EP1347078A2 - Process for reducing the solubility of copper at the inner surface of a copper pipe - Google Patents

Process for reducing the solubility of copper at the inner surface of a copper pipe Download PDF

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Publication number
EP1347078A2
EP1347078A2 EP03005781A EP03005781A EP1347078A2 EP 1347078 A2 EP1347078 A2 EP 1347078A2 EP 03005781 A EP03005781 A EP 03005781A EP 03005781 A EP03005781 A EP 03005781A EP 1347078 A2 EP1347078 A2 EP 1347078A2
Authority
EP
European Patent Office
Prior art keywords
copper
tin
crystals
plane
solubility
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.)
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Application number
EP03005781A
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German (de)
French (fr)
Other versions
EP1347078A3 (en
Inventor
Achim Dr.-Ing. Baukloh
Ulrich Dr.-Ing. Reiter
Stefan Dr. Rer Nat Priggemeyer
Christian Dipl.-Ing. Triquet
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KME Special Products GmbH and Co KG
Original Assignee
KM Europa Metal AG
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Publication date
Application filed by KM Europa Metal AG filed Critical KM Europa Metal AG
Publication of EP1347078A2 publication Critical patent/EP1347078A2/en
Publication of EP1347078A3 publication Critical patent/EP1347078A3/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C23C18/16—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 reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals

Definitions

  • the invention relates to a method for reducing the copper solubility at the inner surface of a copper pipe.
  • the invention is based on the object To create processes that significantly reduce the copper solubility at the guaranteed inner surface of a copper pipe.
  • the invention has recognized that in the case of directional crystal growth the tin coating a high packing density of the tin crystals can be achieved can.
  • the high packing density of the tin layer leads to a very homogeneous, evenly formed and extremely stable copper / tin phase.
  • the Tin layer evenly and with a small thickness on the order of about 0.1 ⁇ m to 3 ⁇ m applied with a small number of pores. That directed Crystal growth is achieved through a targeted adjustment of the process parameters Surface pre-treatment (degreasing and pickling), flow conditions (Flow rate ⁇ 1 m / s), temperature (50 ° C to 80 ° C) and time (1 min up to 10 min).
  • the determination of the crystal structure of tin is preferred using the results performed by X-ray diffraction experiments.
  • X-ray diffraction experiments When interacting between X-rays and single crystals are the incident waves because of the lattice structure of the tin crystals bent in discrete spatial directions. While the position of a diffraction direction by the orientation of the crystal lattice to Primary beam, the grating dimensions and the wavelength used is determined The intensity of the diffracted beam depends on the distribution of the tin atoms in the Unit cell.
  • Claim 2 the plane (101) of the tin crystals parallel to the inner Surface of the copper pipe aligned.
  • a further improvement going beyond that is defined in claim 4 achieved in that the plane (101) of the copper and tin crystals parallel to each other and the directions [101] are aligned perpendicular to each other.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Inner surface of a copper pipe is sealed by a layer of tin coating, to prevent copper ions dispersing into drinking water flowing through it. The process parameters of the tin coating are set to give a consistent tin crystal growth during degreasing and pickling, adjusting the flow speed to at most 1 m/second, at a temperature of 50-80 degreesC in a working time of 1-10 minutes. The plane of the tin crystals is parallel to the plane of the copper crystals, and their directions are at right angles to each other.

Description

Die Erfindung betrifft ein Verfahren zur Verringerung der Kupferlöslichkeit an der inneren Oberfläche eines Kupferrohrs.The invention relates to a method for reducing the copper solubility at the inner surface of a copper pipe.

Es ist bekannt, die innere Oberfläche eines Kupferrohrs mit Zinn zu beschichten, um mit Hilfe einer derartigen Zinnschicht aus dem Kupfer gelöste Kupferionen daran zu hindern, in Trinkwasser überzutreten, sofern ein derartiges Kupferrohr als Bestandteil einer Trinkwasserleitung verwendet wird. In diesem Zusammenhang ist auch die europäische Richtlinie für die Trinkwasserverordnung zu beachten.It is known to coat the inner surface of a copper pipe with tin copper ions released from the copper with the aid of such a tin layer Prevent from entering into drinking water, provided that such a copper pipe as a component a drinking water pipe is used. In this context, too European guidelines for the drinking water regulation to be observed.

Bei den bislang bekannten Verfahren zum Aufbringen einer Zinnschicht auf die innere Oberfläche eines Kupferrohrs werden nur ungeordnete Kristalle gebildet. Die Packungsdichte der Zinnkristalle war damit unbefriedigend. Kupferionen können daher über die Zinnschicht in das Trinkwasser übertreten.In the previously known methods for applying a tin layer on the only disordered crystals are formed on the inner surface of a copper tube. The The packing density of the tin crystals was unsatisfactory. Copper ions can therefore enter the drinking water via the tin layer.

