EP0647723A1 - Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes - Google Patents
Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes Download PDFInfo
- Publication number
- EP0647723A1 EP0647723A1 EP94114354A EP94114354A EP0647723A1 EP 0647723 A1 EP0647723 A1 EP 0647723A1 EP 94114354 A EP94114354 A EP 94114354A EP 94114354 A EP94114354 A EP 94114354A EP 0647723 A1 EP0647723 A1 EP 0647723A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hard
- tubes
- roughened
- oxygen
- temperature
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000010949 copper Substances 0.000 title claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000007669 thermal treatment Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 238000005422 blasting Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 238000009428 plumbing Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001431 copper ion Inorganic materials 0.000 abstract description 14
- 239000003651 drinking water Substances 0.000 abstract description 13
- 235000020188 drinking water Nutrition 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000009434 installation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000907663 Siproeta stelenes Species 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
-
- 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
- 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
Definitions
- the invention relates to a method for producing seamless drawn semi-hard / hard plumbing pipes made of copper, in which the inner surfaces of the pipes are roughened.
- EP 0 306 810 A2 discloses a method for producing pitting-resistant, hard-drawn tubes made of copper or copper alloys, in which the tubes are first degreased and then the inner surfaces of the tubes are additionally treated with an abrasive. Hereby a roughening of the inner surfaces is achieved, by which the formation of harmful films, e.g. avoid carbon-containing films on the inner surfaces of hard-drawn copper pipes.
- pitting corrosion processes involve copper ion migration, but they follow other laws.
- a high corrosion resistance of copper materials, in particular one against pitting corrosion type 1 does not at the same time result in a lower copper ion release to water.
- the invention has for its object to improve this method in such a way that a reduced copper ion release to drinking water with a normal pH in the range of 6.5 to 9.0 can be guaranteed.
- semi-hard or hard copper installation pipes can now be made available, in which the copper ion release to the drinking water can be kept decisively below the required limit values even over a long period of time.
- Such installation pipes are also resistant to pitting corrosion and can be installed with the known connection and bending techniques.
- the process also allows economical production in bar form with the commonly available manufacturing facilities for seamless copper tubes.
- the method according to the invention can advantageously be used in the manufacture of fittings with reduced copper ion release.
- a first process step there is a so-called preference, in which hot-formed front tubes are cold-formed from cast rods by pulling to an intermediate dimension.
- the inner surfaces of these intermediate tubes are then roughened. This is not only intended to promote the oxidic reaction with the inner surfaces, but also to prevent the oxide layer from no longer uniformly covering during the later hardening process in which the inner surfaces are stretched.
- the roughness depth Ra can range between 0.3 ⁇ m and 1.0 ⁇ m.
- the final dimension of the installation pipes is generated by a hardness train to semi-hard / hard.
- a thermal treatment is carried out again at 175 ° C. to 275 ° C. while introducing an oxygen-containing gas mixture into the interior of the tube in order to achieve an oxide layer in a composition of approximately 12% to 21% oxygen with the residual copper content.
- the production process according to the invention substantially reduces the copper ion release compared to the semi-hard / hard copper installation pipes in the form of bars, which have previously been used for the central drinking water supply, with constant resistance to pitting corrosion.
- the maximum copper ion solubility in installation pipes made in this way surprisingly only reaches a value of 1 mg / l.
- the roughening of the inner surfaces of the intermediate tubes can be carried out according to the features of claim 2 by using blasting agents or by pickling.
- an abrasive e.g. Silicon oxide are used.
- the intermediate tubes are preferably annealed in accordance with the features of claim 3 with a protective gas which has an oxygen content of 1% to 7%.
- the annealing process is preferably carried out at a temperature of about 650 ° C.
- a thin, adherent oxide layer with a thickness of approximately 0.05 ⁇ m to 0.2 ⁇ m can thereby be produced.
- the thermal treatment after the hardening train is advantageously carried out at a temperature of about 250 ° C.
- the hardening tension is carried out in particular with an internal mandrel.
- the degree of deformation here is on average 20%.
- the heating can be carried out convectively, electrically inductively or conductively according to claim 8.
- phosphorus deoxidized copper (SF-Cu) was melted and cast into bars. The bars were then further processed into tubes by means of hot forming and then cold formed to an intermediate dimension.
- the intermediate tubes were then continuously heat-treated at a temperature of 650 ° C. while introducing a gas mixture into the interior of the tube.
