EP0012399B2 - Process for applying metallic coatings to metallic workpieces by a mechano-chemical treatment of said pieces - Google Patents

Process for applying metallic coatings to metallic workpieces by a mechano-chemical treatment of said pieces Download PDF

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Publication number
EP0012399B2
EP0012399B2 EP79105012A EP79105012A EP0012399B2 EP 0012399 B2 EP0012399 B2 EP 0012399B2 EP 79105012 A EP79105012 A EP 79105012A EP 79105012 A EP79105012 A EP 79105012A EP 0012399 B2 EP0012399 B2 EP 0012399B2
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Prior art keywords
bath
process according
workpieces
reaction mixture
tin
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German (de)
French (fr)
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EP0012399A1 (en
EP0012399B1 (en
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Bernd Tolkmit
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Tolkmit Bernd
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Tolkmit Bernd
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Priority claimed from DE19782854159 external-priority patent/DE2854159C2/en
Priority claimed from DE19792919726 external-priority patent/DE2919726A1/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C24/00Coating starting from inorganic powder
    • C23C24/02Coating starting from inorganic powder by application of pressure only
    • C23C24/04Impact or kinetic deposition of particles
    • C23C24/045Impact or kinetic deposition of particles by trembling using impacting inert media

Definitions

  • the invention relates to a method for applying metallic coatings to metallic workpieces by treating the workpieces in a bath containing inert impact bodies, by immersing the workpieces in the bath and creating a relativization between workpieces and impact bodies or bath, with an aqueous solution Bath containing nonylphenol polyglycol ether as activator after cleaning the workpieces metal ions and further a reaction mixture and the metal powder forming the coating are added.
  • Such a method has the advantage over galvanically operating methods that the danger of hydrogen embrittlement of the treated workpieces is largely excluded.
  • a process is carried out in such a way that the workpieces are cleaned, an intermediate layer of a thin tin coating being applied at the same time. Then the metal powder that forms the actual coating is added to the bath, and only when this has been distributed in the bath after further relative movement and the pH of the bath has risen to about 5 is acidic sodium sulfate added, under the effect of which further movement moves then the coating forms on the workpieces.
  • the degreased workpieces are introduced into a drum together with the impact bodies, which usually consist of a glass ball mixture.
  • the workpieces are freed of rust and scale and the surface is prepared for receiving an intermediate layer of a non-ferrous metal, in particular copper, which is then to be applied.
  • the intermediate layer is deposited from a copper solution, which is filled into the drum.
  • a so-called promoter chemical is entered, which ensures that the powdered coating metal also added is cleaned and a uniform surface distribution is achieved.
  • the size of the glass balls is chosen so that the powdered coating metal also in recesses, for. B. gets to the bottom of thread grooves and thus an optimal coating is achieved.
  • the contents of the drum are fed to a separator in which the workpieces are separated from the glass balls.
  • a separator in which the workpieces are separated from the glass balls.
  • a disadvantage of the known method is the relatively high outlay for the application of the intermediate layer and for the production of the so-called promoters, which act as catalysts in the production of the intermediate layer.
  • the intermediate layer is often applied in a separate chemical bath in one or more other treatment containers before the workpieces are treated to apply the actual metallic coating. But even if the application of the intermediate layer is not carried out in a separate treatment container, a relatively large amount of time and the aforementioned expenditure of promoters and the like are required for this.
  • the object of the invention is to provide a method of the type described in the opening paragraph in which the binding of an intermediate layer is no longer necessary and with which metallic coatings can be applied more quickly to metallic workpieces.
  • the bath set to a pH between 1 and 2 simultaneously contains the metal powder and a reaction mixture of hydrazine chloride and / or hydrazine sulfate with metal ions for local element formation and with tin-II and / or antimony-III sulfate Formation of a spongy tin or antimony layer adhering to the metal powder particles is added.
  • copper and / or tin ions can be added to the reaction mixture.