Der Erfindung liegt - ausgehend vom Stand der Technik - die Aufgabe zugrunde, ein Verfahren zu schaffen, das eine deutliche Verringerung der Kupferlöslichkeit an der inneren Oberfläche eines Kupferrohrs gewährleistet. Starting from the prior art, the invention is based on the object To create processes that significantly reduce the copper solubility at the guaranteed inner surface of a copper pipe.

Diese Aufgabe wird mit den im Patentanspruch 1 angegebenen Merkmalen gelöst.This object is achieved with the features specified in claim 1.

Die Erfindung hat erkannt, daß bei einem gerichteten Kristallwachstum im Verlaufe der Zinnbeschichtung eine hohe Packungsdichte der Zinnkristalle erreicht werden kann. Die hohe Packungsdichte der Zinnschicht führt zu einer sehr homogenen, gleichmäßig ausgebildeten und äußerst stabilen Kupfer/Zinn-Phase. Dazu wird die Zinnschicht gleichmäßig und mit einer geringen Dicke in einer Größenordnung von etwa 0,1 µm bis 3 µm bei geringer Porenanzahl aufgebracht. Das gerichtete Kristallwachstum wird durch eine gezielte Einstellung der Prozeßparameter Oberflächenvorbehandlung (Entfetten und Beizen), Strömungsbedingungen (Strömungsgeschwindigkeit < 1 m/s), Temperatur (50 °C bis 80 °C) und Zeit (1 min bis 10 min) erreicht.The invention has recognized that in the case of directional crystal growth the tin coating a high packing density of the tin crystals can be achieved can. The high packing density of the tin layer leads to a very homogeneous, evenly formed and extremely stable copper / tin phase. For this, the Tin layer evenly and with a small thickness on the order of about 0.1 µm to 3 µm applied with a small number of pores. That directed Crystal growth is achieved through a targeted adjustment of the process parameters Surface pre-treatment (degreasing and pickling), flow conditions (Flow rate <1 m / s), temperature (50 ° C to 80 ° C) and time (1 min up to 10 min).

Trotz des Sachverhalts, daß schon nach relativ kurzer Betriebszeit kein metallisches Zinn mehr an der Rohroberfläche festgestellt werden kann, bleibt dennoch die Eigenschaft der geringen Kupferlöslichkeit aufgrund der äußerst stabilen Cu/Sn-Phase erhalten. Erfindungsgemäß behandelte Rohroberflächen zeichnen sich durch eine sehr geringe Kupferlöslichkeit und hohe Beständigkeit aus.Despite the fact that after a relatively short period of operation no metallic Tin can still be found on the pipe surface, but remains Property of low copper solubility due to the extremely stable Cu / Sn phase receive. Pipe surfaces treated according to the invention are notable for a very low copper solubility and high resistance.

Die Ermittlung der Kristallstruktur von Zinn wird bevorzugt mit Hilfe der Ergebnisse von Röntgenbeugungsexperimenten durchgeführt. Bei der Wechselwirkung zwischen der Röntgenstrahlung und Einkristallen werden die einfallenden Wellen wegen des gitterhaften Aufbaus der Zinnkristalle in diskrete Raumrichtungen gebeugt. Während die Lage einer Beugungsrichtung durch die Orientierung des Kristallgitters zum Primärstrahl, die Gitterdimensionen und die verwendete Wellenlänge bestimmt wird, hängt die Intensität des abgebeugten Strahls von der Verteilung der Zinnatome in der Elementarzelle ab. The determination of the crystal structure of tin is preferred using the results performed by X-ray diffraction experiments. When interacting between X-rays and single crystals are the incident waves because of the lattice structure of the tin crystals bent in discrete spatial directions. While the position of a diffraction direction by the orientation of the crystal lattice to Primary beam, the grating dimensions and the wavelength used is determined The intensity of the diffracted beam depends on the distribution of the tin atoms in the Unit cell.