- the gas mixture consisted of a protective gas with an oxygen content of 3%.
- a firmly adhering thin copper oxide layer with a layer thickness of 0.15 ⁇ m was formed on the inner surface, the oxygen content of which was determined to be 11.2% by means of X-ray diffractometry.
- the intermediate tubes were hard-drawn to their final dimensions using a standard drawing oil with a degree of deformation of 20% and then degreased on the inside by passing a commercially available degreasing agent through the tubes.
- Pipe sections cut to length and deburred to 300 mm were then subjected to oxidizing heat treatment in a laboratory furnace with circulated air as furnace atmosphere at 250 ° C. for a period of 30 minutes.
- the oxygen content (O2 content) of the copper oxide layer now formed on the inner surface of the tubes was determined by means of energy dispersive analysis (EDX) to 13.8%.
- test pipe sections were arranged vertically and filled with drinking water.
- the copper ion release was determined in a series of tests lasting several months.
- the amount of copper released in mg / l was measured in 24-hour intervals with an absorption spectrometer.
- the pH of the drinking water used was 7.6.
- the upper limit of the measured values for the copper content in drinking water was 1 mg / l.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von nahtlos gezogenen halbharten/harten Installationsrohren aus Kupfer, bei welchem die Innenoberflächen der Rohre aufgerauht werden.The invention relates to a method for producing seamless drawn semi-hard / hard plumbing pipes made of copper, in which the inner surfaces of the pipes are roughened.
Zum Transport von kalten oder erwärmten Trinkwässern ist es bekannt, korrosionsgeschützte nahtlose Installationsrohre aus phosphordesoxidiertem Kupfer (SF-Cu) einzusetzen. Derartige Installationsrohre weisen bei bestimmten Wasserqualitäten die Eigenschaft auf, daß Kupferionen in fließendes oder stehendes Wasser abgegeben werden.For the transport of cold or heated drinking water, it is known to use corrosion-protected seamless installation pipes made of phosphorus-deoxidized copper (SF-Cu). Such installation pipes have the property with certain water qualities that copper ions are released into flowing or standing water.
Gemäß der im offiziellen Journal der EG-Kommission vom 30.08. 1980 veröffentlichten Richtlinie des EG-Rates vom 15.07.1980 über die Qualitätsansprüche an zum menschlichen Verbrauch bestimmten Wässern beträgt der geforderte Maximalgrenzwert der Kupferionenabgabe an das Wasser 3 mg/l nach zwölf Stunden Stagnation in einer Rohrleitung. Ferner haben Untersuchungen ergeben (Zeitschrift "Tribune de l'eau" Vol. 41, Dezember 1988 (Nr. 4) Seiten 29 bis 35), daß korrosionsgeschützte innen oxidierte Kupferrohre für Normalwässer bei etwa 2 mg/l liegende Maximalwerte aufweisen. Das bedeutet, daß die für Hausinstallationen bislang verwendeten Qualitäts-Kupferrohre die Anforderungen der EG-Richtlinie in der Regel erfüllen.According to the in the official journal of the EC commission from 30.08. In 1980, the EC Council Directive of July 15, 1980 on the quality requirements for water intended for human consumption required a maximum limit of copper ion release to water of 3 mg / l after twelve hours of stagnation in a pipeline. Furthermore, studies have shown (Journal "Tribune de l'eau" Vol. 41, December 1988 (No. 4) pages 29 to 35) that corrosion-protected internally oxidized copper pipes for normal water have maximum values of around 2 mg / l. This means that the quality copper pipes previously used for domestic installations generally meet the requirements of the EC directive.
Dennoch kann nicht ausgeschlossen werden, daß die in der Praxis unvermeidlichen Schwankungen in der Qualität der Trinkwässer in dem einen oder anderen Fall diese Maximalwerte überschreiten. Der sich hieraus ergebende Unsicherheitsfaktor wird indessen in der Praxis zwangsläufig in Kauf genommen.Nevertheless, it cannot be ruled out that the inevitable fluctuations in the quality of the drinking water in one case or another exceed these maximum values. The resulting uncertainty factor is inevitably accepted in practice.