  • the method according to the invention is particularly suitable for the use of zinc, tin, cadmium, silver, gold or their alloys as coating material.
  • the metal powder should have a grain size of less than 10m.
  • metallic coatings can be applied to metallic workpieces without an intermediate layer having been applied beforehand.
  • the use of oxyethylated nonylphenol polyglycol ether strengthens and levels the coating to be applied.
  • local elements are formed. Such local elements arise during the development of hydrogen when metal and acid meet. However, a coherent hydrogen skin often forms, which prevents further reactions. This is especially true when pure zinc meets acid. - If, however, impurities in the form of copper or tin ions are added to the zinc, a local element forms because Zn 2 + dissolves in the zinc, the electrons migrate to the copper and discharge the hydrogen ion there, thus avoiding the formation of the hydrogen skin.
  • tin 11 is converted into metallic tin or antimony 111 into metallic antimony by reduction with hydrazine dichloride and / or hydrazine sulfate, which deposits in a spongy manner, enveloping one or more zinc particles. Due to the presence of oxyethylated nonylphe nol-polyglycol ether prevents the individual particles from redissolving, oxidizing or agglomerating until they reach the surface of the material and are firmly connected to the workpiece surface by mechanical action (impact of the glass balls) and the resulting short-term temperature increase.
  • the workpieces treated with it have a corresponding corrosion resistance.
  • coating metals that have only a low corrosion resistance such as. B. zinc, it is desirable to improve the corrosion resistance.
  • a further reaction mixture with a metal salt of a metal other than the coating metal or with a plastic can be added to the bath.
  • the additional reaction mixture can contain in particular 50% metal salt or plastic, 30% potassium chloride, 15% sodium acetate and 5% silica.
  • tin-II sulfate or antimony-III sulfate or lead chloride are particularly recommended as metal salts.
  • plastic it should be in granulate form with a grain size of less than 8 ⁇ m.
  • Granules made of PVC or melamine resin are particularly suitable as plastics.
  • the procedure is carried out in such a way that the metallic workpieces are placed in an acid-proof drum rotating about their own axis or hung on a rotating frame that rotates in a bath. In the bath or in the drum are then sponged with water baffle, z. B. glass balls introduced. The diameter of the impact body is kept so that it also in recesses, for. B. thread grooves of screws.
  • the pH of the bath is adjusted to a value of approx. 1 to 2 with mineral acids.
  • metal powder particles e.g. B. zinc particles, the diameter of which is 10 micrometers, and dispersed by a few revolutions in the bath.
  • the metal powder particles are activated and held in this activated form by the presence of the oxyethylated nonylphenol polyglycol ether until they come into contact with the workpiece surface, which is also activated, and remain there.
  • the pH value of the bath increases during the treatment of the workpieces in the bath. When the pH has reached 3 to 4, a further reaction mixture, if any, is introduced into the bath.
  • This consists of a metal salt or plastic granulate as well as potassium chloride, sodium acetate and silica.
  • a metal salt or plastic granulate as well as potassium chloride, sodium acetate and silica.
  • potassium chloride sodium acetate
  • silica silica
  • the pH is adjusted to 1-2.
  • the zinc powder was activated immediately, deposited on the base metal and formed a uniform, matt gloss coating of 8 gm.
  • the running time was 10-15 minutes, after which the pH rose to pH 5-6.
  • the screws were separated from the glass balls by unloading them onto a sieve plate.
  • the zinc powder was deposited and formed a 100 ⁇ m thick coating on the wheel springs.
  • the pH had risen to 5-6.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen metallischer Überzüge auf metallische Werkstücke durch Behandeln der Werkstücke in einem inerte Prallkörper enthaltenden Bad, indem die Werkstücke in das Bad getaucht werden und eine Relativierung zwischen Werkstücken und Prallkörpern bzw. Bad erzeugt wird, wobei dem eine wässrige Lösung mit Nonylphenol-Polyglykoläther als Aktivator enthaltenden Bad nach dem Reinigen der Werkstücke Metallionen und ferner ein Reaktionsgemisch sowie das den Überzug bildende Metallpulver zugegeben werden.The invention relates to a method for applying metallic coatings to metallic workpieces by treating the workpieces in a bath containing inert impact bodies, by immersing the workpieces in the bath and creating a relativization between workpieces and impact bodies or bath, with an aqueous solution Bath containing nonylphenol polyglycol ether as activator after cleaning the workpieces metal ions and further a reaction mixture and the metal powder forming the coating are added.

