EP1361297B1 - Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc - Google Patents

Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc Download PDF

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Publication number
EP1361297B1
EP1361297B1 EP02008422A EP02008422A EP1361297B1 EP 1361297 B1 EP1361297 B1 EP 1361297B1 EP 02008422 A EP02008422 A EP 02008422A EP 02008422 A EP02008422 A EP 02008422A EP 1361297 B1 EP1361297 B1 EP 1361297B1
Authority
EP
European Patent Office
Prior art keywords
phosphoric acid
solution
zinc
cleaning
treatment step
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 - Lifetime
Application number
EP02008422A
Other languages
German (de)
English (en)
Other versions
EP1361297A1 (fr
Inventor
Wolf-Dieter Franz
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.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AT02008422T priority Critical patent/ATE272133T1/de
Priority to DE50200704T priority patent/DE50200704D1/de
Priority to EP02008422A priority patent/EP1361297B1/fr
Priority to PCT/EP2002/010195 priority patent/WO2003087438A1/fr
Priority to AU2002329277A priority patent/AU2002329277A1/en
Publication of EP1361297A1 publication Critical patent/EP1361297A1/fr
Application granted granted Critical
Publication of EP1361297B1 publication Critical patent/EP1361297B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

  • This invention relates to a new method for treating surfaces of die cast parts made of zinc and zinc alloys.
  • the aim of the treatment is one Cleaning and some preservation of the cleaned surface.
  • the zinc alloys to which this invention aims contain a substantial proportion of Zn, in particular at least 90% by weight Zn.
  • this invention is based on the technical problem, both in terms of its cleaning properties as well as its insensitivity against the alloy composition as well as economically efficient Process for cleaning and passivating zinc and zinc alloy surfaces of die-cast parts.
  • US 4133724 discloses a method for anodizing metal layers Compound semiconductor surfaces with a mixture of an acid and a Means for preventing the dissolution of the metal.
  • metal et al Called zinc In addition to aluminum is used as metal et al Called zinc.
  • the metal layers become complete anodized.
  • the invention is directed to a method in which the surface is passivated, characterized by a treatment step in a solution, the phosphoric acid and contains an alcohol in which the surface is connected anodically.
  • the anodic cleaning step in the solution with phosphoric acid and the alcohol has both degreasing and surface etching good efficiency and is also able to remove problematic residues such as removing polysilane release agents.
  • the cleaning method according to the invention especially with a low water content of the solution (electrolyte) a certain inhibitory Effect inherent, so that excessive material removal is prevented.
  • the water content is preferably at most 5 vol%.
  • a thin zinc phosphate layer After the treatment step according to the invention with the phosphoric acid and alcohol containing solution arises from phosphoric acid residues on the treated Surface in a subsequent dilution, for example in a rinsing step, a thin zinc phosphate layer.
  • This zinc phosphate layer forms an effective passivation the surface. It can be used in subsequent steps, such as galvanic Copper coating, can be removed again.
  • the cleaning and passivation method according to the invention can advantageously with a neutral rinsing step, for example in water, with a pH of about 7 to be completed.
  • a neutral rinsing step for example in water
  • a pH of about 7 to be completed can be completed.
  • other steps are also conceivable in which a zinc phosphate passivation layer is formed, in particular aqueous rinse and Treatment steps with deviating pH values, as long as these with the zinc phosphate layer are tolerated.
  • the cleaning effect and in particular the etching effect can be carried out in detail set the choice of the electrical parameters of the anodic cleaning operation and thus optimize it depending on the alloy in question. For example, a certain anodic current density can be used become. This means that you have an optimization parameter in hand that determines the composition of the solution not changed. It can also be used for one and the same Solution with different alloys can be worked optimally. Of course leaves the solution composition can also be optimized depending on the alloy, albeit the inventors could not find any critical dependencies here.
  • alcohols such as methanol, ethanol, propanol and butanol come as alcohol and higher alcohols and their derivatives such as isopropanol. But also diols, polyethers and other alcohols. Are a cheap choice Butanol and isopropanol. Of course, two or more alcohols can be mixed occur.
  • the anodic current density on the anodically polarized surface can advantageously be between 10, 30 or 50 A / m 2 as the lower limit and 500 A / m 2 as the upper limit and, as already explained above, is an optimization parameter depending on the alloy composition, the justifiable material removal and the required cleaning effect.
  • the total treatment time of the anodic cleaning steps can be, for example, between 10 seconds and 5 minutes and depends heavily on the set current density, the justifiable material removal and the degree of pollution.
  • the proportion of phosphoric acid in the solutions for the anodic cleaning steps is 30-90 vol.%, with the phosphoric acid within this volume fraction Can be 50-95 percent by weight.
  • the solutions advantageously consist of the stated volume fraction of phosphoric acid of 30-90 vol.% in the rest essentially from the alcohol (mixture).
  • the cleaning effect of the method according to the invention is so thorough and broad scattered that chemical pretreatment steps before incorporation into the phosphoric acid and the alcohol-containing solution can be dispensed with and for reasons of economy should also advantageously be eliminated.
  • the surfaces to be treated can therefore be applied directly and dry.
  • a particular advantage of the invention lies in the fact that it can also regenerate Alloys give good results, especially no sludge arises.
  • the metallic contaminants from regenerated material have with conventional Procedures led to significant problems in cleaning and often cleaning and subsequent good coating completely prevented.
  • a preferred application of the invention is in the preparation of zinc alloy surfaces for a subsequent coating of any kind.
  • the coating depends on the cleanliness of the surface, and both in terms of the optical properties and the resilience the coating.
  • the invention relates to a subsequent one Metallization that can be done galvanically or without external current. in this respect The invention is also directed to the overall process from that described Cleaning and passivation and the subsequent coating, in particular Metallization.
  • a part made of a standard zinc die-cast alloy (for example, the alloys Z400 to Z430) is put into a bath made of 60 percent phosphoric acid (H 3 PO 4 ) with 40 vol poled anodically.
  • the current density is, for example, 20 A / m 2 at a temperature of 25 ° C. and a treatment time that can be approximately 30 s.
  • the parts are then rinsed in neutral water (pH approx. 7).
  • neutral water pH approx. 7
  • the surface is now passivated and can be metallized in a conventional manner.
  • an electrolytic coating with Ni or Cu or an alloy selected from it.
  • the zinc alloys come from a die casting process, they are usually contaminated with mold release agents. These are also used in the cleaning processes shown removed reliably and completely.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electroplating Methods And Accessories (AREA)
  • ing And Chemical Polishing (AREA)