Durch die EP 0 306 810 A2 ist ein Verfahren zur Herstellung lochfraßbeständiger hartgezogener Rohre aus Kupfer oder Kupferlegierungen bekannt, bei welchem die Rohre zunächst entfettet und dann die Innenoberflächen der Rohre zusätzlich mit einem Strahlmittel behandelt werden. Hierdurch wird eine Aufrauhung der inneren Oberflächen erzielt, durch das es gelingt, die Bildung von schädlichen Filmen, z.B. kohlenstoffhaltigen Filmen, auf den Innenoberflächen von hartgezogenen Kupferrohren zu vermeiden. In diesem Zusammenhang ist es außerdem bekannt, daß Lochfraßkorrosionsprozesse zwar eine Kupferionenwanderung beinhalten, diese jedoch nach anderen Gesetzmäßigkeiten ablaufen. So zählt es allgemein zum Stand der Technik, daß eine hohe Korrosionsfestigkeit von Kupferwerkstoffen, insbesondere eine solche gegen Lochfraßkorrosion Typ 1, nicht zugleich eine geringere Kupferionenabgabe an Wasser zur Folge hat.EP 0 306 810 A2 discloses a method for producing pitting-resistant, hard-drawn tubes made of copper or copper alloys, in which the tubes are first degreased and then the inner surfaces of the tubes are additionally treated with an abrasive. Hereby a roughening of the inner surfaces is achieved, by which the formation of harmful films, e.g. avoid carbon-containing films on the inner surfaces of hard-drawn copper pipes. In this context, it is also known that pitting corrosion processes involve copper ion migration, but they follow other laws. Thus, it generally belongs to the state of the art that a high corrosion resistance of copper materials, in particular one against pitting corrosion type 1, does not at the same time result in a lower copper ion release to water.
Ausgehend von dem im Oberbegriff des Patentanspruchs 1 beschriebenen Verfahren liegt der Erfindung die Aufgabe zugrunde, dieses Verfahren dahingehend zu verbessern, daß eine verminderte Kupferionenabgabe an Trinkwasser mit einem normalen pH-Wert im Bereich von 6,5 bis 9,0 gewährleistet werden kann.Based on the method described in the preamble of claim 1, the invention has for its object to improve this method in such a way that a reduced copper ion release to drinking water with a normal pH in the range of 6.5 to 9.0 can be guaranteed.
Die Lösung dieser Aufgabe besteht nach der Erfindung in den im kennzeichnenden Teil des Patentanspruchs 1 aufgeführten Merkmalen.This object is achieved according to the invention in the features listed in the characterizing part of claim 1.
Unter Anwendung des erfindungsgemäßen Verfahrens können nunmehr halbharte oder harte Installationsrohre aus Kupfer zur Verfügung gestellt werden, bei denen die Kupferionenabgabe an das Trinkwasser auch über einen langen Zeitraum entscheidend unter den geforderten Grenzwerten gehalten werden kann. Derartige Installationsrohre sind überdies widerstandsfähig gegen Lochfraßkorrosion und können mit den bekannten Verbindungs- und Biegetechniken installiert werden. Das Verfahren erlaubt außerdem eine wirtschaftliche Herstellung in Stangenform mit den üblicherweise verfügbaren Fertigungsanlagen für nahtlose Kupferrohre. Darüberhinaus kann das erfindungsgemäße Verfahren in vorteilhafter Weise bei der Herstellung von Fittings mit verminderter Kupferionenabgabe angewendet werden.Using the method according to the invention, semi-hard or hard copper installation pipes can now be made available, in which the copper ion release to the drinking water can be kept decisively below the required limit values even over a long period of time. Such installation pipes are also resistant to pitting corrosion and can be installed with the known connection and bending techniques. The process also allows economical production in bar form with the commonly available manufacturing facilities for seamless copper tubes. In addition, the method according to the invention can advantageously be used in the manufacture of fittings with reduced copper ion release.
