EP0091627A2 - Process for cleaning, degreasing and activating metallic surfaces - Google Patents

Process for cleaning, degreasing and activating metallic surfaces Download PDF

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Publication number
EP0091627A2
EP0091627A2 EP83103267A EP83103267A EP0091627A2 EP 0091627 A2 EP0091627 A2 EP 0091627A2 EP 83103267 A EP83103267 A EP 83103267A EP 83103267 A EP83103267 A EP 83103267A EP 0091627 A2 EP0091627 A2 EP 0091627A2
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EP
European Patent Office
Prior art keywords
treated
composite parts
cleaning
solutions
steel
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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EP83103267A
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German (de)
French (fr)
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EP0091627A3 (en
Inventor
Wolfgang Dr. Morlock
Raschad Mady
Lutz Schellenberg
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Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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Publication of EP0091627A2 publication Critical patent/EP0091627A2/en
Publication of EP0091627A3 publication Critical patent/EP0091627A3/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Withdrawn legal-status Critical Current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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling

Definitions

  • the invention relates to an improved method for cleaning and degreasing and activating composite parts made of iron or steel and zinc or galvanized steel or aluminum or aluminized steel before a subsequent phosphating treatment of the same, at elevated temperatures and with the aid of aqueous cleaner and / or activation solutions.
  • Composite parts of this type are increasingly being used by the automotive industry in the construction of automobile bodies in order to achieve improved corrosion protection of the bodies.
  • the iron materials or steel sheets commonly used for body construction are used in combination with both electrolytic and hot-dip galvanized steel.
  • zinc alloys are becoming established for this purpose, which can contain, for example, 2 to 10% of iron, nickel, cobalt or aluminum as an alloy partner.
  • Composite parts made of steel and zinc may also be considered here.
  • Corresponding composite parts made from body steel and aluminum or from steel and aluminized steel - preferably fire-aluminized steel - are also used.
  • Such cleaning solutions generally contain surface-active substances, such as wetting agents and emulsifiers, and so-called builder substances, for example sodium hydroxide, alkali metal carbonates, alkali metal phosphates, such as orthophosphates and corresponding condensed phosphates, for example sodium pyrophosphate or sodium triphosphate, for strengthening the emulsifying, saponification and dirt-carrying capacity optionally also silicates and borates.
  • surface-active substances such as wetting agents and emulsifiers
  • builder substances for example sodium hydroxide, alkali metal carbonates, alkali metal phosphates, such as orthophosphates and corresponding condensed phosphates, for example sodium pyrophosphate or sodium triphosphate, for strengthening the emulsifying, saponification and dirt-carrying capacity optionally also silicates and borates.
  • builder substances for example sodium hydroxide, alkali metal carbonates, alkali metal phosphates, such as orthophosphat
  • the cleaning and degreasing solutions as well as the phosphating solutions are usually applied to the metal surfaces to be treated in a spray, dip or combined spray-dip process.
  • the workpieces - including the composite parts discussed above - are usually cleaned after cleaning or degreasing Rinsed water and then subjected to a phosphating process in a known manner. If necessary, however, the activation can also take place after the cleaning and degreasing stage in a separate process step.
  • the cleaned and phosphated workpieces, i.e. automobile bodies are then painted, usually using the electro-dip painting process.
  • the metals zinc and aluminum contained in the composite parts discussed above dissolve due to their amphoteric character both in acids and in bases with evolution of hydrogen. In the pH range from. 7 to about 12.5, however, these metals are considered to be relatively stable, since the dissolution of the metal surface is reduced by the formation of protective layers thereon.
  • the commonly used alkaline cleaning solutions are in the previously mentioned pH range, so that no corrosion problems would be expected here. In practice, however, it has been shown that with the composite construction described above - conductive composite - corrosion of the zinc and aluminum surfaces also occurs in the pH range which is considered to be harmless. This results in punctiform, pitting-like corrosion phenomena as well as extensive damage to the zinc or aluminum surfaces.
  • the object of the present invention is therefore to develop a method for cleaning and degreasing and activating composite parts made of steel and galvanized or aluminized steel prior to phosphating, in which the corrosion phenomena described above, due to the use of alkaline and also weakly acidic cleaning - and degreasing solutions - are avoided.
  • the flow according to the invention completely prevents the flow of galvanic currents - and thus the occurrence of corrosive phenomena.
  • the bath container made of steel of the cleaning or degreasing bath can serve as a counter electrode to the composite part. If, for example, bath containers made of non-conductive material - plastic are used in the process, an electrode made of sheet steel is introduced into the cleaning bath and the counter potential is built up between this and the composite part. In the sense of the method according to the invention, however, an electrode additionally arranged in the bath can also be present in a steel bath container. It is only essential to the invention that a counter potential is present between the composite part on the one hand and the bath container and / or additional electrode on the other hand, both composite both the part and the electrode are in contact with the bath liquid.
  • customary cleaning and degreasing solutions can be used which have a pH in the range from 6 to 13.
  • cleaning solutions which may have the ingredients listed above.
  • phosphates, carbonates, borates, silicates or hydroxides of alkali metals are suitable as builder substances.
  • Corresponding ammonium compounds can also be used for this.
  • Further constituents of the cleaning solutions to be used according to the invention are customary anionic, cationic or nonionic wetting agents and emulsifiers. Of these, however, the nonionic types are preferably used, for example addition products of ethylene oxide with fatty alcohols, alkylphenols, fatty amines or polyoxypropylene glycols.
  • hydroxypolycarboxylic acids such as citric acid
  • aminopolycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid
  • phosphonic acids such as ethane-1-hydroxy-1,1-diphosphonic acid or aminotrimethylenephosphonic acid
  • the layer refiners and activators for example titanium orthophosphate, which are customary and known for this purpose, can also be added to the cleaning solutions.
  • the method according to the invention can be used in the usual standing baths or also in the continuous systems frequently used in the automotive industry.
  • the cleaning solutions can be applied either by immersion or spraying or in a combined spray-immersion process.
  • the composite parts are treated with solutions which have a pH in the range from 7 to 11.
  • the temperature of the aqueous cleaning and degreasing solutions should preferably be in the range from 35 to 70.degree.
  • the composite parts are treated with a 0.1 to 3 percent by weight aqueous solution containing 72.5 percent by weight sodium tetraborate x 10 H 2 0 18 percent by weight sodium dihydrogen orthophosphate and 9.5 percent by weight of an addition product Contains 10 moles of ethylene oxide in nonylphenol.
  • a counter potential is applied which is at least twice as high as the potential which arises due to the voltage series in the solution in question. In this way, possible fluctuations in the potential that is established can be absorbed, so that constant potential measurements for monitoring purposes are unnecessary.
  • the phosphating and the subsequent painting of the composite parts or workpieces takes place in the customary manner.
  • the cleaning solution was in a bath tank made of structural steel.
  • a composite workpiece made of electrolytically galvanized steel and steel material No. 11 405 body steel
  • a potential of 655 millivolts was measured.
  • a potential of 575 millivolts was measured when immersing a corresponding composite workpiece with hot-dip galvanized steel (sendzimir-galvanized steel, redressed).
  • a bath container made of non-conductive material (plastic) was used.
  • the previously mentioned cleaning solution was used as the electrolyte under the conditions mentioned.
  • a steel sheet was immersed in the bath solution as an additional electrode.
  • a potential of 193 millivolts was measured between the composite workpiece made of body steel and electrolytically galvanized steel, which was immersed in the cleaning bath. Signs of corrosion on the galvanized steel were clearly visible.
  • "counter potentials of 400 millivolts, 500 millivolts and 1,000 millivolts were applied. With all the cathodic counter potentials mentioned, there were no visible signs of corrosion on the electrolytically galvanized steel after 5 minutes of immersion in the cleaner.
  • a counter potential of 400 millivolts was applied when using composite workpieces made of body steel and hot-dip galvanized steel. No signs of corrosion occurred after the same dive time. Even subsequent layer-forming phosphating of the samples treated according to the invention - in a phosphating bath containing zinc oxide, phosphoric acid and nitric acid - resulted in completely defect-free zinc surfaces; whereas the corrosion damage clearly appeared in the samples not pretreated according to the invention.

