EP0012399A1 - 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 PDFInfo
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- EP0012399A1 EP0012399A1 EP79105012A EP79105012A EP0012399A1 EP 0012399 A1 EP0012399 A1 EP 0012399A1 EP 79105012 A EP79105012 A EP 79105012A EP 79105012 A EP79105012 A EP 79105012A EP 0012399 A1 EP0012399 A1 EP 0012399A1
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- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
- C23C24/045—Impact 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 mechanical-chemical treatment of the workpieces in a bath containing an inner impact body from an aqueous acidic solution, the workpieces being immersed in the bath and producing a relative movement between workpieces and impact bodies or bath and an activator and a little later the powdered coating metal and a reaction mixture are added to the bath.
- Such a method has the advantage over galvanically operating methods that the risk of hydrogen embrittlement of the treated workpieces is largely eliminated.
- the process is carried out in such a way that the degreased workpieces are introduced into a drum together with the impact bodies, which generally consist of a glass ball mixture.
- the impact bodies which generally 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 what is also added powdered coating metal cleaned and a uniform surface distribution is achieved.
- the glass balls act as carriers for the metal powder particles and bring them to the workpiece surface 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 spheres is chosen so that the powdered coating metal also gets into recesses, for example to the bottom due to thread grooves, and thus an optimal coating is achieved.
- a disadvantage of the known method is the relatively large 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 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 does not take place in a separate treatment container, it takes a relatively large amount of time and the above-mentioned expenditure on promoters and the like. the like
- the object of the invention is to provide a method of the type described in the introduction in which the formation of an intermediate layer is no longer necessary and with which metallic coatings can be applied more quickly to metallic workpieces.
- This object is achieved in that the pH of the bath is adjusted between 1 and 2, in that an oxyethylated nonylphenol polyglycol ether is used as activator and in that metal ions are added to the reaction mixture to form local elements.
- reaction mixture can contain hydrazine dichloride and / or hydrazine sulfate and / or iron (II) sulfate as well as tin (II) and / or antimony (II) compounds to form a spongy tin or antimony layer adhering to the metal powder particles.
- 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 ⁇ 10 ⁇ m.
- metallic coatings can be applied to metallic workpieces without an intermediate layer having been applied beforehand.
- the use of oxyethylated nonylphenol polyglycol ether achieves solidification and leveling of the coating to be applied.
- local elements arise during the development of hydrogen when metal and acid meet.
- a coherent hydrogen often forms skin that prevents further reactions. This is especially true when pure zinc meets acid.
- 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 II is converted into metallic tin or antimony II into metallic antimony, which deposits spongily, enveloping one or more zinc particles.
- ethylated nonylphenol 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 them have a corresponding corrosion resistance.
- coating metals e.g. Tin, zinc, cadmium, lead, but also silver or gold
- the workpieces treated with them have a corresponding corrosion resistance.
- coating metals that have only a low corrosion resistance e.g. Zinc
- 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-II 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 for carrying out the method is such that the metallic workpieces are placed in an acid-proof drum which rotates about its own axis or are hung on a rotating frame which rotates in a bath.
- Impact bodies which have been washed out with water, e.g. Glass balls, introduced.
- the diameter of the impact body is kept so that it also fits in depressions, e.g. Thread grooves of screws can get.
- the pH of the bath is adjusted to a value of approx. 1 to 2 with mineral acids.
- a quantity of metal powder particles for example zinc particles, the diameter of which is 10 micrometers, which is determined with regard to surface and desired layer thickness, is used and dispersed in the bath by a few revolutions.
- 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 zinc powder was activated immediately, deposited on the base metal and formed a uniform, matt glossy coating of 8 my.
- 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 frame was continuously passed through 50 1 glass balls (composition as in test 1), which 1 1 of an activator consisting of: 1 were added to adjust the pH. Then immediately 1000 g of zinc powder and 100 g of a reaction mixture consisting of:
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Aufbringen metallischer Überzüge auf metallische Werkstücke durch mechanisch-chemisches Behandeln der Werkstücke in einem innerte Prallkörper enthaltenden Bad aus einer wässrigen sauren Lösung, wobei die Werkstücke in das Bad getaucht werden und eine Relativbewegung zwischen Werkstücken und Prallkörpern bzw. Bad erzeugt wird und dem Bad ein Aktivator sowie etwas später das pulverförmige Überzugmetall sowie ein Reaktionsgemisch beigegeben werden.The invention relates to a method for applying metallic coatings to metallic workpieces by mechanical-chemical treatment of the workpieces in a bath containing an inner impact body from an aqueous acidic solution, the workpieces being immersed in the bath and producing a relative movement between workpieces and impact bodies or bath and an activator and a little later the powdered coating metal and a reaction mixture are added to the bath.