In einem ersten Verfahrensschritt erfolgt ein sogenannter Vorzug, bei welchem aus gegossenen Stangen warm umgeformte Vorrohre durch Ziehen auf eine Zwischenabmessung kalt umgeformt werden. Im Anschluß daran werden die Innenoberflächen dieser Zwischenrohre aufgerauht. Hiermit soll nicht nur die oxidische Reaktion mit den Innenoberflächen begünstigt werden, sondern es soll auch verhindert werden, daß bei dem späteren Härtezug, bei dem eine Streckung der Innenoberflächen erfolgt, die Oxidschicht nicht mehr gleichmäßig deckt. Die Rauhtiefe Ra kann sich hierbei zwischen 0,3 µm und 1,0 µm bewegen. In dem sich anschließenden Glühvorgang bei 350 °C bis 650 °C mit einer Einleitung einer Gasmischung in das Rohrinnere, welche aus einem Schutzgas und Sauerstoff besteht, soll eine dünne haftende Oxidschicht hergestellt werden. Nunmehr wird durch einen Härtezug auf halbhart/hart die Endabmessung der Installationsrohre erzeugt. Im Anschluß an den Härtezug erfolgt nochmals eine thermische Behandlung bei 175 °C bis 275 °C unter Einleitung eines sauerstoffhaltigen Gasgemisches in das Rohrinnere, um eine Oxidschicht in einer Zusammensetzung von etwa 12 % bis 21 % Sauerstoff mit dem Restgehalt Kupfer zu erzielen.In a first process step, there is a so-called preference, in which hot-formed front tubes are cold-formed from cast rods by pulling to an intermediate dimension. The inner surfaces of these intermediate tubes are then roughened. This is not only intended to promote the oxidic reaction with the inner surfaces, but also to prevent the oxide layer from no longer uniformly covering during the later hardening process in which the inner surfaces are stretched. The roughness depth Ra can range between 0.3 µm and 1.0 µm. In the subsequent annealing process at 350 ° C to 650 ° C with the introduction of a gas mixture into the interior of the tube, which consists of a protective gas and oxygen, a thin, adherent oxide layer is to be produced. Now the final dimension of the installation pipes is generated by a hardness train to semi-hard / hard. Following the hardening process, a thermal treatment is carried out again at 175 ° C. to 275 ° C. while introducing an oxygen-containing gas mixture into the interior of the tube in order to achieve an oxide layer in a composition of approximately 12% to 21% oxygen with the residual copper content.
Durch das erfindungsgemäße Fertigungsverfahren wird die Kupferionenabgabe im Vergleich zu den bisher für die zentrale Trinkwasserversorgung eingesetzten halbharten/harten Installationsrohren in Stangenform aus Kupfer wesentlich reduziert bei gleichbleibendem Widerstand gegen Lochfraßkorrosion. Wie interne Langzeituntersuchungen mit Trinkwässern mit einem pH-Wert im Bereich von 6,5 bis 9,0 ergeben haben, erreicht die maximale Kupferionenlöslichkeit bei so gefertigten Installationsrohren überraschenderweise nur einen bei 1 mg/l liegenden Wert.The production process according to the invention substantially reduces the copper ion release compared to the semi-hard / hard copper installation pipes in the form of bars, which have previously been used for the central drinking water supply, with constant resistance to pitting corrosion. As internal long-term investigations with drinking water with a pH value in the range of 6.5 to 9.0 have shown, the maximum copper ion solubility in installation pipes made in this way surprisingly only reaches a value of 1 mg / l.
Dieses in der Fachwelt bislang nicht bekannte Ergebnis dürfte auf den erhöhten Sauerstoffanteil der Kupferoxidschicht im Rohrinnern beruhen. Hierbei ist die eigentliche Bremse für die Kupferionenabgabe eine dichte grüne Malachitdeckschicht, die sich bei Kontakt mit dem Trinkwasser üblicher Qualität auf der Rohrinnenoberfläche ausbildet. Malachit hat die chemische Formel Cu₂[CO₃,(OH)₂]. Zur Bildung von Malachit besteht also ein hoher Bedarf an Sauerstoff, der teils aus dem Trinkwasser und teils aus der Oxidschicht der Rohroberfläche gedeckt wird. Da nun die Rohrinnenoberfläche aufgrund der Erfindung einen höheren Sauerstoffgehalt aufweist, bildet sich erwiesenermaßen die Malachitschicht in kürzester Zeit aus und reduziert damit stark die Kupferionenabgabe.This result, which was previously unknown in the specialist world, may be due to the increased oxygen content of the copper oxide layer in the interior of the tube. The actual brake for the copper ion release is a dense green malachite top layer, which forms on the inner surface of the pipe when it comes into contact with the usual quality drinking water. Malachite has the chemical formula Cu₂ [CO₃, (OH) ₂]. For the formation of malachite there is therefore a high demand for oxygen, which is partly covered by the drinking water and partly by the oxide layer of the pipe surface. Since the inner surface of the tube now has a higher oxygen content due to the invention, it has been proven that the malachite layer forms in a very short time and thus greatly reduces the copper ion release.
