EP1290242B1 - Procede pour traiter ou pretraiter des pieces comportant des surfaces en aluminium - Google Patents

Procede pour traiter ou pretraiter des pieces comportant des surfaces en aluminium Download PDF

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Publication number
EP1290242B1
EP1290242B1 EP01953946A EP01953946A EP1290242B1 EP 1290242 B1 EP1290242 B1 EP 1290242B1 EP 01953946 A EP01953946 A EP 01953946A EP 01953946 A EP01953946 A EP 01953946A EP 1290242 B1 EP1290242 B1 EP 1290242B1
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EP
European Patent Office
Prior art keywords
fluoride
bath
solution
phosphatizing
parts
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
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EP01953946A
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German (de)
English (en)
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EP1290242A2 (fr
Inventor
Edgar Busch
Jörg Hieke
Thomas Kolberg
Dr. Peter Schubach
Harald Jaschke
Christoph Klocke
Alfred Rutka
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Bayerische Motoren Werke AG
Chemetall GmbH
Original Assignee
Bayerische Motoren Werke AG
Chemetall GmbH
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Publication of EP1290242A2 publication Critical patent/EP1290242A2/fr
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Publication of EP1290242B1 publication Critical patent/EP1290242B1/fr
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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
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations

Definitions

  • the invention relates to a method for treating or pretreating parts with aluminum surfaces.
  • Phosphating processes for aluminum and aluminum alloys are fundamental known.
  • fluoride has been modified Phosphating process with at least 150 mg / l free fluoride especially proven. These processes are particularly important in the automotive industry are mainly used when a mix of substrates from different Metals or alloys are given by the plants.
  • DE-A1-197 35 314 describes a method for pretreating components with Aluminum surfaces - possibly in the presence of magnesium, steel and / or zinc surfaces -
  • a phosphating plant in which the components with a Degreasing solution degreased by treatment with a fluoride-containing Phosphating solution phosphated and then by treatment with a Passivation solution to be passivated.
  • the proportion of aluminum or / and Magnesium surface on the entire surface of the components to be treated is at least 10%.
  • the fluoride of the phosphating solution The content should only be added as complex-bound fluoride the free fluoride ions formed therefrom in the phosphating solution Phosphating of the steel and / or zinc surfaces without phosphating the Aluminum and / or magnesium surfaces kept at less than 100 mg / l become.
  • the passivation solution should be composed so that it the phosphated steel and / or zinc surfaces passivated and on the Aluminum or / and magnesium surfaces forms a conversion layer.
  • this method has the disadvantage that it is only comparatively small Area shares on aluminum surfaces, mostly only up to about 20% by area of all surfaces to be treated on the mix of substrates can. It also has the disadvantages that cryolite or / and related ones Precipitation products continue to be formed in the pretreatment bath and that the Layering reactions, especially on iron and steel surfaces in one increased aluminum content of the phosphating solution are affected, so that no longer the entire mix of substrates made of different metal and Alloy surfaces can be coated equally well in the bathroom.
  • EP-A2-0 454 361 describes a zinc phosphating process in which the body is involved metallic surfaces are immersed in a zinc phosphating bath, which is next to a fluoride complex has a content of simple fluoride in the range from 200 to 300 mg / L contains and in which the molar ratio of the contents of complex fluoride to simple fluoride ⁇ 0.01, and then the body with a second zinc phosphating solution are sprayed, which contains simple Fluoride ⁇ 500 mg / L, but a higher content than the first Zinc phosphating solution.
  • An external precipitation container can be used here be used.
  • EP-A2-0 434 358 teaches a similar zinc phosphating process in which such bodies are brought into contact with a zinc phosphate solution only once with a solution of simple fluoride in the range of 200. up to 500 mg / L and at which the molar ratio of the contents Complex fluoride to simple fluoride is kept in the range of 0.01 to 0.5.
  • the object of the invention is to overcome the disadvantages of the prior art and in particular a process for phosphating aluminum and aluminum-containing To propose alloys, even with increased proportions of aluminum-containing Surfaces of the components to be treated or pre-treated a good conversion layer that can be applied on an industrial scale or / and one appropriate passivation layer on the surfaces of aluminum or Alloys containing aluminum - possibly in a mix of substrates different metals or alloys - allowed to apply.
  • the method according to the invention can be used for this be ensured that increasing levels of aluminum in the phosphating solution in a separate zone of the phosphating bath to contents less than or be reduced to 100 mg / l Al ions.
  • the pickling attack dissolves aluminum on the metallic surface, and an aluminum content is taken up in the phosphating solution.
  • someone specific Aluminum content can also be from other sources in the phosphating solution come like from registered chemicals of the rinse solution.
  • the Aluminum content can be predominantly or entirely by precipitation, but also partially be lowered by complexation.
  • the free fluoride content in the Phosphating solution is preferably in a range from 6 to 120 mg / l, particularly preferably in a range from 10 to 80 mg / l, very particularly preferably kept in a range of 20 to 50 mg / l.
  • the aluminum content in the Phosphating solution is preferred especially at values ⁇ 80 mg / l preferably ⁇ 60 mg / l, very particularly preferably ⁇ 30 mg / l.