Abstract

A process for cleaning, degreasing and activating composite parts of iron or steel and zinc or galvanised steel or aluminium or aluminised steel, before a subsequent phosphating treatment thereof. The composite parts are treated with aqueous cleaning and/or activating solutions which have a pH in the range from 6 to 13, an opposite potential, which is at least as high as the potential which establishes itself in the particular solution in accordance with the electrochemical series, being applied simultaneously between the composite part to be treated on the one hand and the bath container and/or an electrode arranged in the bath on the other hand. Preferably, the composite parts are treated with a 0.1 to 3 per cent by weight aqueous solution which contains 72.5 per cent by weight of sodium tetraborate x 10 H2O, 18 per cent by weight of sodium dihydrogen orthophosphate and 9.5 per cent by weight of an addition product of 10 mol of ethylene oxide with nonylphenol. Preferably, the opposite potential to be applied is at least twice as high as the potential which establishes itself in the particular solution in accordance with the electrochemical series.

Description

Die Erfindung betrifft ein verbessertes Verfahren zum Reinigen und Entfetten sowie Aktivieren von Verbundteilen aus Eisen oder Stahl und Zink beziehungsweise verzinktem Stahl oder Aluminium- beziehungsweise aluminiertem Stahl vor einer nachfolgenden Phosphatierungsbehandlung derselben, bei erhöhten Temperaturen sowie mit Hilfe von für diesen Zweck gebräuchlichen wäßrigen Reiniger- und/oder Aktivierungslösungen.The invention relates to an improved method for cleaning and degreasing and activating composite parts made of iron or steel and zinc or galvanized steel or aluminum or aluminized steel before a subsequent phosphating treatment of the same, at elevated temperatures and with the aid of aqueous cleaner and / or activation solutions.

Derartige Verbundteile werden seitens der Automobilindustrie in zunehmendem Maße beim Bau von Automobilkarossen eingesetzt, um einen verbesserten Korrosionsschutz der Karossen zu erzielen. Üblicherweise werden hierbei die für den Karosseriebau gebräuchlichen Eisenwerkstoffe beziehungsweise Stahlbleche im Verbund mit sowohl elektrolytisch- als auch feuerverzinktem Stahl verwendet. Außer "reinem" Zink bürgern sich für diesen Zweck mehr und mehr Zinklegierungen ein, die beispielsweise von 2 bis 10 % an Eisen, Nickel, Kobalt oder Aluminium als Legierungspartner enthalten können. Auch Verbundteile aus Stahl und Zink kommen hier gegebenenfalls in Frage. Ferner finden auch entsprechende Verbundteile aus Karosseriestahl und Aluminium beziehungsweise aus Stahl und aluminiertem Stahl - vorzugsweise feueraluminiertem Stahl - Verwendung.Composite parts of this type are increasingly being used by the automotive industry in the construction of automobile bodies in order to achieve improved corrosion protection of the bodies. Usually, the iron materials or steel sheets commonly used for body construction are used in combination with both electrolytic and hot-dip galvanized steel. In addition to "pure" zinc, more and more zinc alloys are becoming established for this purpose, which can contain, for example, 2 to 10% of iron, nickel, cobalt or aluminum as an alloy partner. Composite parts made of steel and zinc may also be considered here. Corresponding composite parts made from body steel and aluminum or from steel and aluminized steel - preferably fire-aluminized steel - are also used.