Dazu wurde von einem erfindungsgemäß mit Zinn beschichteten Kupferrohr ein Längenabschnitt als Probe abgeteilt. Diese Probe wurde dann in Längsrichtung geschlitzt und diese längsgeschlitzte Probe anschließend zu einem Flachmaterial aufgebogen. Dieses Flachmaterial mit der Zinnbeschichtung nach oben wurde dann mit Röntgenstrahlen mit λ(FeKα) = 1.9373 Å bestrahlt, wobei der Röntgenstrahl unter verschiedenen Beugungswinkeln auf die ebene Probe gerichtet wurde. Die Ergebnisse zeigen, daß unter verschiedenen Winkeln eine hohe Röntgenstrahl-Beugungsintensität festgestellt wurde, womit der Beweis erbracht ist, daß die Röntgenstrahlen nahezu 100% reflektiert werden. Die Zinnatome weisen folglich eine sehr hohe Packungsdichte auf. Es wird eine zufriedenstellende Sperrschicht für die Kupferionen gegen einen Übertritt in das Trinkwasser gebildet.For this purpose, a length section was divided as a sample from a copper pipe coated with tin according to the invention. This sample was then slit in the longitudinal direction and this longitudinally slit sample was then bent into a flat material. This flat material with the tin coating facing upwards was then irradiated with X-rays with λ (FeK α ) = 1.9373 Å, the X-ray beam being directed onto the flat sample at different diffraction angles. The results show that a high X-ray diffraction intensity was found at different angles, which proves that the X-rays are reflected almost 100%. The tin atoms therefore have a very high packing density. A satisfactory barrier layer for the copper ions is prevented from entering the drinking water.

In vorteilhafter Weitergestaltung des erfindungsgemäßen Grundgedankens wird nach Patentanspruch 2 die Ebene (101) der Zinnkristalle parallel zu der inneren Oberfläche des Kupferrohrs ausgerichtet.In an advantageous further development of the basic idea of the invention Claim 2 the plane (101) of the tin crystals parallel to the inner Surface of the copper pipe aligned.

In diesem Zusammenhang ist es dann gemäß Patentanspruch 3 ferner von Vorteil, wenn die Ebene (101) der Zinnkristalle parallel zu der Ebene (101) der Kupferkristalle ausgerichtet wird.In this context, it is then also advantageous according to claim 3, if the plane (101) of the tin crystals is parallel to the plane (101) of the copper crystals is aligned.

Eine darüber hinausgehende weitere Verbesserung wird nach Patentanspruch 4 dadurch erzielt, daß die Ebene (101) der Kupfer- und Zinnkristalle parallel zueinander und die Richtungen [101] senkrecht aufeinander ausgerichtet werden.A further improvement going beyond that is defined in claim 4 achieved in that the plane (101) of the copper and tin crystals parallel to each other and the directions [101] are aligned perpendicular to each other.

Die vorteilhafte Zinnbeschichtung wurde durch folgende interne Vergleichsuntersuchung bestätigt: The advantageous tin coating was determined by the following internal comparison test approved:

Ein erfindungsgemäß beschichtetes Kupferrohr wurde 15 Monate mit Trinkwasser in Kontakt gebracht. Aufgrund dieses Kontakts entstand auf der inneren Oberfläche eine Zinnhydroxidschicht (Sn3O2(OH)2). Von diesem Kupferrohr wurde ebenfalls ein Längenabschnitt abgetrennt, in Längsrichtung aufgeschnitten, flach gebogen und dann einer Röntgenbestrahlung mit λ (FeKα) = 1.9373 Å unterworfen. Hierbei wurde festgestellt, daß die Reflektion der Röntgenstrahlen (Röntgenstrahlenbeugungsintensität) deutlich unter 100 % lag. Man hätte also annehmen können, daß das Ziel der Erfindung nicht erreicht wurde.A copper pipe coated according to the invention was brought into contact with drinking water for 15 months. As a result of this contact, a tin hydroxide layer (Sn 3 O 2 (OH) 2 ) was formed on the inner surface. A length section was also cut from this copper tube, cut open in the longitudinal direction, bent flat and then subjected to X-ray radiation with λ (FeK α ) = 1.9373 Å. It was found that the reflection of the X-rays (X-ray diffraction intensity) was significantly below 100%. One might have assumed that the object of the invention was not achieved.

Anschließend wurde die Zinnhydroxidschicht vollkommen entfernt, so daß der ursprüngliche Beschichtungszustand wieder vorhanden war. Das heißt, auf dem Kupfer lag eine Kupfer/Zinn-Phase (Cu6Sn5).The tin hydroxide layer was then completely removed, so that the original coating state was restored. This means that there was a copper / tin phase (Cu 6 Sn 5 ) on the copper.

Dann wurde wiederum eine Röntgenbestrahlung vorgenommen, bei der eine nahezu 100%ige Reflektion festgestellt wurde. Hiermit ist das Verfahren gemäß der Erfindung vollauf in seiner Vorteilhaftigkeit bestätigt.Then an X-ray was again performed, in which an almost 100% reflection was found. This is the procedure according to Invention fully confirmed in its advantageousness.