Ein derartiges Verfahren hat gegenüber galvanisch arbeitenden Verfahren den Vorteil, dass die Gefahr einer Wasserstoffversprödung der behandelten Werkstücke weitgehend ausgeschlossen ist. Im allgemeinen geht man bei einem solchen Verfahren so vor, dass die Werkstücke gereinigt werden, wobei gleichzeitig eine Zwischenschicht aus einem dünnen Zinnüberzug aufgebracht wird. Dann wird dem Bad das den eigentlichen Überzug bildende Metallpulver zugeführt, und erst wenn dieses sich nach weiterer Relativbewegung im Bad verteilt hat und der pH-Wert des Bades auf ca. 5 angestiegen ist, wird saures Natriumsulfat zugegeben, unter dessen Wirkung bei weiterer Relativbewegung sich dann der Überzug auf den Werkstücken bildet. - Man kann aber auch so vorgehen, dass die entfetteten Werkstücke zusammen mit den Prallkörpern, die in der Regel aus einer Glaskugel-Mischung bestehen, in eine Trommel eingebracht werden. Durch Zugabe einer Entzunderungschemikalie werden die Werkstücke von Rost und Zunder befreit und die Oberfläche für die Aufnahme einer dann aufzubringenden Zwischenschicht aus einem NE-Metall, insbesondere Kupfer, vorbereitet. Die Zwischenschicht wird aus einer Kupferlösung abgeschieden, die in die Trommel eingefüllt wird. Dann wird eine sogenannte Promoterchemikalie eingegeben, die dafür Sorge trägt, dass das ebenfalls zugefügte pulverförmige Überzugsmetall gereinigt und eine gleichmässige Oberflächenverteilung erzielt wird. Während der Relativbewegung zwischen Werkstücken und Bad bzw. Glaskugeln, d. h. während des Drehens der Trommel, wirken die Glaskugeln als Träger für die Metallpulverteilchen und bringen diese an die Werkstückoberfläche heran, an der sie durch Kaltverschweissung haften bleiben. Der bei der Relativbewegung entstehende mechanische Druck sorgt für die entsprechende Verfestigung des Gefüges. Die Grösse der Glaskugeln wird so gewählt, dass das pulverförmige Überzugmetall auch in Vertiefungen, z. B. auf den Grund von Gewinderillen gelangt und damit eine optimale Beschichtung erreicht wird. Nach einer bestimmten Behandlungszeit wird der Trommelinhalt einem Separator zugeleitet, in dem die Werkstücke von den Glaskugeln getrennt werden. Ein derartiges Verfahren ist in der DE-C-1 771 816 beschrieben.Such a method has the advantage over galvanically operating methods that the danger of hydrogen embrittlement of the treated workpieces is largely excluded. In general, such a process is carried out in such a way that the workpieces are cleaned, an intermediate layer of a thin tin coating being applied at the same time. Then the metal powder that forms the actual coating is added to the bath, and only when this has been distributed in the bath after further relative movement and the pH of the bath has risen to about 5 is acidic sodium sulfate added, under the effect of which further movement moves then the coating forms on the workpieces. - However, one can also proceed in such a way that the degreased workpieces are introduced into a drum together with the impact bodies, which usually consist of a glass ball mixture. By adding a descaling chemical, the workpieces are freed of rust and scale and the surface is prepared for receiving an intermediate layer of a non-ferrous metal, in particular copper, which is then to be applied. The intermediate layer is deposited from a copper solution, which is filled into the drum. Then a so-called promoter chemical is entered, which ensures that the powdered coating metal also added is cleaned and a uniform surface distribution is achieved. During the relative movement between workpieces and bath or glass balls, i.e. H. As the drum rotates, the glass balls act as a carrier for the metal powder particles and bring them to the surface of the workpiece to which they adhere due to cold welding. The mechanical pressure generated during the relative movement ensures that the structure is strengthened accordingly. The size of the glass balls is chosen so that the powdered coating metal also in recesses, for. B. gets to the bottom of thread grooves and thus an optimal coating is achieved. After a certain treatment time, the contents of the drum are fed to a separator in which the workpieces are separated from the glass balls. Such a method is described in DE-C-1 771 816.

Nachteilig bei dem bekannten Verfahren ist der verhältnismässig grosse Aufwand für das Aufbringen der Zwischenschicht und für die Herstellung der sogenannten Promotoren, die als Katalysatoren bei der Erzeugung der Zwichenschicht mitwirken. Vielfach wird nämlich die Zwischenschicht noch in einem gesonderten chemischen Bad in einem oder mehreren anderen Behandlungsbehältern aufgebracht, bevor die Werkstükke zum Aufbringen des eigentlichen metallischen Überzuges behandelt werden. Aber selbst wenn das Aufbringen der Zwichenschicht nicht in einem gesonderten Behandlungsbehälter erfolgt, benötigt man dafür verhältnismässig viel Zeit und den genannten Aufwand an Promotoren und dergleichen.A disadvantage of the known method is the relatively high outlay for the application of the intermediate layer and for the production of the so-called promoters, which act as catalysts in the production of the intermediate layer. In fact, the intermediate layer is often applied in a separate chemical bath in one or more other treatment containers before the workpieces are treated to apply the actual metallic coating. But even if the application of the intermediate layer is not carried out in a separate treatment container, a relatively large amount of time and the aforementioned expenditure of promoters and the like are required for this.