Zur Vorbereitung der Automobilkarossen und insbesondere auch der vorstehend angesprnchenen Verbundteile für die heutzutage gebräuchliche Elektrotauchlackierung ist es üblich, die Werkstücke zu reinigen, mit Wasser zu spülen und anschließend zu phosphatieren. Verfahren zur Erzeugung von Phosphatschichten auf Eisen- und Stahloberflächen sowie auf Oberflächen der vorstehend erörterten Verbundteile mit Hilfe saurer Lösungen, die Phosphate mehrwertiger Metalle sowie - zur Beschleunigung der Schichtausbildung - Oxidationsmittel oder andere Beschleunigerkomponenten enthalten, sind seit langem bekannt. Gleichfalls bekannt ist die Verwendung schwach saurer beziehungsweise alkalisch eingestellter Reinigungs- und Entfettungslösungen vor dem Phosphatieren, um die zu behandelnden Metalloberflächen, insbesondere von anhaftenden ölen und Fetten sowie anderen, auch mechanischen Verunreinigungen zu befreien. Derartige Reinigungslösungen enthalten in der Regel grenzflächenaktive Substanzen, wie Netzmittel und Emulgatoren, sowie zur Verstärkung des Emulgier-, Verseifungs- und Schmutztragevermögens sogenannte Builder-Substanzen, beispielsweise Natriumhydroxid, Alkalimetallcarbonate, Alkalimetallphosphate, wie Orthophosphate sowie entsprechende kondensierte Phosphate, beispielsweise Natriumpyrophosphat oder Natriumtriphosphat, sowie gegebenenfalls auch Silikate und Borate. Ferner werden solchen Reinigungs- und Entfettungslösungen häufig schichtverfeinernd und aktivierend wirkende Substanzen, zum Beispiel Titanverbindungen, wie Titanphosphate, zugesetzt. Die Reinigungs- und Entfettungslösungen sowie auch die Phosphatierungslösungen werden üblicherweise im Spritz-, Tauch- oder kombiniertem Spritz-Tauch- Verfahren auf die zu behandelnden Metalloberflächen aufgebracht. Die Werkstücke - einschließlich der vorstehend erörterten Verbundteile - werden nach erfolgter Reinigung beziehungsweise Entfettung in der Regel mit Wasser gespült und anschließend einem Phosphatierungsverfahren in bekannter Weise unterworfen. Gegebenenfalls kann die Aktivierung jedoch auch nach der Reinigungs-und Entfettungsstufe in einem getrennten Verfahrensschritt erfolgen. Die gereinigten und phosphatierten Werkstücke, das heißt Automobilkarossen, werden anschließend lackiert, üblicherweise im Elektrotauchlackier-Verfahren.In order to prepare the automobile bodies and in particular the composite parts mentioned above for today's electro-dip painting, it is customary to clean the workpieces, rinse them with water and then phosphate them. Processes for producing phosphate layers on iron and steel surfaces and on surfaces of the composite parts discussed above with the aid of acidic solutions which contain phosphates of polyvalent metals and - to accelerate the layer formation - contain oxidizing agents or other accelerator components have long been known. It is also known to use weakly acidic or alkaline cleaning and degreasing solutions before phosphating in order to free the metal surfaces to be treated, in particular from adhering oils and greases and other mechanical contaminants. Such cleaning solutions generally contain surface-active substances, such as wetting agents and emulsifiers, and so-called builder substances, for example sodium hydroxide, alkali metal carbonates, alkali metal phosphates, such as orthophosphates and corresponding condensed phosphates, for example sodium pyrophosphate or sodium triphosphate, for strengthening the emulsifying, saponification and dirt-carrying capacity optionally also silicates and borates. Furthermore, such cleaning and degreasing solutions are often added to substances which have a layer-refining and activating effect, for example titanium compounds, such as titanium phosphates. The cleaning and degreasing solutions as well as the phosphating solutions are usually applied to the metal surfaces to be treated in a spray, dip or combined spray-dip process. The workpieces - including the composite parts discussed above - are usually cleaned after cleaning or degreasing Rinsed water and then subjected to a phosphating process in a known manner. If necessary, however, the activation can also take place after the cleaning and degreasing stage in a separate process step. The cleaned and phosphated workpieces, i.e. automobile bodies, are then painted, usually using the electro-dip painting process.

Die in den vorstehend erörterten Verbundteilen enthaltenen Metalle Zink und Aluminium lösen sich aufgrund ihres amphoteren Charakters sowohl in Säuren als auch in Basen unter Wasserstoffentwicklung auf. Im pH-Bereich von. 7 bis etwa 12,5 gelten diese Metalle jedoch als relativ beständig, da die Auflösung der Metalloberfläche durch Bildung von Schutzschichten auf derselben gemindert wird. Die üblicherweise verwendeten alkalischen Reinigerlösungen liegen im zuvor genannten pH-Bereich, so daß hier keine Korrosionsprobleme zu erwarten wären. In der Praxis hat es sich jedoch gezeigt, daß bei der vorstehend geschilderten Verbundbauweise - leitender Verbund - auch in dem als unbedenklich geltenden pH-Bereich Korrosionen der Zink- und Aluminium-Oberflächen'auftreten. Hierbei resultieren sowohl punktförmige, lochfraßähnliche Korrosionserscheinungen als auch flächige Schädigungen der Zink- beziehungsweise Aluminium-Oberflächen. Diese in der Reinigungs- beziehungsweise Entfettungsstufe initiierten Korrosionserscheinungen führen zu Störungen der Metalloberfläche, die sich auch im nachfolgenden Phosphatierungsschritt auswirken und darüber hinaus das Bild der lackierten Metalloberfläche in beträchtlichem Maße beeinträchtigen. Eine wirkungsvolle Beseitigung derartiger Korrosionserscheinungen müßte unmittelbar nach der erfolgten Reinigung der Metalloberfläche durchgeführt werden, und würde eine beträchtliche, finanziell nicht vertretbare Nachbearbeitung der Metalloberflächen bedingen.The metals zinc and aluminum contained in the composite parts discussed above dissolve due to their amphoteric character both in acids and in bases with evolution of hydrogen. In the pH range from. 7 to about 12.5, however, these metals are considered to be relatively stable, since the dissolution of the metal surface is reduced by the formation of protective layers thereon. The commonly used alkaline cleaning solutions are in the previously mentioned pH range, so that no corrosion problems would be expected here. In practice, however, it has been shown that with the composite construction described above - conductive composite - corrosion of the zinc and aluminum surfaces also occurs in the pH range which is considered to be harmless. This results in punctiform, pitting-like corrosion phenomena as well as extensive damage to the zinc or aluminum surfaces. These corrosion phenomena initiated in the cleaning or degreasing stage lead to faults in the metal surface, which also have an effect in the subsequent phosphating step and moreover impair the image of the painted metal surface to a considerable extent. An effective removal of such corrosion phenomena would have to be carried out immediately after the metal surface had been cleaned and would require a considerable, financially unjustifiable reworking of the metal surfaces.