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 gattungsgemäßen Verfahren so vor, daß die entfetteten Werkstücke zusammen mit den Prallkörpern, die in der Regel aus einer Glaskugel-Mischung bestehen, in eine Trommel eingebracht werden. Durch Zugabe einerEntzunderungschemikalie 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 Uberzugmetall 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 aufgrund 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 z.B. in der DE-PS 17 71 816 beschrieben.Such a method has the advantage over galvanically operating methods that the risk of hydrogen embrittlement of the treated workpieces is largely eliminated. In general, the process is carried out in such a way that the degreased workpieces are introduced into a drum together with the impact bodies, which generally 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 what is also added powdered coating metal cleaned and a uniform surface distribution is achieved. During the relative movement between workpieces and the bath or glass balls, ie during the rotation of the drum, the glass balls act as carriers for the metal powder particles and bring them to the workpiece surface 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 spheres is chosen so that the powdered coating metal also gets into recesses, for example to the bottom due to 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 for example in DE-PS 17 71 816.
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 Zwischenschicht mitwirken. Vielfach wird nämlich die Zwischenschicht noch in einem gesonderten chemischen Bad in einem oder mehreren anderen Behandlungsbehältern aufgebracht, bevor die Werkstücke zum Aufbringen des eigentlichen metallischen Überzuges behandelt werden. Aber selbst wenn das Aufbringen der Zwischenschicht nicht in einem gesonderten Behandlungsbehälter erfolgt, benötigt man dafür verhältnismäßig viel Zeit und den genannten Aufwand an Promotoren u. dgl.A disadvantage of the known method is the relatively large 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 many cases, the intermediate layer is 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 does not take place in a separate treatment container, it takes a relatively large amount of time and the above-mentioned expenditure on promoters and the like. the like
Aufgabe der Erfindung ist es, ein Verfahren der eingangs beschriebenen Gattung anzugeben, bei dem die Bildung 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 introduction in which the formation 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 der pH-Wert des Bades zwischen 1 und 2 eingestellt wird, daß als Aktivator ein oxäthylierter Nonylphenol-Polyglykoläther verwendet wird und daß dem Reaktionsgemisch zur Lokalelementbildung Metallionen zugesetzt werden.This object is achieved in that the pH of the bath is adjusted between 1 and 2, in that an oxyethylated nonylphenol polyglycol ether is used as activator and in that metal ions are added to the reaction mixture to form local elements.
Insbesondere können dem Reaktionsgemisch Kupfer- und/ oder Zinnionen zugesetzt werden. Das Reaktionsgemisch kann Hydrazindichlorid und/oder Hydrazinsulfat und/ oder Eisen-II-sulfat sowie Zinn-II- und/oder Antimon-II-Verbindungen zur Bildung einer schwammigen, auf den Metallpulverpartikeln haftenden Zinn- oder Antimonschicht enthalten.In particular, copper and / or tin ions can be added to the reaction mixture. The reaction mixture can contain hydrazine dichloride and / or hydrazine sulfate and / or iron (II) sulfate as well as tin (II) and / or antimony (II) compounds to form a spongy tin or antimony layer adhering to the metal powder particles.
Das erfindungsgemäße Verfahren eignet sich insbesondere für die Verwendung Zink, Zinn, Kadmium, Silber, Gold oder deren Legierungen als Uberzugsmaterial.Das Metallpulver sollte eine Korngröße von< 10µm besitzen.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 <10 μm.
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 insbesondere 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 Hydrazin und/oder Eisen-II-Sulfat Zinn II in metallisches Zinn oder Antimon II in metallisches Antimon überführt, das sich schwammig,.ein oder mehrere Zinkpartikel umhüllend, abscheidet. Durch die Anwesenheit oxäthylierter Nonylphenol-Polyglykoläther wird ein Rücklösen, Oxydieren oder Zusammenballen der einzelnen Partikel solange 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 achieves solidification and leveling of 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 often forms skin that 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, by reduction with hydrazine dichloride and / or hydrazine and / or iron-II-sulfate, tin II is converted into metallic tin or antimony II into metallic antimony, which deposits spongily, enveloping one or more zinc particles. The presence of ethylated nonylphenol 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 Uberzugmetalls, das z.B. Zinn, Zink, Kadmium, Blei aber auch Silber oder Gold sein kann, besitzen die damit behandelten Werkstücke eine entsprechende Korrosionsbeständigkeit. Bei Uberzugsmetallen, die eine nur geringe Korrosionsbeständigkeit besitzen, wie z.B. Zink, ist es wünschenswert, die Korrosionsbeständigkeit zu verbessern. Hier kann kurz vor Beendigung der Überzugbildung dem Bad ein weiteres Reaktionsgemisch mit einem Metallsalz eines anderen Metalls als dem Uberzugsmetall oder mit einem Kunststoff zugesetzt werden.Depending on the type of coating metal used, e.g. Tin, zinc, cadmium, lead, but also silver or gold, the workpieces treated with them have a corresponding corrosion resistance. For coating metals that have only a low corrosion resistance, e.g. Zinc, it is desirable to improve 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 emfpiehlt 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 increase in the pH of the bath. It is therefore advisable to add the further reaction mixture if 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-II-Sulfat oder Bleichlorid.In the case of zinc coatings, tin-II sulfate or antimony-II 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 infrage.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 for carrying out the method is such that the metallic workpieces are placed in an acid-proof drum which rotates about its own axis or are hung on a rotating frame which rotates in a bath. Impact bodies which have been washed out with water, e.g. Glass balls, introduced. The diameter of the impact body is kept so that it also fits in depressions, e.g. Thread grooves of screws can get.