Claims (13)

  1. Procédé de nettoyage de surfaces en zinc ou en alliages de zinc de pièces moulées sous pression, dans lequel la surface est passivée
       caractérisé par une étape de traitement dans une solution contenant de l'acide phosphorique et un alcool, dans laquelle la surface est branchée à l'anode.
  2. Procédé selon la revendication 1 avec une étape suivante de rinçage neutre.
  3. Procédé selon la revendication 1 ou 2, dans lequel la solution présente une teneur en eau de 5% de volume maximum.
  4. Procédé selon l'une des revendications précédentes, dans lequel, pendant l'étape de traitement dans la solution d'acide phosphorique, dans laquelle la surface est polarisée de manière anodique, la densité de courant anodique étant de l'ordre de 10 à 500 A/m2.
  5. Procédé selon l'une des revendications précédentes, dans lequel, pendant l'étape de traitement dans la solution d'acide phosphorique, dans laquelle la surface est polarisée de manière anodique, la température de la solution est entre 10 et 40°C.
  6. Procédé selon l'une des revendications précédentes, dans lequel, pendant l'étape de traitement dans la solution d'acide phosphorique, dans laquelle la surface est polarisée de manière anodique, le temps total de traitement est de l'ordre de 10 secondes à 5 minutes.
  7. Procédé selon l'une des revendications précédentes, dans lequel, pendant l'étape de traitement dans la solution d'acide phosphorique, dans laquelle la surface est polarisée de manière anodique, la teneur en acide phosphorique est de l'ordre de 30 à 90 % en volume.
  8. Procédé selon la revendication 7, dans lequel le reste de la solution est constitué essentiellement d'au moins un alcool.
  9. Procédé selon la revendication 7 ou 8, dans lequel la teneur en acide phosphorique dans le teneur en volume est de 50 à 95 % en poids.
  10. Procédé selon l'une des revendications précédentes, dans lequel la surface est plongée dans la solution d'acide phosphorique et d'alcool sans pré-traitement chimique.
  11. Procédé selon l'une des revendications précédentes, dans lequel l'alliage de zinc est constitué de matériau récupéré.
  12. Procédé de revêtement d'une surface en zinc ou en alliage de zinc, dans lequel la surface est d'abord nettoyée et passivée puis revêtue à l'aide d'un procédé selon l'une des revendications 1 à 11.
  13. Procédé selon la revendication 12, dans lequel le revêtement est une métallisation.
EP02008422A 2002-04-12 2002-04-12 Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc Expired - Lifetime EP1361297B1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT02008422T ATE272133T1 (de) 2002-04-12 2002-04-12 Verfahren zum reinigen und passivieren von zink- und zinklegierungsoberflächen
DE50200704T DE50200704D1 (de) 2002-04-12 2002-04-12 Verfahren zum Reinigen und Passivieren von Zink- und Zinklegierungsoberflächen
EP02008422A EP1361297B1 (fr) 2002-04-12 2002-04-12 Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc
PCT/EP2002/010195 WO2003087438A1 (fr) 2002-04-12 2002-09-11 Procede de nettoyage et de passivation de surfaces de zinc et d'alliage de zinc
AU2002329277A AU2002329277A1 (en) 2002-04-12 2002-09-11 Method for cleaning and passivating zinc and zinc alloy surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02008422A EP1361297B1 (fr) 2002-04-12 2002-04-12 Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc

Publications (2)

Publication Number Publication Date
EP1361297A1 EP1361297A1 (fr) 2003-11-12
EP1361297B1 true EP1361297B1 (fr) 2004-07-28

Family

ID=29225588

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02008422A Expired - Lifetime EP1361297B1 (fr) 2002-04-12 2002-04-12 Procédé pour nettoyage et passivation des couches de zinc ou des alliages de zinc

Country Status (5)

Country Link
EP (1) EP1361297B1 (fr)
AT (1) ATE272133T1 (fr)
AU (1) AU2002329277A1 (fr)
DE (1) DE50200704D1 (fr)
WO (1) WO2003087438A1 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3716462A (en) * 1970-10-05 1973-02-13 D Jensen Copper plating on zinc and its alloys
US3663386A (en) * 1971-02-08 1972-05-16 Basf Wyandotte Corp Electrocleaner composition and process
GB1536177A (en) * 1976-12-07 1978-12-20 Nat Res Dev Anodising a compound semiconductor
JPS60248898A (ja) * 1983-06-30 1985-12-09 Chobe Taguchi 電解用脱錆液

Also Published As

Publication number Publication date
AU2002329277A1 (en) 2003-10-27
ATE272133T1 (de) 2004-08-15
DE50200704D1 (de) 2004-09-02
WO2003087438A1 (fr) 2003-10-23
EP1361297A1 (fr) 2003-11-12

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