Die Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren zum Reinigen und Entfetten sowie Aktivieren von Verbundteilen aus Stahl und verzinktem beziehungsweise aluminiertem Stahl vor dem Phosphatieren zu entwickeln, bei dem die vorstehend beschriebenen Korrosionserscheinungen, - bedingt durch die Anwendung alkalischer sowie auch schwach saurer Reinigungs- und Entfettungslösungen - vermieden werden.The object of the present invention is therefore to develop a method for cleaning and degreasing and activating composite parts made of steel and galvanized or aluminized steel prior to phosphating, in which the corrosion phenomena described above, due to the use of alkaline and also weakly acidic cleaning - and degreasing solutions - are avoided.

Gegenstand der Erfindung ist dementsprechend ein Verfahren zum Reinigen und Entfetten sowie Aktivieren von Verbundteilen aus Eisen oder Stahl und Zink beziehungsweise verzinktem Stahl oder Aluminium beziehungsweise aluminiertem Stahl vor einer nachfolgenden Phosphatierungsbehandlung derselben, bei erhöhten Temperaturen sowie mit Hilfe von für diesen Zweck gebräuchlichen wäßrigen Reiniger- und/oder Aktivierungslösungen, welches dadurch gekennzeichnet ist, daß man

  • a) die Verbundteile mit Lösungen behandelt, die einen pH-Wert im Bereich von 6 bis 13 aufweisen und
  • b) gleichzeitig zwischen zu behandelndem Verbundteil einerseits und dem Badbehälter und/oder einer im Bad angeordneten Elektrode andererseits ein Gegenpotential anlegt, das mindestens so hoch ist, wie das aufgrund der Spannungsreihe in der betreffenden Lösung sich einstellende Potential.
The invention accordingly relates to a method for cleaning and degreasing and activating composite parts made of iron or steel and zinc or galvanized steel or aluminum or aluminized steel before a subsequent phosphating treatment thereof, at elevated temperatures and with the aid of aqueous cleaning agents and those customary for this purpose / or activation solutions, which is characterized in that
  • a) the composite parts are treated with solutions which have a pH in the range from 6 to 13 and
  • b) at the same time, between the composite part to be treated on the one hand and the bath container and / or an electrode arranged in the bath, on the other hand, applies a counter potential which is at least as high as the potential which arises due to the voltage series in the solution in question.

überraschenderweise wurde nämlich gefunden, daß sich auch bei Anwendung der nach dem Stand der Technik üblichen und gebräuchlichen-Reiniger- und Entfettungslösungen - im pH-Bereich von 6 bis 13 - sämtliche Korrosionserscheinungen auf den Zink- beziehungsweise Aluminium-Oberflächen verhindern lassen, sofern man zwischen dem in das Reinigerbad eintauchende Verbundteil einerseits und beispielsweise dem aus Baustahl gefertigten Badbehälter andererseits eine elektrische Spannung anlegt. Messungen haben nämlich gezeigt, daß zwischen dem unedleren Teil des Verbundwerkstoffes - das heißt der Zink- beziehungsweise Aluminium-Oberfläche - und der Stahloberfläche galvanische Ströme fließen, die eine Korrosion der Zink- beziehungsweise Aluminim-Oberflächen bedingen. Als Elektrolyt wirkt hierbei die Reinigungs- beziehungsweise Entfettungslösung. Durch das Anlegen eines Gegenpotentials, das mindestens so hoch ist, wie das aufgrund der Spannungsreihe in der betreffenden Lösung sich einstellende Potential, wird bei dem erfindungsgemäßen Verfahren ein Fließen galvanischer Ströme - und damit das Auftreten korrosiver Erscheinungen vollständig unterbunden. Als eine Gegenelektrode zum Verbundteil kann - wie bereits gesagt - der aus Stahl gefertigte Badbehälter des Reinigungs- oder Entfettungsbades dienen. Sofern beim Verfahren beispielsweise Badbehälter aus nicht leitendem Material - Kunststoff - Verwendung finden, wird in das Reinigungsbad eine Elektrode aus Stahlblech eingebracht und zwischen dieser und dem Verbundteil das Gegenpotential aufgebaut. Im Sinne des erfindungsgemäßen Verfahrens kann jedoch auch in einem Badbehälter aus Stahl eine zusätzlich im Bad angeordnete Elektrode vorhanden sein. Erfindungswesentlich ist nur, daß zwischen Verbundteil einerseits und Badbehälter und/oder zusätzlicher Elektrode andererseits ein Gegenpotential anliegt, wobei sowohl Verbundteil als auch Elektrode mit der Badflüssigkeit in Berührung stehen.Surprisingly, it was found that even when using the cleaning and degreasing solutions customary and customary in the prior art - in the pH range from 6 to 13 - all signs of corrosion on the zinc or aluminum surfaces can be prevented, provided that there is a difference between the composite part immersed in the detergent bath on the one hand and, for example, the bath container made of structural steel on the other hand applies an electrical voltage. Measurements have shown that galvanic currents flow between the less noble part of the composite material - that is, the zinc or aluminum surface - and the steel surface, causing corrosion of the zinc or aluminum surfaces. The cleaning or degreasing solution acts as the electrolyte. By applying a counter potential that is at least as high as the potential that arises due to the voltage series in the solution in question, the flow according to the invention completely prevents the flow of galvanic currents - and thus the occurrence of corrosive phenomena. As already mentioned, the bath container made of steel of the cleaning or degreasing bath can serve as a counter electrode to the composite part. If, for example, bath containers made of non-conductive material - plastic are used in the process, an electrode made of sheet steel is introduced into the cleaning bath and the counter potential is built up between this and the composite part. In the sense of the method according to the invention, however, an electrode additionally arranged in the bath can also be present in a steel bath container. It is only essential to the invention that a counter potential is present between the composite part on the one hand and the bath container and / or additional electrode on the other hand, both composite both the part and the electrode are in contact with the bath liquid.