Das Aufrauhen der Innenoberflächen der Zwischenrohre kann gemäß den Merkmalen des Patentanspruchs 2 durch Verwendung von Strahlmitteln oder durch Beizen durchgeführt werden. Als Strahlmittel kann z.B. Siliziumoxid zum Einsatz gelangen.The roughening of the inner surfaces of the intermediate tubes can be carried out according to the features of claim 2 by using blasting agents or by pickling. As an abrasive, e.g. Silicon oxide are used.
Das Glühen der Zwischenrohre erfolgt entsprechend den Merkmalen des Patentanspruchs 3 bevorzugt mit einem Schutzgas, das einen Sauerstoffanteil von 1 % bis 7 % aufweist.The intermediate tubes are preferably annealed in accordance with the features of claim 3 with a protective gas which has an oxygen content of 1% to 7%.
Nach Patentanspruch 4 wird der Glühvorgang vorzugsweise bei einer Temperatur von etwa 650 °C durchgeführt. Dadurch kann eine dünne haftende Oxidschicht mit einer Dicke von etwa 0,05 µm bis 0,2 µm erzeugt werden.According to claim 4, the annealing process is preferably carried out at a temperature of about 650 ° C. A thin, adherent oxide layer with a thickness of approximately 0.05 μm to 0.2 μm can thereby be produced.
Die thermische Behandlung nach dem Härtezug erfolgt entsprechend Patentanspruch 5 zweckmäßig bei einer Temperatur von etwa 250 °C. Der Härtezug wird insbesondere mit einem Innendorn durchgeführt. Der Umformgrad beträgt hierbei im Mittel 20 %.The thermal treatment after the hardening train is advantageously carried out at a temperature of about 250 ° C. The hardening tension is carried out in particular with an internal mandrel. The degree of deformation here is on average 20%.
Es kann zweckmäßig sein, die Innenoberfläche der Rohre nach dem Härtezug zu entfetten (Patentanspruch 6). Zum Entfetten kann ein handelsübliches Entfettungsmittel verwendet werden.It may be expedient to degrease the inner surface of the tubes after the hardening process (claim 6). A commercially available degreasing agent can be used for degreasing.
Desweiteren ist es gemäß Patentanspruch 7 sinnvoll, im Zuge der thermischen Behandlung nach dem Härtezug ein Gasgemisch mit mindestens 20 % Sauerstoff in das Rohrinnere zur Bildung einer Oxidschicht einzuleiten.Furthermore, according to claim 7, it makes sense to introduce a gas mixture with at least 20% oxygen into the interior of the tube in the course of the thermal treatment after the hardening train to form an oxide layer.
Die Erwärmung kann nach Patentanspruch 8 konvektiv, elektrisch induktiv oder konduktiv durchgeführt werden.The heating can be carried out convectively, electrically inductively or conductively according to claim 8.
Ein Ausführungsbeispiel der Erfindung ist nachfolgend näher erläutert.An embodiment of the invention is explained in more detail below.
Zunächst wurde phosphordesoxidiertes Kupfer (SF-Cu) geschmolzen und zu Stangen gegossen. Mittels Warmumformung wurden die Stangen dann zu Rohren weiterverarbeitet und anschließend bis auf eine Zwischenabmessung kaltumgeformt.First, phosphorus deoxidized copper (SF-Cu) was melted and cast into bars. The bars were then further processed into tubes by means of hot forming and then cold formed to an intermediate dimension.
Sodann wurde die Innenoberfläche der Zwischenrohre mit Siliziumoxid als Strahlmittel behandelt. Als Ergebnis wurde eine Rauhigkeit Ra = 0,52 µm gemessen.The inner surface of the intermediate tubes was then treated with silicon oxide as the blasting agent. As a result, a roughness Ra = 0.52 µm was measured.
Die Zwischenrohre wurden dann bei einer Temperatur von 650 °C unter Einleitung eines Gasgemisches in das Rohrinnere kontinuierlich wärmebehandelt. Das Gasgemisch setzte sich aus einem Schutzgas mit einem sauerstoffanteil von 3 % zusammen. Es bildete sich auf der Innenoberfläche eine fest haftende dünne Kupferoxidschicht mit einer Schichtdicke von 0,15 µm aus, deren Sauerstoffgehalt mittels Röntgendiffraktometrie auf 11,2 % bestimmt wurde.The intermediate tubes were then continuously heat-treated at a temperature of 650 ° C. while introducing a gas mixture into the interior of the tube. The gas mixture consisted of a protective gas with an oxygen content of 3%. A firmly adhering thin copper oxide layer with a layer thickness of 0.15 μm was formed on the inner surface, the oxygen content of which was determined to be 11.2% by means of X-ray diffractometry.
