EP0012399B2 - Procédé d'application de couches métalliques sur des objets métalliques par un traitement mécano-chimique desdits objets - Google Patents

Procédé d'application de couches métalliques sur des objets métalliques par un traitement mécano-chimique desdits objets 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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EP
European Patent Office
Prior art keywords
bath
process according
workpieces
reaction mixture
tin
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.)
Expired
Application number
EP79105012A
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German (de)
English (en)
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EP0012399B1 (fr
EP0012399A1 (fr
Inventor
Bernd Tolkmit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tolkmit Bernd
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Tolkmit Bernd
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25776868&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0012399(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE19782854159 external-priority patent/DE2854159C2/de
Priority claimed from DE19792919726 external-priority patent/DE2919726A1/de
Application filed by Tolkmit Bernd filed Critical Tolkmit Bernd
Priority to AT79105012T priority Critical patent/ATE1823T1/de
Publication of EP0012399A1 publication Critical patent/EP0012399A1/fr
Publication of EP0012399B1 publication Critical patent/EP0012399B1/fr
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Publication of EP0012399B2 publication Critical patent/EP0012399B2/fr
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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
    • 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 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)

Claims (10)

1. Procédé d'application de couches métalliques sur des objets métalliques, par un traitement mécanochimique desdits objets dans un bain contenant des corps inertes, dans lequel les objets sont plongés, et en produisant un mouvement relatif entre les objets et les corps d'impact et le bain, traitement pendant lequel on ajoute au bain contenant, comme agent activant, une solution aqueuse de nonyl-phénol-polyglycol-éther, et après nettoyage des objets, des ions métalliques, et, en outre, un mélange de réaction, ainsi que la poudre métallique devant former la couche de revêtement désirée, procédé caractérisé en ce que, à un bain dont la valeur de pH a été réglée entre 1 et 2, on ajoute simultanément la poudre de métal et un mélange de réaction consistant en chlorure d'hydrazine et/ou sulfate d'hydrazine, avec des ions métalliques pour la formation d'éléments localisés, ainsi que sulfate d'étain Il ou sulfate d'antimoine III pour la formation d'une couche spongieuse d'étain ou d'antimoine sur les particules de métal.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on ajoute au mélange de réaction des ions de cuivre et/ou d'étain.
3. Procédé suivant la revendication 1, caractérisé en ce que, comme matériau de couche de revêtement, on utilise le zinc, le cadmium, l'argent, l'or ou leurs alliages.
4. Procédé suivant l'une quelconque des revendications 1 à 3, caractérisé en ce que la poudre de métal utilisée présente une grosseur de grain inférieure à 10 microns.
5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que, peu avant la fin de la formation de la couche de revêtement, on ajoute au bain un autre mélange de réaction contenant un sel métallique d'un autre métal que celui de revêtement, ou une matière synthétique.
6. Procédé suivant la revendication 5, caractérisé en ce que l'autre mélange de réaction est ajouté lorsque la valeur de pH du bain s'est accrue jusqu'à 3 à 4.
7. Procédé suivant l'une quelconque des revendications 5 ou 6, caractérisé en ce que le mélange de réaction supplémentaire contient 50% de sel métallique ou de matière synthétique, 30% de chlorure de potassium, 15% d'acétate de sodium et 5% de silice.
8. Procédé suivant l'une quelconque des revendications 5 à 7, caractérisé en ce que, comme sel métallique, on utilise le sulfate d'étain Il et/ou le sulfate d'antimoine III, et/ou le chlorure de plomb.
9. Procédé suivant l'une quelconque des revendications 5 à 8, caractérisé en ce que, comme matière synthétique, on utilise un granulat ayant une grosseur de grain inférieure à 8 microns.
10. Procédé suivant la revendication 9, caractérisé en ce que, comme matière synthétique, on utilise un granulat de chlorure de polyvinyle et/ou une résine mélamine.
EP79105012A 1978-12-15 1979-12-08 Procédé d'application de couches métalliques sur des objets métalliques par un traitement mécano-chimique desdits objets Expired EP0012399B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79105012T ATE1823T1 (de) 1978-12-15 1979-12-08 Verfahren zum aufbringen metallischer ueberzuege auf metallische werkstuecke durch mechanischchemisches behandeln der werkstuecke.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2854159 1978-12-15
DE19782854159 DE2854159C2 (de) 1978-12-15 1978-12-15 Verfahren zum Aufbringen metallischer Überzüge auf metallische Werkstücke durch mechanisch-chemisches Behandeln der Werkstücke
DE2919726 1979-05-16
DE19792919726 DE2919726A1 (de) 1979-05-16 1979-05-16 Verfahren zum aufbringen metallischer ueberzuege auf metallische werkstuecke durch mechanisch-chemisches behandeln der werkstuecke

Publications (3)

Publication Number Publication Date
EP0012399A1 EP0012399A1 (fr) 1980-06-25
EP0012399B1 EP0012399B1 (fr) 1982-11-17
EP0012399B2 true EP0012399B2 (fr) 1986-09-17

Family

ID=25776868

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79105012A Expired EP0012399B2 (fr) 1978-12-15 1979-12-08 Procédé d'application de couches métalliques sur des objets métalliques par un traitement mécano-chimique desdits objets

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Country Link
EP (1) EP0012399B2 (fr)
DE (1) DE2964070D1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57500568A (fr) * 1980-05-12 1982-04-01
DE3720379A1 (de) * 1986-06-19 1988-01-28 Neugebauer Erich Dr Verfahren zum aufbringen metallischer ueberzuege auf metallische werkstuecke durch mechanisch-chemisches behandeln der werkstuecke
JPH01501071A (ja) * 1986-10-22 1989-04-13 マクダーミッド，インコーポレーテッド 酸化し易い金属の機械的メツキ

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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
US4062990A (en) * 1976-06-10 1977-12-13 Waldes Kohinoor, Inc. Non-polluting system for metal surface treatments

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Publication number Publication date
DE2964070D1 (en) 1982-12-23
EP0012399B1 (fr) 1982-11-17
EP0012399A1 (fr) 1980-06-25

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