Im Sinne der Erfindung können alle diejenigen gebräuchlichen Reinigungs- und Entfettungslösungen Verwendung finden, die einen pH-Wert im Bereich von 6 bis 13 aufweisen. Hierzu zählen insbesondere Reinigerlösungen, die die vorstehend aufgezählten Inhaltsstoffe aufweisen können. So kommen als Builder-Stoffe insbesondere Phosphate, Carbonate, Borate, Silikate oder Hydroxide von Alkalimetallen in Frage. Auch entsprechende Ammonium-Verbindungen können hierzu Verwendung finden. Weitere Bestandteile der erfindungsgemäß zu verwendenden Reinigenlösungen sind gebräuchliche anionenaktive, kationenaktive oder nichtionogene Netzmittel und Emulgatoren. Von diesen werden jedoch bevorzugt die nichtionogenen Typen eingesetzt, beispielsweise Anlagerungsprodukte des Ethylenoxids an Fettalkohole, Alkylphenole, Fettamine oder Polyoxypropylenglykole. Gegebenenfalls können neben den als Builderstoff gebräuchlichen kondensierten Phosphaten auch sonstige komplexierende Verbindungen Verwendung finden, die für derartige Zwecke üblicherweise eingesetzt werden. Als solche kommen beispielsweise Hydroxypolycarbonsäuren, wie Zitronensäure, Aminopolycarbonsäuren, wie Nitrilotriessigsäure oder Ethylendiamintetraessigsäure, Phosphonsäuren, wie Ethan-1-hydroxy-1,1-diphosphonsäure oder Aminotrimethylenphosphonsäure, die wasserlöslichen Alkalimetallsalze derartiger Säuren sowie sonst gebräuchliche Komplexbildner in Frage. Zur Aktivierung der zu behandelnden Metalloberflächen können den Reinigerlösungen ferner die für diesen Zweck gebräuchlichen und bekannten Schichtverfeinerer und Aktivatoren, beispielsweise Titanorthophosphat, zugesetzt werden. Gebräuchliche Reiniger nach dem Stand der Technik sind beispielsweise in der deutschen Offenlegungsschrift 29 51 600 oder der deutschen Auslegeschrift 11 70 220 beschrieben. Die Nennung dieser Literaturstellen soll jedoch keineswegs eine Begrenzung des erfindungsgemäßen Verfahrens auf die in diesen Patentanmeldungen beschriebenen Reinigerlösungen bezwecken; sie ist vielmehr lediglich beispielhafter Natur.For the purposes of the invention, all those customary cleaning and degreasing solutions can be used which have a pH in the range from 6 to 13. These include, in particular, cleaning solutions, which may have the ingredients listed above. For example, phosphates, carbonates, borates, silicates or hydroxides of alkali metals are suitable as builder substances. Corresponding ammonium compounds can also be used for this. Further constituents of the cleaning solutions to be used according to the invention are customary anionic, cationic or nonionic wetting agents and emulsifiers. Of these, however, the nonionic types are preferably used, for example addition products of ethylene oxide with fatty alcohols, alkylphenols, fatty amines or polyoxypropylene glycols. In addition to the condensed phosphates commonly used as builders, other complexing compounds which are usually used for such purposes can optionally be used. As such, for example, hydroxypolycarboxylic acids, such as citric acid, aminopolycarboxylic acids, such as nitrilotriacetic acid or ethylenediaminetetraacetic acid, phosphonic acids, such as ethane-1-hydroxy-1,1-diphosphonic acid or aminotrimethylenephosphonic acid, the water-soluble alkali metal salts of such acids and other commonly used complexing agents are suitable. To activate the metal surfaces to be treated, the layer refiners and activators, for example titanium orthophosphate, which are customary and known for this purpose, can also be added to the cleaning solutions. Current state-of-the-art cleaners are used, for example, in Germany Laid-open specification 29 51 600 or the German interpretation 11 70 220. However, the mention of these references is in no way intended to limit the method according to the invention to the cleaning solutions described in these patent applications; rather, it is merely exemplary in nature.

Das erfindungsgemäße Verfahren läßt sich in den gebräuchlichen Standbädern oder auch in den in der Automobilindustrie häufig eingesetzten Durchlaufanlagen verwenden. Das Aufbringen der Reinigerlösungen kann hierbei sowohl im Tauch- oder Spritz-Verfahren als auch i m kombinierten Spritz-Tauch-Verfahren erfolgen.The method according to the invention can be used in the usual standing baths or also in the continuous systems frequently used in the automotive industry. The cleaning solutions can be applied either by immersion or spraying or in a combined spray-immersion process.