Aufgabe der Erfindung ist es, ein Verfahren der eingangs beschriebenen Gattung anzugeben, bei dem die Bindung einer Zwischenschicht nicht mehr erforderlich ist und mit dem metallische Überzüge schneller auf metallische Werkstücke aufgebracht werden können.The object of the invention is to provide a method of the type described in the opening paragraph in which the binding of an intermediate layer is no longer necessary and with which metallic coatings can be applied more quickly to metallic workpieces.

Diese Aufgabe wird dadurch gelöst, dass dem auf einen pH-Wert zwischen 1 und 2 eingestellten Bad gleichzeitig das Metallpulver und ein Reaktionsgemisch aus Hydrazinchlorid und/oder Hydrazinsulfat mit Metallionen zur Lokalelementbildung sowie mit Zinn-II- und/oder Antimon-III-Sulfat zur Bildung einer schwammigen, auf den Metallpulverpartikeln anhaftenden Zinn- oder Antimonschicht zugegeben wird.This object is achieved in that the bath set to a pH between 1 and 2 simultaneously contains the metal powder and a reaction mixture of hydrazine chloride and / or hydrazine sulfate with metal ions for local element formation and with tin-II and / or antimony-III sulfate Formation of a spongy tin or antimony layer adhering to the metal powder particles is added.

Insbesondere können dem Reaktionsgemisch Kupfer- und/oder Zinnionen zugesetzt werden. Das erfindungsgemässe Verfahren eignet sich insbesondere für die Verwendung von Zink, Zinn, Kadmium, Silber, Gold oder deren Legierungen als Überzugsmaterial. Das Metallpulver sollte eine Korngrösse von kleiner 10m besitzen.In particular, copper and / or tin ions can be added to the reaction mixture. The method according to the invention is particularly suitable for the use of zinc, tin, cadmium, silver, gold or their alloys as coating material. The metal powder should have a grain size of less than 10m.

Mit dem erfindungsgemässen Verfahren lassen sich metallische Überzüge auf metallische Werkstücke aufbringen, ohne dass vorher eine Zwischenschicht aufgebracht worden ist. Dabei wird insbesondere durch den Einsatz oxäthylierter Nonylphenol-Polyglykoläther eine Verfestigung und Einebnung des aufzubringenden Überzuges erreicht. Wesentlich bei der Durchführung des erfindungsgemässen Verfahrens ist, dass Lokalelemente gebildet werden. Derartige Lokalelemente entstehen bei der Entwicklung von Wasserstoff beim Zusammentreffen von Metall und Säure. Dabei bildet sich jedoch häufig eine zusammenhängende Wasserstoffhaut, die weitere Reaktionen verhindert. Das gilt insbesonders, wenn reines Zink mit Säure zusammentrifft. - Werden dem Zink jedoch Verunreinigungen in Form von Kupfer- oder Zinnionen zugesetzt, dann bildet sich ein Lokalelement weil am Zink Zn2+ in Lösung geht, die Elektronen zum Kupfer wandern und dort das Wasserstoffion entladen und somit die Bildung der Wasserstoffhaut vermieden wird. Gleichzeitig wird durch Reduktion mit Hydrazindichlorid und/oder Hydrazinsulfat Zinn 11 in metallisches Zinn oder Antimon 111 in metallisches Antimon überführt, das sich schwammig, ein oder mehrere Zinkpartikeln umhüllend, abscheidet. Durch die Anwesenheit oxäthylierter Nonylphenol-polyglykoläther wird ein Rücklösen, Oxydieren oder Zusammenballen der einzelnen Partikeln so lange vermieden, bis sie an die Werkstoffoberfläche gelangen und dort durch mechanische Einwirkung (Schlagwirkung der Glaskugeln) sowie die dabei entstehende kurzzeitige Temperaturerhöhung fest mit der Werkstückoberfläche verbunden werden.With the method according to the invention, metallic coatings can be applied to metallic workpieces without an intermediate layer having been applied beforehand. In particular, the use of oxyethylated nonylphenol polyglycol ether strengthens and levels the coating to be applied. It is essential when carrying out the method according to the invention that local elements are formed. Such local elements arise during the development of hydrogen when metal and acid meet. However, a coherent hydrogen skin often forms, which prevents further reactions. This is especially true when pure zinc meets acid. - If, however, impurities in the form of copper or tin ions are added to the zinc, a local element forms because Zn 2 + dissolves in the zinc, the electrons migrate to the copper and discharge the hydrogen ion there, thus avoiding the formation of the hydrogen skin. At the same time, tin 11 is converted into metallic tin or antimony 111 into metallic antimony by reduction with hydrazine dichloride and / or hydrazine sulfate, which deposits in a spongy manner, enveloping one or more zinc particles. Due to the presence of oxyethylated nonylphe nol-polyglycol ether prevents the individual particles from redissolving, oxidizing or agglomerating until they reach the surface of the material and are firmly connected to the workpiece surface by mechanical action (impact of the glass balls) and the resulting short-term temperature increase.

