EP0281176B1 - Procédé de prétraitement avant laquage de pièces en aluminium ou ses alliages - Google Patents

Procédé de prétraitement avant laquage de pièces en aluminium ou ses alliages Download PDF

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Publication number
EP0281176B1
EP0281176B1 EP88200205A EP88200205A EP0281176B1 EP 0281176 B1 EP0281176 B1 EP 0281176B1 EP 88200205 A EP88200205 A EP 88200205A EP 88200205 A EP88200205 A EP 88200205A EP 0281176 B1 EP0281176 B1 EP 0281176B1
Authority
EP
European Patent Office
Prior art keywords
workpieces
treatment
hydrofluoric acid
process according
hno3
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
EP88200205A
Other languages
German (de)
English (en)
Other versions
EP0281176A1 (fr
Inventor
Werner Dr. Rausch
Gisela Beege
Gerhard Müller
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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
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Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention relates to a method for the preparation of workpieces with surfaces of aluminum and its alloys, which have at least partially been subjected to a mechanical, metal-removing surface treatment, for subsequent painting and its application to the treatment of workpieces with surfaces of alloys of the type AlMg or AlMgMn or the thermosetting type AlMgSi.
  • the work leading to the present invention initially provided the knowledge that the poor paint adhesion and resistance to infiltration occurs particularly strongly on pre-ground or similarly metal-machined aluminum surfaces, while the undisturbed rolled surface usually provides a much better quality profile.
  • the object of the invention is to provide a method for the preparation of workpieces with surfaces of aluminum or its alloys, which have at least partially been subjected to a mechanical, metal-removing surface treatment, for the subsequent painting, which does not have the disadvantages described.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the workpieces are first treated by annealing and / or pickling in oxidizing acid medium and then by green chromating, yellow chromating, colorless chromating, chromium-free treatment based on titanium and / or zirconium hydrofluoric acid or a fluoride-activated phosphating based on alkali and / or zinc and / or nickel and / or manganese and / or calcium and / or magnesium phosphate coated with a conversion layer.
  • mechanical, metal-removing surface treatment means a surface treatment, such as Grinding, scratching, turning, milling, blasting.
  • the glow level can be in the temperature range of e.g. 150 to 500 ° C at times of e.g. 5 minutes to several hours in the presence of air. It is believed that the beneficial effect of annealing is due to the build-up and densification of a natural oxide layer.
  • Solutions proved to be favorable which contain HNO3, H2SO4 + peroxide, H2SO4 + FeIII.
  • simple and / or complex fluorides e.g. in amounts of 0.2 to 50 g / l, added.
  • HNO3 can be present, for example, in concentrations of 10 to 500 g / l, preferably 200 to 450 g / l, H2SO4, for example in concentrations of 10 to 150 g / l, F-containing acids, for example in concentrations of 5 to 100 g / l.
  • the oxidizing agent FeIII is used, for example, in amounts of 5 to 50 g / l, peroxide, for example in amounts of 0.5 to 30 g / l.
  • Proven pickling solutions have e.g. the following composition: 350 to 400 g / l HNO3 + 5 to 15 g / l HF; 250 to 400 g / l HNO3; 75 to 100 g / l H2SO4 + 10 to 25 g / l FeIII (as sulfate) + 0.5 to 2 g / l HF.
  • the pickling solutions can be used by spraying and dipping in the temperature range from 15 to 45 ° C and with exposure times from 20 sec to 5 min.
  • the surface Before the treatment in the acidic oxidizing medium or by annealing, the surface must be freed from disturbing amounts of oils, fats, dust and dirt. This can be done by the action of cleaners based on organic solvents or mildly acidic, neutral or alkaline aqueous cleaning agents. Furthermore, a treatment in sodium hydroxide or potassium hydroxide solution, if appropriate with additives to complexing agents, can be carried out for cleaning and pickling the surface.
  • a particularly preferred embodiment of the invention is to first pickle the workpieces in HNO3 + HF and / or HNO3 and then to coat them with a conversion layer by yellow chromating or fluoride-activated zinc manganese phosphating.
  • the process according to the invention is suitable as a pretreatment for all known painting processes. However, it proves to be particularly advantageous before the application of powder, high-solid and anodic and cathodic electrocoat materials.
  • the method according to the invention is for the treatment of workpieces made of aluminum or aluminum alloys, for example with Si, Fe, Cu, Mn, Mg, Cr, Zn and Ti as an alloy component. It is particularly advantageously applicable to the treatment of workpieces with surfaces of alloys of the AlMg or AlMgMn type or the thermosetting AlMgSi type.
  • the workpieces can be, for example, sheet metal, solid or hollow profiles and cast parts.
  • the sheets were then coated with a cathodic electrocoat and a two-layer automotive paint system, scribed with a hard metal pen to the metal surface and subjected to various tests (see Tables 1 and 2).