Bei den gebräuchlichen Durchlaufanlagen wird die Stromübertragung auf das sich bewegende Werkstück mit Hilfe eines Schleifkontaktes bewerkstelligt. Bei nicht leitenden Badbehältern ist es hier sinnvoll, mehrere Zusatzelektroden in regelmäßigen Abständen in das Bad einzubringen. Ansonsten können für das erfindungsgemäße Verfahren die auch sonst für eine Reinigung beziehungsweise Entfettung vor dem Phosphatieren üblichen Verfahrensbedingungen-Anwendung finden.In the conventional continuous systems, the current transfer to the moving workpiece is accomplished with the help of a sliding contact. In the case of non-conductive bath containers, it makes sense to insert several additional electrodes into the bath at regular intervals. Otherwise, the usual process conditions for cleaning or degreasing before phosphating can also be used for the process according to the invention.

Im Sinne des erfindungsgemäßen Verfahrens ist es bevorzugt, daß man die Verbundteile mit Lösungen behandelt, die einen pH-Wert im Bereich von 7 bis 11 aufweisen. Vorzugsweise sollte die Temperatur der wäßrigen Reiniger-und Entfettungslösungen im Bereich von 35 bis 70 °C liegen.For the purposes of the process according to the invention, it is preferred that the composite parts are treated with solutions which have a pH in the range from 7 to 11. The temperature of the aqueous cleaning and degreasing solutions should preferably be in the range from 35 to 70.degree.

Im Sinne des erfindungsgemäßen Verfahrens ist es ferner bevorzugt, daß man die Verbundteile mit wäßrigen Lösungen behandelt, die

  • c) mindestens ein Alkalimetallborat, mindestens ein Alkalimetallphosphat und mindestens ein nichtionisches Tensid und/oder
  • d) mindestens eine Aktivierungskomponente, vorzugsweise auf Basis einer Titanverbindung, enthalten. Die Aktivierungskomponente muß nicht notwendigerweise ein Bestandteil der Reinigerlösung sein. Sie kann - falls erwünscht - ganz entfallen oder aber - wie vorstehend bereits erörtert - in einem der Reinigerstufe nachgeschalteten Bad enthalten sein. Im letzteren Falle werden die wesentlichen Maßnahmen des erfindungsgemäßen Verfahrens in der gleichen Weise wie bei einer Reinigungs- oder Entfettungslösung angewendet. In der Regel finden jedoch solche Reinigerlösungen Verwendung, die bereits eine Aktivierungskomponente enthalten.
In the sense of the method according to the invention it is further preferred that the composite parts are treated with aqueous solutions which
  • c) at least one alkali metal borate, at least one alkali metal phosphate and at least one nonionic surfactant and or
  • d) contain at least one activation component, preferably based on a titanium compound. The activation component does not necessarily have to be part of the cleaning solution. If desired, it can be omitted entirely or, as already discussed above, can be contained in a bath downstream of the cleaning stage. In the latter case, the essential measures of the method according to the invention are applied in the same way as for a cleaning or degreasing solution. As a rule, however, such cleaning solutions are used that already contain an activation component.

Im Sinne des erfindungsgemäßen Verfahrens ist es besonders bevorzugt, daß man die Verbundteile mit einer 0,1- bis 3-gewichtsprozentigen wäßrigen Lösung behandelt, die 72,5 Gewichtsprozent Natriumtetraborat x 10 H20 18 Gewichtsprozent Natriumdihydrogenorthophosphat und 9,5 Gewichtsprozent eines Additionsproduktes von 10 Mol Ethylenoxid an Nonylphenol enthält..In the sense of the process according to the invention, it is particularly preferred that the composite parts are treated with a 0.1 to 3 percent by weight aqueous solution containing 72.5 percent by weight sodium tetraborate x 10 H 2 0 18 percent by weight sodium dihydrogen orthophosphate and 9.5 percent by weight of an addition product Contains 10 moles of ethylene oxide in nonylphenol.

Ferner ist es erfindungsgemäß besonders bevorzugt, wenn man ein Gegenpotential anlegt, das mindestens doppelt so hoch ist, wie das aufgrund der Spannungsreihe in der betreffenden Lösung sich einstellende Potential. Auf diese Weise lassen sich mögliche Schwankungen des sich einstellenden Potentials abfangen, so daß sich ständige Potentialmessungen zu Überwachungszwecken erübrigen.Furthermore, it is particularly preferred according to the invention if a counter potential is applied which is at least twice as high as the potential which arises due to the voltage series in the solution in question. In this way, possible fluctuations in the potential that is established can be absorbed, so that constant potential measurements for monitoring purposes are unnecessary.

Im Anschluß an die erfindungsgemäße Reinigungs- beziehungsweise Entfettungsbehandlung erfolgt die Phosphatierung und die nachfolgende Lackierung der Verbundteile beziehungsweise Werkstücke in der gebräuchlichen Weise.Following the cleaning or degreasing treatment according to the invention, the phosphating and the subsequent painting of the composite parts or workpieces takes place in the customary manner.

Die nachstehenden Beispiele erläutern die Durchführung des erfindungsgemäßen Verfahrens.The following examples illustrate the implementation of the method according to the invention.

BeispieleExamples

Für die nachfolgenden Beispiele wurde eine 0,6-gewichtsprozentige wäßrige Reinigerlösung der folgenden Zusammensetzung verwendet:

  • 72,5 Gewichtsprozent Natriumtetraborat x 10 H20
  • 18 Gewichtsprozent Natriumdihydrogenorthophosphat
  • 9,5 Gewichtsprozent eines Additionsproduktes von 10 Mol Ethylenoxid an Nonylphenol
  • Der pH-Wert der Reinigerlösung betrug 8,9; die Anwendungstemperatur 50 °C.
A 0.6% by weight aqueous cleaning solution of the following composition was used for the examples below:
  • 72.5% by weight sodium tetraborate x 10 H 2 0
  • 18% by weight sodium dihydrogen orthophosphate
  • 9.5 percent by weight of an addition product of 10 moles of ethylene oxide with nonylphenol
  • The pH of the cleaning solution was 8.9; the application temperature 50 ° C.