Je nach Art des verwendeten Überzugsmetalls, das z. B. Zinn, Zink, Kadmium, Blei, aber auch Silber oder Gold sein kann, besitzen die damit behandelten Werkstücke eine entsprechende Korrosionsbeständigkeit. Bei Überzugsmetallen, die eine nur geringe Korrosionsbeständigkeit besitzen, wie z. B. Zink, ist es wünschenswert, die Korrosionsbeständigkeit zu verbessern. Hier kann kurz vor Beendigung der Überzugsbildung dem Bad ein weiteres Reaktionsgemisch mit einem Metallsalz eines anderen Metalls als dem Überzugsmetall oder mit einem Kunststoff zugesetzt werden.Depending on the type of coating metal used, the z. B. tin, zinc, cadmium, lead, but also silver or gold, the workpieces treated with it have a corresponding corrosion resistance. With coating metals that have only a low corrosion resistance, such as. B. zinc, it is desirable to improve the corrosion resistance. Here, just before the formation of the coating has ended, a further reaction mixture with a metal salt of a metal other than the coating metal or with a plastic can be added to the bath.

Die Beendigung der Überzugsbildung lässt sich am Ansteigen des pH-Wertes des Bades ablesen. Deswegen empfiehlt es sich, das weitere Reaktionsgemisch zuzusetzen, wenn der pH-Wert des Bades auf 3 bis 4 angestiegen ist.The completion of the coating formation can be seen from the rise in the pH of the bath. It is therefore advisable to add the further reaction mixture when the pH of the bath has risen to 3 to 4.

Das zusätzliche Reaktionsgemisch kann insbesondere 50% Metallsalz oder Kunststoff, 30% Kaliumchlorid, 15% Natriumacetat und 5% Kieselsäure enthalten.The additional reaction mixture can contain in particular 50% metal salt or plastic, 30% potassium chloride, 15% sodium acetate and 5% silica.

Bei Überzügen aus Zink empfehlen sich als Metallsalze insbesondere Zinn-II-Sulfat oder Antimon-III-Sulfat oder Bleichlorid.In the case of zinc coatings, tin-II sulfate or antimony-III sulfate or lead chloride are particularly recommended as metal salts.

Bei Verwendung von Kunststoff sollte dieser in Granulatform mit einer Korngrösse kleiner 8 µm vorliegen. Als Kunststoffe kommen insbesondere Granulate aus PVC oder Melamin-Harz in Frage.If plastic is used, it should be in granulate form with a grain size of less than 8 µm. Granules made of PVC or melamine resin are particularly suitable as plastics.

Im einzelnen geht man bei der Durchführung des Verfahrens so vor, dass die metallischen Werkstücke in eine säurefeste, um die eigene Achse rotierende Trommel gebracht oder an ein rotierendes Gestell gehängt werden, das in einem Bad rotiert. In das Bad bzw. in die Trommel werden dann mit Wasser ausgeschwämmte Prallkörper, z. B. Glaskugeln, eingebracht. Der Durchmesser der Prallkörper wird so gehalten, dass sie auch in Vertiefungen, z. B. Gewinderillen von Schrauben, gelangen können.In detail, the procedure is carried out in such a way that the metallic workpieces are placed in an acid-proof drum rotating about their own axis or hung on a rotating frame that rotates in a bath. In the bath or in the drum are then sponged with water baffle, z. B. glass balls introduced. The diameter of the impact body is kept so that it also in recesses, for. B. thread grooves of screws.