  • the process according to the invention is also characterized in that aluminum is precipitated in the phosphating solution in the precipitation tank or in the separate zone of the bath by adding alkali metal ions, fluoride complexes and / or fluoride ions, in particular with Na or K Ion or with at least one easily dissociating fluoride such as NaF, NH 4 F, NaHF 2 or KF.
  • alkali metal ions, fluoride complexes and / or fluoride ions in particular with Na or K Ion or with at least one easily dissociating fluoride such as NaF, NH 4 F, NaHF 2 or KF.
  • the AlF x complex can already be pre-complexed. It is advantageous to control the process according to the invention in such a way that, despite the F addition, there is no increase in the free fluoride content in the bath.
  • the contents of alkali ions in the phosphating bath are preferably 1 to 20 g / l and are preferably also kept in this range, in particular 3 to 10 g / l.
  • the alkali ion content can also be far above the concentration of 20 g / l, for example 30 g / l. With such a high alkali concentration, instability of the bath can occur in many cases. In the case of a mixture of different alkali ions next to one another, a dominant content of sodium and / or potassium ions is preferred.
  • the concentration of free fluoride is advantageously Phosphating solution in the phosphating bath 8 to 80 mg / l and in particular 10 up to 50 mg / l or in the precipitation tank or in the separate zone of the bath tank 5 to 500 mg / l free fluoride, in particular 20 to 200 mg / l, particularly preferably 30 up to 120 mg / l. It is therefore also preferred to have these levels in these concentrations to keep. Since usually below 5 mg / l there is no pickling attack on aluminum by free Fluoride occurs and because this pickling attack is needed as the subsequent one Passivation e.g.
  • the inventive method will be used so that the Residence time of the phosphating solution in the precipitation tank or in the separate one Precipitation zone is up to 1 h, often up to 0.5 h.
  • the volume flow from the bathroom to the Precipitation container and back is according to the selected volumes or Partial volumes and the desired aluminum content in the phosphating bath set.
  • part in the sense of this application encompasses all types and forms of Sheets, strip and profile sections, shaped bodies, semi-finished products, components, Assemblies etc.
  • the parts, profiles, to be treated or pretreated are usually Tapes and / or wires in the method according to the invention before pickling / phosphating cleaned, rinsed and, if necessary, separated from the rinsing and Cleaning stages with an activation solution, e.g. based on colloidal distribution Titanium phosphate contacted.
  • Wires can rinsed and / or passivated after pickling / phosphating, in particular with a passivation solution based on a chromate-containing compound, Titanium fluoride, zirconium fluoride, soluble rare earth compound - especially cerium-containing Connection, self-organizing molecules e.g. based on phosphonate, based Silane, solvent-soluble and / or dispersible polymer.
  • a passivation solution based on a chromate-containing compound, Titanium fluoride, zirconium fluoride, soluble rare earth compound - especially cerium-containing Connection, self-organizing molecules e.g. based on phosphonate, based Silane, solvent-soluble and / or dispersible polymer.
  • the treated or pretreated and / or passivated parts, profiles, strips or / and wires can be after pickling / phosphating or after Passivation can be dried. In some cases such as at the immediate subsequent electrodeposition, however, drying is not necessary.
  • the precipitation of the aluminum can be carried out under normal pressure and at a temperature in the Range from room temperature to 70 ° C, especially at one temperature in the range of 40 to 60 ° C.
  • the pH is usually in the range of 2 to 4.
  • the pH of Phosphating baths are always in the range around pH 3. at Values of pH ⁇ 4.0 are usually unstable, while values of pH ⁇ 4.0 2.0 the bath is so stable that usually no good layer formation occurs because the The pH value shift on the freshly pickled metallic surface does not increase a separation of the conversion layer is sufficient.
  • the products thus produced according to the invention can be found in the Automotive industry, in the aviation industry, in apparatus and mechanical engineering, in the Furniture industry, construction, for household appliances, electrical appliances, measuring devices, Control devices, test devices, construction elements, housings, Cladding, shelves, frames, frames, room dividers, partitions, facings, Lighting fixtures, crash barriers, radiator or fence elements as well as small parts, especially for body parts or bodies.
  • FIG. 1 shows a flow diagram which shows one possible of several principles of separate aluminum deposition schematically.
  • the phosphating process according to the invention has been described in comparison with previously and practiced methods the advantage that the cryolite or / and related Sludge containing precipitation products largely in a separate Precipitation zone or in a separate precipitation container and from there can be disposed of. It is also with the method according to the invention possible to treat different metallic substrates in one mix or pretreatment without affecting the layer formation e.g. on Steel is coming. Due to the reduced levels of free fluoride in the Phosphating solution also occurs less pickling attack on those containing aluminum Surfaces that also cause a correspondingly lower sludge formation. In addition, it was possible to ensure with the method according to the invention that due to the fact that there is less and less precipitated on the phosphated surface deposited particles after the subsequent painting no annoying Markings such as Roughness, streaking or other irregularities were recognizable.
  • a standard phosphating solution with the following composition was prepared from pa chemicals: Zn 1.5 g / l Mn 1.0 g / l Ni 1.0 g / l P 2 O 5 14.0 g / l NO 3 3.0 g / l SiF 6 1.0 g / l FS 2.0 Free acid.
  • This entry corresponds to approx. 40 bodies per hour with 50% aluminum surface area and a pickling attack of approx. 1 g / m 2 during the contact time.
  • Al (ppm) ((((200m 3 - partial flow) • conc. Al in ppm after 1 h + (partial flow • rest Al in ppm after precipitation)) / 200) + Al in ppm from entry via pickling attack / h.