Die nachstehenden Versuche wurden in einem Standbad im Tauchverfahren ausgeführt.The following tests were carried out in a standing bath using the immersion method.

Beispiel 1example 1

Die Reinigerlösung befand sich in einem Badbehälter aus Baustahl. Beim Eintauchen eines Verbundwerkstücks aus elektrolytisch verzinktem Stahl und Stahlwerkstoff Nr. 11 405 (Karosseriestahl) wurde ein Potential von 655 Millivolt gemessen. Beim Eintauchen eines entsprechenden Verbundwerkstückes mit feuerverzinktem Stahl (sendzimirverzinkter Stahl, nachdressiert) wurde ein Potential von 575 Millivolt gemessen.The cleaning solution was in a bath tank made of structural steel. When a composite workpiece made of electrolytically galvanized steel and steel material No. 11 405 (body steel) was immersed, a potential of 655 millivolts was measured. A potential of 575 millivolts was measured when immersing a corresponding composite workpiece with hot-dip galvanized steel (sendzimir-galvanized steel, redressed).

In beiden Fällen waren die vorstehend erwähnten durch Korrosion hervorgerufenen Veränderungen der Zinkoberfläche deutlich sichtbar. Beim Anlegen eines kathodischen Gegenpotentials auf den Werkstücken von 655 Millivolt war die Korrosion des elektrolytisch verzinkten Stahls deutlich vermindert, bei Anlegen eines Gegenpotentials von 700 Millivolt traten auf elektrolytisch verzinktem Stahl keinerlei Korrosionserscheinungen mehr auf, bei 800 Millivolt Gegenpotential waren sowohl der elektrolytisch verzinkte Stahl als auch der feuerverzinkte Stahl nach einer Eintauchzeit in den Reiniger von 5 Minuten völlig frei von jeglichen Korrosionserscheinungen.In both cases the above-mentioned changes in the zinc surface caused by corrosion were clearly visible. When a cathodic counter potential was applied to the workpieces of 655 millivolts, the corrosion of the electrolytically galvanized steel was significantly reduced; when a counter potential of 700 millivolts was applied, there were no more signs of corrosion on the electrolytically galvanized steel, at 800 millivolts counter potential Both the electrolytically galvanized steel and the hot-dip galvanized steel were completely free of any signs of corrosion after an immersion time in the cleaner of 5 minutes.

Beispiel 2Example 2

Es wurde ein Badbehälter aus nicht leitendem Material (Kunststoff) verwendet. Als Elektrolyt diente die bereits erwähnte Reinigerlösung unter den genannten Bedingungen. Als zusätzliche Elektrode wurde ein Stahlblech in die.Badlösung eingetaucht. Zwischen dem in das Reinigerbad eintauchenden Verbundwerkstück aus Karosseriestahl und elektrolytisch verzinktem Stähl sowie der Elektrode aus Stahl wurde ein Potential von 193 Millivolt gemessen. Korrosionserscheinungen auf dem elektrolytisch verzinktem Stahl waren deutlich sichtbar. Bei weiteren entsprechenden Verbundwerkstück-Proben wurden jeweils "Gegenpotentiale von 400 Millivolt, 500 Millivolt und 1 000 Millivolt angelegt. Bei allen genannten kathodischen Gegenpotentialen traten nach 5 Minuten Tauchzeit im Reiniger keine sichtbaren Korrosionserscheinungen auf dem elektrolytisch verzinktem Stahl auf.A bath container made of non-conductive material (plastic) was used. The previously mentioned cleaning solution was used as the electrolyte under the conditions mentioned. A steel sheet was immersed in the bath solution as an additional electrode. A potential of 193 millivolts was measured between the composite workpiece made of body steel and electrolytically galvanized steel, which was immersed in the cleaning bath. Signs of corrosion on the galvanized steel were clearly visible. In the case of further corresponding composite workpiece samples, "counter potentials of 400 millivolts, 500 millivolts and 1,000 millivolts were applied. With all the cathodic counter potentials mentioned, there were no visible signs of corrosion on the electrolytically galvanized steel after 5 minutes of immersion in the cleaner.

Bei Verwendung von Verbundwerkstücken aus Karosseriestahl und feuerverzinktem Stahl wurde ein Gegenpotential von 400 Millivolt angelegt. Nach der gleichen Tauchzeit traten auch hierbei keinerlei Korrosionserscheinungen auf. Auch bei einer nachfolgenden schichtbildenden Phosphatierung der erfindungsgemäß behandelten Proben - in einem Zinkoxid, Phosphorsäure und Salpetersäure enthaltenden Phosphatierungsbad - resultierten vollkommen fehlerfreie Zinkoberflächen; wohingegen bei den nicht erfindungsgemäß vorbehandelten Proben die Korrosionsschäden deutlich in Erscheinung traten.A counter potential of 400 millivolts was applied when using composite workpieces made of body steel and hot-dip galvanized steel. No signs of corrosion occurred after the same dive time. Even subsequent layer-forming phosphating of the samples treated according to the invention - in a phosphating bath containing zinc oxide, phosphoric acid and nitric acid - resulted in completely defect-free zinc surfaces; whereas the corrosion damage clearly appeared in the samples not pretreated according to the invention.