Der pH-Wert des Bades wird mit Mineralsäuren auf einen Wert von ca. 1 bis 2 eingestellt. Nach einigen Umdrehungen der Trommel oder des Gestells wird eine im Hinblick auf Oberfläche und gewünschte Schichtdicke bestimmte Menge an Metallpulverpartikeln, z. B. Zinkpartikeln, deren Durchmesser 10 Micrometer ist, eingesetzt und durch einige Umdrehungen im Bad dispergiert. Durch Zusatz eines Reaktionsgemisches aus Hydrazindichlorid und/oder Hydrazinsulfat unter Anwesenheit von Zinn-II-Sulfat oder Antimon-III-Sulfat und Kupferionen und/oder Zinnionen werden die Metallpulverpartikel aktiviert und durch die Anwesenheit der oxäthylierten Nonylphenol-Polyglykoläther in dieser aktivierten Form gehalten, bis sie mit der gleichfalls aktivierten Werkstückoberfläche in Berührung kommen und dort haften bleiben. Während der Behandlung der Werkstücke im Bad steigt der pH-Wert des Bades an. Wenn der pH-Wert 3 bis 4 erreicht hat, wird ein gegebenenfalls weiteres Reaktionsgemisch in das Bad eingegeben. Dieses besteht aus einem Metallsalz oder Kunststoffgranulat sowie zusätzlich Kaliumchlorid, Natriumacetat und Kieselsäure. Durch Ionenaustausch bildet sich innerhalb von 5 bis 10 Min. eine elementare Metall-oder Kunststoffschicht auf dem vorher gebildeten Überzug (aus Zink), wobei die Metall- oder Kunststoffschicht fest im Überzug verankert ist. Das führt zu einer ganz wesentlichen Erhöhung der Korrosionsbeständigkeit.The pH of the bath is adjusted to a value of approx. 1 to 2 with mineral acids. After a few revolutions of the drum or the frame, a certain amount of metal powder particles, e.g. B. zinc particles, the diameter of which is 10 micrometers, and dispersed by a few revolutions in the bath. By adding a reaction mixture of hydrazine dichloride and / or hydrazine sulfate in the presence of tin (II) sulfate or antimony (III) sulfate and copper ions and / or tin ions, the metal powder particles are activated and held in this activated form by the presence of the oxyethylated nonylphenol polyglycol ether until they come into contact with the workpiece surface, which is also activated, and remain there. The pH value of the bath increases during the treatment of the workpieces in the bath. When the pH has reached 3 to 4, a further reaction mixture, if any, is introduced into the bath. This consists of a metal salt or plastic granulate as well as potassium chloride, sodium acetate and silica. Through ion exchange, an elementary metal or plastic layer forms on the previously formed coating (made of zinc) within 5 to 10 minutes, the metal or plastic layer being firmly anchored in the coating. This leads to a very substantial increase in corrosion resistance.

Im folgenden werden zwei Versuchsergebnisse wiedergegeben.Two test results are given below.

Versuch 1Trial 1

In eine achteckige säurefeste Trommel mit einem Volumen von 200 die auf beiden Seiten eine Be- und Entladungsöffnung hat, werden 100 I Glaskugeln mit einem Durchmesser von 0,2 bis 6,2mm gefüllt und 400kg vorgereinigte Schrauben M 8 x 12 zugesetzt und mit Wasser überdeckt. Anschliessend wurde mit 1,5-2,21 eines Aktivators, bestehend aus:

  • 300-400 g/I H2S02
  • 10- 20g/l oxäthylierter Nonylphenol-Polyglykoläther
  • 1- 5 g/I Korrosionsinhibitor
In an octagonal acid-proof drum with a volume of 200, which has a loading and unloading opening on both sides, 100 I glass balls with a diameter of 0.2 to 6.2 mm are filled and 400 kg of pre-cleaned M 8 x 12 screws are added and covered with water . Then an activator consisting of:
  • 300-400 g / IH 2 S0 2
  • 10- 20g / l oxyethylated nonylphenol polyglycol ether
  • 1- 5 g / l corrosion inhibitor

der pH-Wert 1-2 eingestellt.the pH is adjusted to 1-2.

Nach 2-Minuten-Drehung bei 10 UpM wurden 2816 g Zinkpulver und 150 g eines Reaktionsgemisches, bestehend aus:

Figure imgb0001
After rotating for 2 minutes at 10 rpm, 2816 g of zinc powder and 150 g of a reaction mixture consisting of:
Figure imgb0001

zugesetzt.added.