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  • 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)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (13)

  1. Procédé pour traiter ou prétraiter des pièces, profilés, feuillards ou câbles ayant des surfaces en aluminium, ou en alliages comprenant de l'aluminium, - si applicable, en présence de surfaces d'alliages d'autres métaux - avec une solution aqueuse acide comprenant un fluorure et un phosphate, caractérisé en ce que le fluorure se présente au moins partiellement sous forme libre dans la solution et en ce que, dans le bain de la solution de phosphatation,
       la teneur en fluorure libre est maintenue à une concentration allant de 6 à 120 mg/l en Flibre, et
       la teneur en aluminium est maintenue à une concentration inférieure ou égale à 100 mg/l en ions A1 (y compris l'A1 lié à un complexe),
       les teneurs croissantes en aluminium, dans un réservoir de précipitation en dehors du bain de phosphatation, étant abaissées à des teneurs inférieures ou égales à 100 mg/l en ions A1 dans le bain en faisant circuler la solution de phosphatation à partir du bain de phosphatation jusqu'au réservoir de précipitation et inversement.
  2. Procédé selon la revendication 1, modifié en ce que, dans une zone séparée du bain de phosphatation, des teneurs croissantes en aluminium sont abaissées à des teneurs inférieures ou égales à 100 mg/l en ions A1.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que, dans le réservoir ou dans la zone séparée du bain, l'aluminium est précipité dans la solution de phosphatation en ajoutant des ions alcalins, des complexes fluorure et/ou des ions fluorure, en particulier à l'aide d'ions Na ou K ou à l'aide d'au moins un fluorure facilement dissociable, comme par exemple NaF, NH4F, NaHF ou KF.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la teneur en ions alcalins dans le bain est maintenue à une concentration allant de 1 à 20 g/l.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la concentration en fluorure libre dans le réservoir de précipitation ou dans la zone séparée du réservoir du bain est comprise entre 5 et 500 mg/l en fluorure libre.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le temps de séjour de la solution de phosphatation dans le réservoir de précipitation ou dans la zone de précipitation séparée va jusqu'à une heure.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, avant le décapage /phosphatation, les pièces, profilés, feuillards ou câbles à traiter ou prétraiter sont lavés, rincés et, si approprié et séparément des étapes de rinçage et de nettoyage, mis en contact avec une solution d'activation, par exemple à base d'un phosphate de titane dispersé de façon colloïdale.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, après le décapage /phosphatation, les pièces, profilés, feuillards ou câbles traités ou prétraités sont rincés et/ou passivés, en particulier à l'aide d'une solution de passivation à base d'un composé contenant un chromate, un fluorure de titane, un fluorure de zirconium, un silane, des molécules s'auto-organisant par exemple à base de phosphonate, un polymère soluble et/ou dispersible dans un solvant, une terre rare soluble, en particulier un composé soluble contenant du cérium, la terre rare pouvant également être le scandium, l'yttrium et le lanthane.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les pièces, profilés, feuillards ou câbles traités ou prétraités sont séchés après le décapage /phosphatation ou après la passivation.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la précipitation de l'aluminium est effectuée à pression normale et à une température allant de la température ambiante à 70°C.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la formation de la couche de conversion ou de passivation est effectuée à pression normale et à une température allant de la température ambiante à 70°C.
  12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les pièces, profilés, feuillards ou câbles traités ou prétraités sont revêtus avec un vernis, avec un autre revêtement organique, avec un film et/ou avec une couche adhésive, si applicable imprimés, si applicable reformés, les portions de métal revêtues de la sorte pouvant en outre être liées entre elles, soudées entre elles et/ou connectées à d'autres portions.
  13. Utilisation des produits obtenus par un procédé selon l'une quelconque des revendications 1 à 12 dans l'industrie automobile, dans l'industrie aéronautique, dans la construction d'appareils et de machines, dans l'industrie du meuble, dans les bâtiments de commerce, pour des appareils ménagers, des appareils électriques, des instruments de mesure, des dispositifs de contrôle, des dispositifs de test, des éléments de construction, des logements, des revêtements, des étagères, des casiers, des charpentes, des claustras, des cloisons, des briques, des appareils d'éclairage, des glissières de sécurité, des radiateurs ou des éléments de clôture ainsi que de petits éléments, en particulier pour des éléments de carrosserie ou des carrosseries.
EP01953946A 2000-05-31 2001-05-19 Procede pour traiter ou pretraiter des pieces comportant des surfaces en aluminium Expired - Lifetime EP1290242B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10026850A DE10026850A1 (de) 2000-05-31 2000-05-31 Verfahren zum Behandeln bzw. Vorbehandeln von Bauteilen mit Aluminium-Oberflächen
DE10026850 2000-05-31
PCT/EP2001/005756 WO2001092597A2 (fr) 2000-05-31 2001-05-19 Procede pour traiter ou pretraiter des pieces comportant des surfaces en aluminium