Claims (6)

1. Verfahren zum Reinigen und Entfetten sowie Aktivieren von Verbundteilen aus Eisen oder Stahl und Zink beziehungsweise verzinktem Stahl oder Aluminium beziehungsweise aluminiertem Stahl vor einer nachfolgenden Phosphatierungsbehandlung derselben, bei erhöhten Temperaturen sowie mit Hilfe von für diesen Zweck gebräuchlichen wäßrigen Reiniger-und/oder Aktivierungslösungen, dadurch gekennzeichnet, daß man a) die. Verbundteile mit Lösungen behandelt, die einen pH-Wert im Bereich von 6 bis 13 aufweisen und b) gleichzeitig zwischen zu behandelndem Verbundteil einerseits und dem Badbehälter und/oder einer im Bad angeordneten Elektrode andererseits ein Gegenpotential anlegt, das mindestens so hoch ist, wie das aufgrund der Spannungsreihe in der betreffenden Lösung sich einstellende Potential. 1. A process for cleaning and degreasing and activating composite parts made of iron or steel and zinc or galvanized steel or aluminum or aluminized steel before a subsequent phosphating treatment thereof, at elevated temperatures and with the aid of aqueous cleaning and / or activation solutions customary for this purpose, characterized in that one a) the. Composite parts treated with solutions that have a pH in the range of 6 to 13 and b) at the same time, between the composite part to be treated on the one hand and the bath container and / or an electrode arranged in the bath, on the other hand, applies a counter potential which is at least as high as the potential which arises due to the voltage series in the solution in question. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Verbundteile mit Lösungen behandelt, die einen pH-Wert im Bereich von 7 bis 11 aufweisen.2. The method according to claim 1, characterized in that the composite parts are treated with solutions which have a pH in the range from 7 to 11. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man die Verbundteile mit Lösungen behandelt, die eine Temperatur im Bereich von 35 bis 70 °C aufweisen.3. The method according to claim 1 and 2, characterized in that the composite parts are treated with solutions which have a temperature in the range of 35 to 70 ° C. 4. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß man die Verbundteile mit wäßrigen Lö- sungen behandelt, die c) mindestens ein Alkalimetallborat, mindestens ein Alkalimetallphosphat und mindestens ein nichtionisches Tensid und/oder d) mindestens eine Aktivierungskomponente, vorzugsweise auf Basis einer Titanverbindung, enthalten. 4. The method according to claim 1 to 3, characterized in that treating the composite parts with aqueous solutions, the c) at least one alkali metal borate, at least one alkali metal phosphate and at least one nonionic surfactant and / or d) contain at least one activation component, preferably based on a titanium compound. 5. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß man die Verbundteile mit einer 0,1- bis 3-gewichtsprozentigen wäßrigen Lösung behandelt, die 72,5 Gewichtsprozent Natriumtetraborat x 10 H20 18 Gewichtsprozent Natriumdihydrogenorthophosphat und 9,5 Gewichtsprozent eines Additionsproduktes von 10 Mol Ethylenoxid an Nonylphenol enthält.5. The method according to claim 1 to 4, characterized in that the composite parts are treated with a 0.1 to 3 percent by weight aqueous solution containing 72.5 percent by weight sodium tetraborate x 10 H 2 0 18 percent by weight sodium dihydrogen orthophosphate and 9.5 percent by weight one Addition product of 10 moles of ethylene oxide with nonylphenol contains. 6. Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, daß man ein Gegenpotential anlegt, das mindestens doppelt so hoch ist, wie das aufgrund der Spannungsreihe in der betreffenden Lösung sich einstellende t Potential.6. The method according to claim 1 to 5, characterized in that one applies a counter potential which is at least twice as high as the t potential arising due to the voltage series in the solution in question.
EP83103267A 1982-04-14 1983-04-02 Process for cleaning, degreasing and activating metallic surfaces Withdrawn EP0091627A3 (en)

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EP0131960A3 (en) * 1983-07-19 1986-12-30 Nippon Steel Corporation Process for producing gold rolled steel strip highly susceptible to conversion treatment
EP0131960A2 (en) * 1983-07-19 1985-01-23 Nippon Steel Corporation Process for producing cold rolled steel strip highly susceptible to conversion treatment
FR2572422A1 (en) * 1984-10-31 1986-05-02 Produits Ind Cie Fse IMPROVED ACTIVATION AND REFINING BATH FOR ZINC PHOSPHATION PROCESS AND CORRESPONDING CONCENTRATE
EP0180523A1 (en) * 1984-10-31 1986-05-07 Compagnie Francaise De Produits Industriels Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor
US4678519A (en) * 1984-10-31 1987-07-07 Compagnie Francaise De Produits Industriels Method of zinc phosphatization, activation and refining bath used in said method and corresponding concentrate
EP0224190A3 (en) * 1985-11-28 1989-01-18 Gerhard Collardin Gmbh Process for activating metallic surfaces prior to zinc phosphating
EP0224190A2 (en) * 1985-11-28 1987-06-03 Gerhard Collardin GmbH Process for activating metallic surfaces prior to zinc phosphating
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EP1705265A1 (en) * 2003-12-04 2006-09-27 Sumitomo Metal Industries, Ltd. Surface adjustment treatment prior to chemical treatment of steel product
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US7666266B2 (en) 2003-12-04 2010-02-23 Sumitomo Metal Industries, Ltd. Surface conditioning prior to chemical conversion treatment of a steel member
EP4148163A1 (en) * 2021-09-13 2023-03-15 Henkel AG & Co. KGaA Method for cleaning and / or corrosion protection of a plurality of components comprising galvanized (zm) steel
WO2023036889A1 (en) * 2021-09-13 2023-03-16 Henkel Ag & Co. Kgaa Method for the cleaning and/or anti-corrosion pretreatment of a plurality of components comprising zinc-coated (zm) steel

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EP0091627A3 (en) 1984-06-06
DE3213649A1 (en) 1983-10-27
JPS58189375A (en) 1983-11-05

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