Das Zinkpulver wurde sofort aktiviert, auf dem Grundmetall abgeschieden und bildete einen gleichförmigen, mattglänzenden Überzug von 8 gm.The zinc powder was activated immediately, deposited on the base metal and formed a uniform, matt gloss coating of 8 gm.

Die Laufzeit betrug 10-15 Minuten, wonach der pH-Wert auf pH 5-6 anstieg. Die Schrauben wurden von den Glaskugeln durch Entladen auf ein Siebblech getrennt.The running time was 10-15 minutes, after which the pH rose to pH 5-6. The screws were separated from the glass balls by unloading them onto a sieve plate.

Der Versuch wurde mit Zinnpulver, Kadmiumpulver, Bleipulver u. a. Metallpulvern und deren Legierungen untereinander mit gleichem Ergebnis wiederholt. Bei einer Variante dieses Versuches wurde nach ca. 10 Minuten und bei einem pH-Wert des Bades von 3 bis 4 ein weiteres Reaktionsgemisch aus

Figure imgb0002
in die Trommel gegeben.The experiment was repeated with tin powder, cadmium powder, lead powder and other metal powders and their alloys with one another with the same result. In a variant of this experiment, another reaction mixture was produced after about 10 minutes and at a bath pH of 3 to 4
Figure imgb0002
placed in the drum.

Durch Ionenaustausch bildete sich innerhalb von 5 bis 10 Minuten eine elementare Schicht aus Zinn oder Antimon oder Blei oder deren Legierungen auf dem vorher gebildeten Zinküberzug, so dass die Korrosionsbeständigkeit nach ASTM B 117 um ca. 300 Stunden anstieg.Through ion exchange, an elementary layer of tin or antimony or lead or their alloys formed on the previously formed zinc coating within 5 to 10 minutes, so that the corrosion resistance according to ASTM B 117 increased by approx. 300 hours.

Versuch 2Trial 2

Auf ein Rotationsgestell wurden 8 Radfedern mit einer Länge von 30 cm und einem Durchmesser von 8 cm gehängt.8 wheel springs with a length of 30 cm and a diameter of 8 cm were hung on a rotating frame.

Das Gestell wurde kontinuierlich durch 501 Glaskugeln (Zusammensetzung wie bei Versuch 1) geführt, denen 11 eines Aktivators, bestehend aus:

  • 100-200g/l H2SO4
  • 40- 60 g/I oxäthylierter Nonylphenol-Polyglykoläther
  • 1 - 5 g/1 Korrosionsinhibitor

zur Einstellung des pH-Wertes 1 zugesetzt wurden. Anschliessend wurden sofort 1000 g Zinkpulver und 100 eines Reaktionsgemisches, bestehend aus:
Figure imgb0003
zugesetzt.The frame was continuously passed through 501 glass balls (composition as in test 1), which 11 of an activator, consisting of:
  • 100-200g / l H 2 SO 4
  • 40-60 g / l oxyethylated nonylphenol polyglycol ether
  • 1 - 5 g / 1 corrosion inhibitor

1 were added to adjust the pH. Subsequently, 1000 g of zinc powder and 100 of a reaction mixture consisting of:
Figure imgb0003
added.

Nach 10 Minuten Laufzeit war das Zinkpulver abgeschieden und bildete einen 100 µm dicken Überzug auf den Radfedern. Der pH-Wert war auf 5-6 angestiegen.After a running time of 10 minutes, the zinc powder was deposited and formed a 100 µm thick coating on the wheel springs. The pH had risen to 5-6.

Dieser Versuch wurde ebenfalls mit den unter Versuch 1 beschriebenen Metallpulvern durchgeführt. Die Ergebnisse waren äquivalent.This experiment was also carried out using the metal powders described in Experiment 1. The results were equivalent.

Bei einer Variante dieses Versuches wurde nach ca. 7 Minuten und bei einem pH-Wert des Bades von 3-4 ein weiteres Reaktionsgemisch aus 50% eines Kunststoffgranulates (PVC-Granulat und/oder Melamin-Harz-Granulat) einer Korngrösse kleiner 8 µm, 30% Kaliumchlorid, 15% Natriumacetat und 5% Kieselsäure in das Bad gegeben. Nach weiteren 5-10 Minuten war auf dem Zinküberzug eine gleichmässig im Zinküberzug verankerte Kunststoffschicht gebildet, die eine Erhöhung der Korrosionsbeständigkeit der Radfedern um ca. 1000 Stunden nach ASTM B 117 bewirkt.In a variant of this experiment, after about 7 minutes and with a bath pH of 3-4, a further reaction mixture composed of 50% of plastic granules (PVC granules and / or melamine resin granules) with a grain size of less than 8 μm was 30% potassium chloride, 15% sodium acetate and 5% silica were added to the bath. After a further 5-10 minutes, a uniformly anchored plastic layer was formed on the zinc coating, which increases the corrosion resistance of the wheel springs by approx. 1000 hours in accordance with ASTM B 117.

