht derart erhitzt, um die Bildung einer zusammenhängenden Schicht und/oder eine Verringerung des Gehalts der Schicht an organischem Material zu fördern.
  20. Behandlung nach dem Anspruch 19,
    bei der man das Rohr auf eine Temperatur im Bereich von 150 bis 950 °C mit Hilfe statischer oder dynamischer Heizmittel erhitzt.
  21. Behandlung nach irgendeinem der Ansprüche 19 oder 20,
    bei der man während der gesamten oder eines Teils der Erhitzung das Innere des Rohres mit einem oxidierenden Gas- und vorzugsweise Luftstrom spült.
  22. Behandlung nach irgendeinem der Ansprüche 20 und 21,
    bei der man die Erhitzung auf niedrige Temperatur derart durchführt, um einen Schutzfilm aus B₂O₃ auf der Oberfläche des Rohres zu bilden.
  23. Behandlung nach irgendeinem der Ansprüche 20 und 21,
    bei der man die Erhitzung auf hohe Temperatur derart durchführt, um einen zusammenhängenden Film aus Cu₂O auf der Oberfläche des Rohres zu bilden.
  24. Rohr aus Kupfer oder Kupferlegierung,
    das gemäß irgendeinem der Ansprüche 1 bis 22 behandelt ist und auf der ganzen oder einem Teil seiner Oberfläche eine dünne, B₂O₃ oder einen Vorläufer von B₂O₃ aufweisende, an der Oberfläche des Rohres haftende Schicht derart aufweist, um seine Beständigkeit gegenüber der Korrosion nach zeitweiliger Erhitzung zu verbessern.
EP19910420463 1990-12-26 1991-12-20 Kupferrohre mit verbesserter Korrosionsbeständigkeit sowie Verfahren zu ihrer Herstellung Expired - Lifetime EP0493280B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9016574A FR2671108B1 (fr) 1990-12-26 1990-12-26 Tubes de cuivre a resistance a la corrosion amelioree et procede pour les obtenir.
FR9016574 1990-12-26

Publications (2)

Publication Number Publication Date
EP0493280A1 EP0493280A1 (de) 1992-07-01
EP0493280B1 true EP0493280B1 (de) 1995-12-06

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EP19910420463 Expired - Lifetime EP0493280B1 (de) 1990-12-26 1991-12-20 Kupferrohre mit verbesserter Korrosionsbeständigkeit sowie Verfahren zu ihrer Herstellung

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EP (1) EP0493280B1 (de)
JP (1) JPH0776429B2 (de)
DE (1) DE69115237T2 (de)
ES (1) ES2080282T3 (de)
FR (1) FR2671108B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19533410B4 (de) * 1995-09-09 2005-11-24 Km Europa Metal Ag Verfahren zur Erzeugung einer Schutzschicht an der inneren Oberfläche eines Kupferrohrs sowie Verwendung von Ziehmitteln

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2566549A (en) * 2017-09-19 2019-03-20 Univ Warwick Method of forming a coating

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1063564A (en) * 1963-09-16 1967-03-30 United States Borax Chem Method for the protection from corrosion of non-ferrous metals
GB1148084A (en) * 1966-12-15 1969-04-10 Foseco Trading Ag Protection of metal surfaces
SU1077950A1 (ru) * 1982-01-20 1984-03-07 Славянский Филиал Всесоюзного Ордена Ленина Научно-Исследовательского И Проектно-Конструкторского Института Металлургического Машиностроения Способ получени защитного покрыти

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19533410B4 (de) * 1995-09-09 2005-11-24 Km Europa Metal Ag Verfahren zur Erzeugung einer Schutzschicht an der inneren Oberfläche eines Kupferrohrs sowie Verwendung von Ziehmitteln

Also Published As

Publication number Publication date
EP0493280A1 (de) 1992-07-01
JPH04301081A (ja) 1992-10-23
FR2671108A1 (fr) 1992-07-03
DE69115237D1 (de) 1996-01-18
JPH0776429B2 (ja) 1995-08-16
DE69115237T2 (de) 1996-05-15
FR2671108B1 (fr) 1994-03-04
ES2080282T3 (es) 1996-02-01

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