Publications (2)

Publication Number Publication Date
EP1290242A2 EP1290242A2 (fr) 2003-03-12
EP1290242B1 true EP1290242B1 (fr) 2004-02-25

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US (2) US20030150527A1 (fr)
EP (1) EP1290242B1 (fr)
JP (1) JP2003535220A (fr)
AT (1) ATE260349T1 (fr)
AU (1) AU7633701A (fr)
DE (2) DE10026850A1 (fr)
ES (1) ES2215920T3 (fr)
WO (1) WO2001092597A2 (fr)
ZA (1) ZA200209670B (fr)

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Publication number Priority date Publication date Assignee Title
MXPA03006677A (es) 2001-02-16 2003-10-24 Henkel Kgaa Proceso para tratar articulos de metales multiples.
US6793738B2 (en) * 2002-03-28 2004-09-21 General Electric Company Method for processing acid treatment solution, solution processed thereby, and method for treating articles therewith
PT1521863E (pt) 2002-07-10 2008-09-19 Chemetall Gmbh Processo para revestir superfícies metálicas
DE102010030697A1 (de) 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion
CN102094195B (zh) * 2011-01-14 2012-07-18 中国科学院宁波材料技术与工程研究所 一种金属材料表面的磷化处理方法
EP2915903B1 (fr) * 2014-03-05 2018-02-21 The Boeing Company Revêtement de conversion exempt de chrome
EP3682042B1 (fr) * 2017-09-14 2021-11-10 Chemetall GmbH Procédé de prétraitement de matériaux en aluminium, en particulier de roues en aluminium
EP3724371A1 (fr) * 2017-12-12 2020-10-21 Chemetall GmbH Composition sans acide borique pour éliminer des dépôts contenant de la cryolithe
DE102020116345B3 (de) * 2020-06-22 2021-04-08 Möller Chemie GmbH & Co. KG Verfahren zur Regeneration einer erschöpften, Schwefelsäure enthaltenden Behandlungsflüssigkeit aus der Aluminiumveredelung

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US5200000A (en) * 1989-01-31 1993-04-06 Nihon Parkerizing Co., Ltd. Phosphate treatment solution for composite structures and method for treatment
KR100197145B1 (ko) * 1989-12-19 1999-06-15 후지이 히로시 금속표면의 인산아연 처리방법
JPH07100870B2 (ja) * 1990-04-24 1995-11-01 日本ペイント株式会社 金属表面のリン酸亜鉛皮膜処理方法
JP2794013B2 (ja) * 1990-10-24 1998-09-03 日本パーカライジング株式会社 鉄―アルミニウム系金属板金構成体用リン酸塩化成処理液
JPH07173643A (ja) * 1993-12-21 1995-07-11 Mazda Motor Corp 金属表面の燐酸塩処理方法及び処理液

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ZA200209670B (en) 2003-11-28
ES2215920T3 (es) 2004-10-16
US20070119520A1 (en) 2007-05-31
DE10026850A1 (de) 2001-12-06
ATE260349T1 (de) 2004-03-15
US20030150527A1 (en) 2003-08-14
JP2003535220A (ja) 2003-11-25
DE50101560D1 (de) 2004-04-01
WO2001092597A3 (fr) 2002-04-25
WO2001092597B1 (fr) 2002-05-23
EP1290242A2 (fr) 2003-03-12
WO2001092597A2 (fr) 2001-12-06
AU7633701A (en) 2001-12-11

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