Claims (10)

1. A process for applying metallic coatings to metallic workpieces by treating the workpieces in a bath containing inert impact bodies, the workpieces being immersed into the bath and a relative movement being produced between the workpieces and impact bodies or bath, and after cleaning of the workpieces metal ions and also a reaction mixture as well as the metal powder forming the coating are added to the bath containing an aqueous acid solution with nonylphenol-polyglycolether as an activator, characterized in that simultaneously the metal powder and a reaction mixture of hydrazine chloride and/or hydrazine sulphate with metal ions for local element formation as well as with tin-II- and/or antimony-III-sulphate to form a spongy tin or antimony layer adhering to the metal powder -particles is added to the bath set at a pH value of between 1 and 2.
2. A process according to claim 1, characterized in that copper and/or tin ions are added to the reaction mixture.
3. A process according to claim 1, characterized in that zinc, tin, cadmium, silver, gold or alloys thereof are used as coating material.
4. A process according to one or several of claims 1-3, characterized in that metal powder with a particle size < 10 µm is used.
5. A process according to one or several of claims 1-4, characterized in that shortly before the end of the formation of the coating a further reaction mixture with a metal salt of another metal as the coating material or with a plastic is added to the bath.
6. A process according to claim 5, characterized in that the further reaction mixture is added when the pH value of the bath has increased to 3 to 4.
7. A process according to claim 5 or 6, characterized in that the additional reaction mixture contains 50% metal salt or plastic, 30% potassium chloride, 15% sodium acetate and 5% silicic acid.
8. A process according to one of claims 5-7, characterized in that tin-II-sulphate and/or antimony-III-sulphate and/or lead chloride is used as a metal salt.
9. A process according to one of claims 5-8, characterized in that a granulated material with a particle size smaller than 8 p.m is used as a plastic.
10. A process according to claim 9, characterized in that a granulated material formed of PVC and/or melamine resin is used as a plastic.
EP79105012A 1978-12-15 1979-12-08 Process for applying metallic coatings to metallic workpieces by a mechano-chemical treatment of said pieces Expired EP0012399B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79105012T ATE1823T1 (en) 1978-12-15 1979-12-08 METHOD OF APPLYING METALLIC COATINGS TO METALLIC WORKPIECES BY MECHANIC-CHEMICAL TREATMENT OF THE WORKPIECES.

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Application Number Priority Date Filing Date Title
DE2854159 1978-12-15
DE19782854159 DE2854159C2 (en) 1978-12-15 1978-12-15 Process for applying metallic coatings to metallic workpieces by mechanical-chemical treatment of the workpieces
DE19792919726 DE2919726A1 (en) 1979-05-16 1979-05-16 Depositing metal coatings on workpieces - from aq. acid bath contg. polyglycol ether activator, powdered coating metal and reducible metal ions
DE2919726 1979-05-16

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EP0012399A1 EP0012399A1 (en) 1980-06-25
EP0012399B1 EP0012399B1 (en) 1982-11-17
EP0012399B2 true EP0012399B2 (en) 1986-09-17

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WO1981003292A1 (en) * 1980-05-12 1981-11-26 Minnesota Mining & Mfg Composition for mechanically depositing heavy metallic coatings
DE3720379A1 (en) * 1986-06-19 1988-01-28 Neugebauer Erich Dr Process for applying metallic coatings to metallic workpieces by mechanical-chemical treatment of the workpieces
EP0288484A4 (en) * 1986-10-22 1989-10-12 Macdermid Inc Mechanical plating with oxidation-prone metals.

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* Cited by examiner, † Cited by third party
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US3268356A (en) * 1959-01-28 1966-08-23 Minnesota Mining & Mfg Metal plating by successive addition of plating ingredients
US4062990A (en) * 1976-06-10 1977-12-13 Waldes Kohinoor, Inc. Non-polluting system for metal surface treatments

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