Im nächsten Arbeitsschritt wurden die Zwischenrohre unter Verwendung eines Standardziehöls auf die Endabmessung mit einem Umformgrad von 20 % hartgezogen und anschließend innenseitig dadurch entfettet, daß ein handelsübliches Entfettungsmittel durch die Rohre geleitet wurde.In the next step, the intermediate tubes were hard-drawn to their final dimensions using a standard drawing oil with a degree of deformation of 20% and then degreased on the inside by passing a commercially available degreasing agent through the tubes.
Auf 300 mm abgelängte und entgratete Rohrabschnitte wurden dann in einem Laborofen mit umgewälzter Luft als Ofenatmosphäre bei 250 °C über eine Dauer von 30 min oxidierend wärmebehandelt. Der Sauerstoffgehalt (O₂-Gehalt) der jetzt ausgebildeten Kupferoxidschicht an der Innenoberfläche der Rohre wurde mittels energiedispersiver Analyse (EDX) auf 13,8 % bestimmt.Pipe sections cut to length and deburred to 300 mm were then subjected to oxidizing heat treatment in a laboratory furnace with circulated air as furnace atmosphere at 250 ° C. for a period of 30 minutes. The oxygen content (O₂ content) of the copper oxide layer now formed on the inner surface of the tubes was determined by means of energy dispersive analysis (EDX) to 13.8%.
Nunmehr wurden diese Rohrabschnitte (Testrohrabschnitte) senkrecht angeordnet und mit Trinkwasser gefüllt. In einer mehrmonatigen Untersuchungsreihe wurde die Kupferionenabgabe bestimmt. Hierzu wurde jeweils im 24-Stunden-Takt die abgegebene Kupfermenge in mg/l mit einem Absorptionsspektrometer gemessen. Der pH-Wert des verwendeten Trinkwassers betrug 7,6.Now these pipe sections (test pipe sections) were arranged vertically and filled with drinking water. The copper ion release was determined in a series of tests lasting several months. For this purpose, the amount of copper released in mg / l was measured in 24-hour intervals with an absorption spectrometer. The pH of the drinking water used was 7.6.
Die obere Grenze der Meßwerte für den Kupfergehalt im Trinkwasser lag bei 1 mg/l.The upper limit of the measured values for the copper content in drinking water was 1 mg / l.
Claims (8)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4334536 | 1993-10-09 | ||
| DE19934334536 DE4334536A1 (en) | 1993-10-09 | 1993-10-09 | Process for the production of seamless drawn semi-hard / hard installation pipes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0647723A1 true EP0647723A1 (en) | 1995-04-12 |
| EP0647723B1 EP0647723B1 (en) | 2000-04-12 |
Family
ID=6499828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19940114354 Expired - Lifetime EP0647723B1 (en) | 1993-10-09 | 1994-09-13 | Process for manufacturing of seamless drawn medium hard/hard copper fitting tubes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0647723B1 (en) |
| DE (2) | DE4334536A1 (en) |
| DK (1) | DK0647723T3 (en) |
| ES (1) | ES2144475T3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0955394A2 (en) * | 1998-05-05 | 1999-11-10 | KM Europa Metal AG | Process for producing a protective coating on the interior surface of a copper pipe |
| EP0976845A1 (en) * | 1998-07-30 | 2000-02-02 | Outokumpu Oyj | Method for producing copper tubes |
| US6434967B2 (en) | 1999-06-18 | 2002-08-20 | Elkay Manufacturing Company | Process for forming copper containing components providing water effluent with lowered copper concentrations |
| WO2004078372A1 (en) * | 2003-03-07 | 2004-09-16 | Outokumpu Oyj | Method for treating the inner surface of a tube |
| DE19533410B4 (en) * | 1995-09-09 | 2005-11-24 | Km Europa Metal Ag | Method for producing a protective layer on the inner surface of a copper pipe and use of drawing agents |