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • ing And Chemical Polishing (AREA)

Claims (7)

1. Procédé de prétraitement, pour peinture ultérieure, de pièces à surface en aluminium ou en alliages d'aluminium, qui ont été soumises au moins partiellement à un traitement de surface mécanique démétallisant, caractérisé en ce que l'on traite d'abord les pièces par recuit et/ou décapage en milieu acide oxydant, puis on les recouvre d'une couche de conversion, par chromatation verte, chromatation jaune, chromatation incolore, traitement sans chrome à base d'acide titano- ou zirconofluorhydrique, ou phosphatation activée par un fluorure à base de phosphate alcalin et/ou phosphate de zinc et/ou phosphate de nickel et/ou phosphate de magnésium.
2. Procédé selon la revendication 1, caractérisé en ce que l'on décape les pièces avec des solutions aqueuses qui renferment
a) HNO₃ ou
b) H₂SO₄ et peroxyde, ou
c) H₂SO₄ et FeIII,

en une étape ou plusieurs étapes successives.
3. Procédé selon la revendication 2, caractérisé en ce que l'on décape les pièces avec des solutions qui renferment un fluorure simple et/ou complexe.
4. Procédé selon la revendication 1, caractérisé en ce que l'on décape, en une étape ou plusieurs étapes successives, les pièces avec des solutions aqueuses qui renferment
a) acide fluorhydrique et FeIII, ou
b) acide fluorhydrique et peroxyde, ou
c) acide fluorhydrique complexe et Fe III, ou
d) acide fluorhydrique complexe et peroxyde.
5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que l'on décape d'abord les pièces dans une solution renfermant HNO₃ + HF ou HNO₃, et en ce qu'on les recouvre ensuite d'une couche de conversion par chromatation jaune ou phosphatation au phosphate de zinc et de manganèse activée par un fluorure.
6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on peint les pièces par électroimmersion par peinture en poudre ou par peinture à forte teneur en solides.
7. Application du procédé selon une ou plusieurs des revendications 1 à 6 au traitement de pièces dont les surfaces sont en alliages du type AlMg ou AlMgMn ou du type thermodurcissable AlMgSi.
EP88200205A 1987-02-21 1988-02-05 Procédé de prétraitement avant laquage de pièces en aluminium ou ses alliages Expired - Lifetime EP0281176B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873705633 DE3705633A1 (de) 1987-02-21 1987-02-21 Verfahren zur vorbereitung von werkstuecken aus aluminium oder dessen legierungen fuer die lackierung
DE3705633 1987-02-21

Publications (2)

Publication Number Publication Date
EP0281176A1 EP0281176A1 (fr) 1988-09-07
EP0281176B1 true EP0281176B1 (fr) 1991-09-25

Family

ID=6321505

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88200205A Expired - Lifetime EP0281176B1 (fr) 1987-02-21 1988-02-05 Procédé de prétraitement avant laquage de pièces en aluminium ou ses alliages

Country Status (4)

Country Link
EP (1) EP0281176B1 (fr)
BR (1) BR8800681A (fr)
DE (2) DE3705633A1 (fr)
ES (1) ES2025763T3 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4131382A1 (de) * 1990-09-21 1992-03-26 Kobe Steel Ltd Oberflaechenbehandeltes aluminiumlegierungsblech fuer den automobilbau und verfahren zu dessen herstellung
EP0557531A1 (fr) * 1991-09-04 1993-09-01 Furukawa Aluminum Co., Ltd. Tole en alliage d'aluminium pour carrosseries d'automobiles et production de cette tole
US6168868B1 (en) * 1999-05-11 2001-01-02 Ppg Industries Ohio, Inc. Process for applying a lead-free coating to untreated metal substrates via electrodeposition
EP1930474B1 (fr) * 2005-08-19 2015-09-16 Chemetall GmbH Composition de conditionnement de surface, procédé de fabrication idoine, et procédé de conditionnement de surface
DE102007037903A1 (de) * 2007-08-10 2009-02-12 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Reinigung von Oberflächen sowie Verwendung des Verfahrens
CN110541169B (zh) * 2018-06-29 2021-12-28 蓝思科技股份有限公司 一种用于脱除工件表面镀层的褪镀液及褪镀方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2705500A (en) * 1953-11-04 1955-04-05 Leon L Deer Cleaning aluminum
DE1149965B (de) * 1957-06-07 1963-06-06 Ver Leichtmetallwerke Gmbh Verfahren zur Verbesserung der Haftfestigkeit von organischen Stoffen auf Aluminium oder Aluminiumlegierungen
US3331710A (en) * 1963-08-23 1967-07-18 Hooker Chemical Corp Method for coating aluminum
ES350042A1 (es) * 1968-02-01 1969-04-16 Gasion Emperador Un procedimiento para el pintado indeleble del aluminio.
US3692583A (en) * 1971-03-01 1972-09-19 Fmc Corp Desmutting etched aluminum alloys
US3728188A (en) * 1971-07-29 1973-04-17 Amchem Prod Chrome-free deoxidizing and desmutting composition and method
JPS61106783A (ja) * 1984-10-30 1986-05-24 Nippon Paint Co Ltd アルミニウム表面洗浄剤

Also Published As

Publication number Publication date
ES2025763T3 (es) 1992-04-01
DE3705633A1 (de) 1988-09-01
EP0281176A1 (fr) 1988-09-07
DE3865045D1 (de) 1991-10-31
BR8800681A (pt) 1988-10-04

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