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 und/oder Eisen-II-Sulfat unter Anwesenheit von Zinn-II-Sulfat oder Antimon-II-Sulfat und Kupferionen und/oder Zinnionen werden die Metallpulverpartikel aktiviert und durch die Anwesenheit der oxäthylierten Nonylphenol-Polyglykoläther in dieser 8 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 quantity of metal powder particles, for example zinc particles, the diameter of which is 10 micrometers, which is determined with regard to surface and desired layer thickness, is used and dispersed in the bath by a few revolutions. By adding a reaction mixture of hydrazine dichloride and / or hydrazine sulfate and / or iron (II) sulfate under Presence of stannous sulfate or antimony-II-sulphate and copper ions and / or tin ions are activated, the metal powder particles and held in place by the presence of the oxyethylated nonylphenol polyglycol ether in this 8 activated form until they come with the likewise activated workpiece surface in contact and stick 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 shown below.
In eine achteckige säurefeste Trommel mit einem Volumen von 200 1, die auf beiden Seiten eine Be- und Entladungsöffnung hat, werden 100 1 Glaskugeln mit einem Durchmesser von 0,2 bis 6,2 mm gefüllt und 400 kg vorgereinigte Schrauben M 8 x 12 zugesetzt und mit Wasser überdeckt. Anschließend wurde mit 1,5 - 2,2 1 eines Aktivators, bestehend aus:
Nach 2 Minuten-Drehung bei 10 UPM wurden 2816g Zinkpulver und 150 g eines Reaktionsgemisches bestehend aus:
Das Zinkpulver wurde sofort aktiviert, auf dem Grundmetall abgeschieden und bildete einen gleichförmigen, mattgländenzen Überzug von 8 my.The zinc powder was activated immediately, deposited on the base metal and formed a uniform, matt glossy coating of 8 my.
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
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.Ion exchange formed within 5 to 10 Minutes an elementary layer of tin or antimony or lead or their alloys on the previously formed zinc coating, so that the corrosion resistance according to ASTM B 117 increased by approx. 300 hours.
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 50 1 Glaskugeln (Zusammensetzung wie bei Versuch 1) geführt, denen 1 1 eines Aktivators bestehend aus:
Nach 10 Minuten Laufzeit war das Zinkpulver abgeschieden und bildete ein 100 my 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 my 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 with 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 my, 30% 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 consisting of 50% of plastic granules (PVC granules and / or melamine resin granules) with a grain size of less than 8 microns was 30% sodium acetate and 5% silica added to the bath. After a further 5 - 10 minutes, a zinc-coated plastic layer was formed on the zinc coating, which increases the corrosion resistance of the wheel springs by approx. 1000 hours according to ASTM B 117.
Claims (11)
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. |
Applications Claiming Priority (4)
| 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 |
| DE2919726 | 1979-05-16 | ||
| 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 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0012399A1 true EP0012399A1 (en) | 1980-06-25 |
| EP0012399B1 EP0012399B1 (en) | 1982-11-17 |
| EP0012399B2 EP0012399B2 (en) | 1986-09-17 |
Family
ID=25776868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79105012A Expired EP0012399B2 (en) | 1978-12-15 | 1979-12-08 | Process for applying metallic coatings to metallic workpieces by a mechano-chemical treatment of said pieces |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0012399B2 (en) |
| DE (1) | DE2964070D1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP0288484A1 (en) * | 1986-10-22 | 1988-11-02 | Macdermid Incorporated | Mechanical plating with oxidation-prone metals |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268356A (en) * | 1959-01-28 | 1966-08-23 | Minnesota Mining & Mfg | Metal plating by successive addition of plating ingredients |
| DE1771816A1 (en) * | 1967-07-17 | 1972-02-03 | Minnesota Mining & Mfg | Mechanical plating |
| US4062990A (en) * | 1976-06-10 | 1977-12-13 | Waldes Kohinoor, Inc. | Non-polluting system for metal surface treatments |
-
1979
- 1979-12-08 DE DE7979105012T patent/DE2964070D1/en not_active Expired
- 1979-12-08 EP EP79105012A patent/EP0012399B2/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268356A (en) * | 1959-01-28 | 1966-08-23 | Minnesota Mining & Mfg | Metal plating by successive addition of plating ingredients |
| DE1771816A1 (en) * | 1967-07-17 | 1972-02-03 | Minnesota Mining & Mfg | Mechanical plating |
| US4062990A (en) * | 1976-06-10 | 1977-12-13 | Waldes Kohinoor, Inc. | Non-polluting system for metal surface treatments |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP0288484A1 (en) * | 1986-10-22 | 1988-11-02 | Macdermid Incorporated | Mechanical plating with oxidation-prone metals |
| EP0288484A4 (en) * | 1986-10-22 | 1989-10-12 | Macdermid Inc | Mechanical plating with oxidation-prone metals. |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0012399B1 (en) | 1982-11-17 |
| DE2964070D1 (en) | 1982-12-23 |
| EP0012399B2 (en) | 1986-09-17 |
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