Claims (4)

Verfahren zur Verringerung der Kupferlöslichkeit an der inneren Oberfläche eines Kupferrohrs, bei welchem zum Erreichen eines gleichmäßigen gerichteten Kristallwachstums im Verlauf der Zinnbeschichtung und Bildung einer Kupfer/Zinn-Phase die Prozeßparameter Oberflächenbehandlung (Entfetten und Beizen), Strömungsbedingungen (Strömungsgeschwindigkeit < 1 m/s), Temperatur (50 °C bis 80 °C) und Zeit (1 min bis 10 min) gezielt aufeinander abgestimmt werden.Process for reducing the copper solubility on the inner surface of a Copper pipe, in which to achieve a uniform directional Crystal growth in the course of the tin coating and formation of a Copper / tin phase the process parameters surface treatment (degreasing and Pickling), flow conditions (flow speed <1 m / s), Temperature (50 ° C to 80 ° C) and time (1 min to 10 min) targeted to each other be coordinated. Verfahren nach Patentanspruch 1, bei welchem die Ebene (101) der Zinnkristalle parallel zu der inneren Oberfläche des Kupferrohrs ausgerichtet wird.Method according to claim 1, in which the plane (101) of the tin crystals is aligned parallel to the inner surface of the copper tube. Verfahren nach Patentanspruch 1 oder 2, bei welchem die Ebene (101) der Zinnkristalle parallel zu der Ebene (101) der Kupferkristalle ausgerichtet wird.Method according to claim 1 or 2, in which the plane (101) of the tin crystals is aligned parallel to the plane (101) of the copper crystals. Verfahren nach einem der Patentansprüche 1 bis 3, bei welchem die Ebenen (101) der Kupfer- und Zinnkristalle parallel zueinander und die Richtungen [101] senkrecht aufeinander ausgerichtet werden.Method according to one of claims 1 to 3, in which the levels (101) the copper and tin crystals parallel to each other and the directions [101] be aligned perpendicular to each other.
EP03005781A 2002-03-23 2003-03-14 Process for reducing the solubility of copper at the inner surface of a copper pipe Withdrawn EP1347078A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10213185 2002-03-23
DE10213185A DE10213185A1 (en) 2002-03-23 2002-03-23 Process for reducing copper solubility on the inner surface of a copper pipe

Publications (2)

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EP1347078A2 true EP1347078A2 (en) 2003-09-24
EP1347078A3 EP1347078A3 (en) 2004-02-11

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EP03005781A Withdrawn EP1347078A3 (en) 2002-03-23 2003-03-14 Process for reducing the solubility of copper at the inner surface of a copper pipe

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US (1) US20030178107A1 (en)
EP (1) EP1347078A3 (en)
JP (1) JP2004043960A (en)
AU (1) AU2003200591B2 (en)
CA (1) CA2419630A1 (en)
DE (1) DE10213185A1 (en)
MX (1) MXPA03001950A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5419275B2 (en) * 2009-11-30 2014-02-19 Ｊｘ日鉱日石金属株式会社 Reflow Sn plating material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0848084A1 (en) * 1996-06-05 1998-06-17 Sumitomo Light Metal Industries, Ltd. Internally tin-plated copper pipe manufacturing method
JPH10317158A (en) * 1997-05-19 1998-12-02 Hitachi Cable Ltd Tube whose inner surface is plated with tin or tin alloy, and its plating method
EP0915183A1 (en) * 1997-11-07 1999-05-12 ATOTECH Deutschland GmbH Tinning of copper tubes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2282511A (en) * 1940-03-20 1942-05-12 American Brass Co Coating cupreous surfaces with tin
JP2804722B2 (en) * 1994-10-26 1998-09-30 株式会社神戸製鋼所 Tin plating method on the inner surface of copper or copper alloy tube
DE19653765A1 (en) * 1996-12-23 1998-06-25 Km Europa Metal Ag Tinned copper pipe and process for coating a copper pipe
DE10003582A1 (en) * 2000-01-28 2001-08-02 Km Europa Metal Ag Production of a tin layer on the inner surface of hollow copper alloy parts e.g., brass comprises reducing the lead content of the inner surface by treating with an aqueous reduction solution and plating with tin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0848084A1 (en) * 1996-06-05 1998-06-17 Sumitomo Light Metal Industries, Ltd. Internally tin-plated copper pipe manufacturing method
JPH10317158A (en) * 1997-05-19 1998-12-02 Hitachi Cable Ltd Tube whose inner surface is plated with tin or tin alloy, and its plating method
EP0915183A1 (en) * 1997-11-07 1999-05-12 ATOTECH Deutschland GmbH Tinning of copper tubes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 03, 31. März 1999 (1999-03-31) & JP 10 317158 A (HITACHI CABLE LTD), 2. Dezember 1998 (1998-12-02) *

Also Published As

Publication number Publication date
MXPA03001950A (en) 2004-10-29
EP1347078A3 (en) 2004-02-11
US20030178107A1 (en) 2003-09-25
DE10213185A1 (en) 2003-10-02
JP2004043960A (en) 2004-02-12
AU2003200591B2 (en) 2008-07-31
AU2003200591A1 (en) 2003-10-09
CA2419630A1 (en) 2003-09-23

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