| TWI719750B (en) * | 2019-12-10 | 2021-02-21 | 金允成企業股份有限公司 | Forging and forming method of aluminum alloy pipe fittings |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007055446A1 (en) * | 2007-11-12 | 2009-05-14 | Hansgrohe Ag | Provision of water-bearing components from brass alloys with reduced metal ion release |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2028184A (en) * | 1978-08-07 | 1980-03-05 | Crane Enfield Metals Pty | Production of copper tubing |
| GB2055061A (en) * | 1979-07-31 | 1981-02-25 | Liege Usines Cuivre Zinc | Improvements concerning copper or copper-alloy tubes for pipes used in sanitary, condenser and other installations |
| GB2075391A (en) * | 1980-05-10 | 1981-11-18 | Kabel Metallwerke Ghh | Process for treating copper tubes |
| EP0128846A1 (en) * | 1983-06-09 | 1984-12-19 | Trefimetaux | Process for improving the flexibility of cold-worked copper tubes by partial annealing |
| EP0281641A1 (en) * | 1987-03-07 | 1988-09-14 | Wieland-Werke Ag | Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes |
| FR2668170A1 (en) * | 1990-10-18 | 1992-04-24 | Trefimetaux | PROCESS FOR IMPROVING THE STRENGTH OF HARD COPPER TUBES BY DYNAMIC THERMAL TREATMENT. |
-
1993
- 1993-10-09 DE DE19934334536 patent/DE4334536A1/en not_active Withdrawn
-
1994
- 1994-09-13 DE DE59409284T patent/DE59409284D1/en not_active Expired - Fee Related
- 1994-09-13 EP EP19940114354 patent/EP0647723B1/en not_active Expired - Lifetime
- 1994-09-13 DK DK94114354T patent/DK0647723T3/en active
- 1994-09-13 ES ES94114354T patent/ES2144475T3/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2028184A (en) * | 1978-08-07 | 1980-03-05 | Crane Enfield Metals Pty | Production of copper tubing |
| GB2055061A (en) * | 1979-07-31 | 1981-02-25 | Liege Usines Cuivre Zinc | Improvements concerning copper or copper-alloy tubes for pipes used in sanitary, condenser and other installations |
| GB2075391A (en) * | 1980-05-10 | 1981-11-18 | Kabel Metallwerke Ghh | Process for treating copper tubes |
| EP0128846A1 (en) * | 1983-06-09 | 1984-12-19 | Trefimetaux | Process for improving the flexibility of cold-worked copper tubes by partial annealing |
| EP0281641A1 (en) * | 1987-03-07 | 1988-09-14 | Wieland-Werke Ag | Process for improving the corrosion resistance of hard or semi-hard copper fitting tubes |
| FR2668170A1 (en) * | 1990-10-18 | 1992-04-24 | Trefimetaux | PROCESS FOR IMPROVING THE STRENGTH OF HARD COPPER TUBES BY DYNAMIC THERMAL TREATMENT. |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19533410B4 (en) * | 1995-09-09 | 2005-11-24 | Km Europa Metal Ag | Method for producing a protective layer on the inner surface of a copper pipe and use of drawing agents |
| EP0955394A2 (en) * | 1998-05-05 | 1999-11-10 | KM Europa Metal AG | Process for producing a protective coating on the interior surface of a copper pipe |
| EP0955394A3 (en) * | 1998-05-05 | 2000-04-12 | KM Europa Metal AG | Process for producing a protective coating on the interior surface of a copper pipe |
| EP0976845A1 (en) * | 1998-07-30 | 2000-02-02 | Outokumpu Oyj | Method for producing copper tubes |
| US6434967B2 (en) | 1999-06-18 | 2002-08-20 | Elkay Manufacturing Company | Process for forming copper containing components providing water effluent with lowered copper concentrations |
| WO2004078372A1 (en) * | 2003-03-07 | 2004-09-16 | Outokumpu Oyj | Method for treating the inner surface of a tube |
| EA007545B1 (en) * | 2003-03-07 | 2006-10-27 | Отокумпу Оюй | Method for treating the inner surface of a tube |
| TWI719750B (en) * | 2019-12-10 | 2021-02-21 | 金允成企業股份有限公司 | Forging and forming method of aluminum alloy pipe fittings |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0647723T3 (en) | 2000-08-28 |
| DE4334536A1 (en) | 1995-04-13 |
| ES2144475T3 (en) | 2000-06-16 |
| EP0647723B1 (en) | 2000-04-12 |
| DE59409284D1 (en) | 2000-05-18 |
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