EP0078866B1 - Formation de revêtements sur des surfaces d'aluminium - Google Patents

Formation de revêtements sur des surfaces d'aluminium Download PDF

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Publication number
EP0078866B1
EP0078866B1 EP81201255A EP81201255A EP0078866B1 EP 0078866 B1 EP0078866 B1 EP 0078866B1 EP 81201255 A EP81201255 A EP 81201255A EP 81201255 A EP81201255 A EP 81201255A EP 0078866 B1 EP0078866 B1 EP 0078866B1
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Prior art keywords
contact
brought
process according
solution
solution containing
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EP81201255A
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German (de)
English (en)
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EP0078866A1 (fr
Inventor
Nobuyuki Oda
Haruyoshi Terada
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Priority to JP55062539A priority Critical patent/JPS5839232B2/ja
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to EP81201255A priority patent/EP0078866B1/fr
Priority to DE8181201255T priority patent/DE3172781D1/de
Publication of EP0078866A1 publication Critical patent/EP0078866A1/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
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium compounds

Definitions

  • the invention relates to a process for the formation of coatings on surfaces of aluminum or aluminum alloys by means of aqueous acidic solutions which contain phosphate ions, at least one di-bis-hexaphosphoric acid ester of inosite or alkali or alkaline earth metal salts thereof and at least one titanium and / or zirconium compound.
  • Chromating solutions have so far gained the greatest importance as coating solutions.
  • due to the environmental impact and toxicity to the human body the use of chromates is increasingly associated with certain requirements.
  • a disadvantage associated with the use of chromates is that considerable expenditure is required for wastewater treatment.
  • the phosphating solutions based on alkali metal phosphate, zinc phosphate or manganese phosphate which are customary for producing phosphate layers have problems with regard to the stability of the phosphating solution and the machinability of the coating.
  • Anodized coatings have excellent properties, but relatively high costs for equipment and processing are required.
  • Another type of process consists in treating metal surfaces, especially aluminum, with an aqueous solution which contains phytic acid (inositol hexaphosphoric acid) and zirconium salts or di-bis-hexaphosphoric acid esters of myoinositol or its salts and titanium fluorides (US Pat. No. 3,076,734, JA- OS 25233/79).
  • phytic acid inositol hexaphosphoric acid
  • zirconium salts or di-bis-hexaphosphoric acid esters of myoinositol or its salts and titanium fluorides US Pat. No. 3,076,734, JA- OS 25233/79.
  • the object of the invention is to provide a process which avoids the disadvantages of the known processes, in particular leads to coatings which are good with regard to moisture resistance and paint adhesion, is simple to use and is not associated with higher costs than the known processes.
  • 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 surfaces are brought into contact with a solution which has a pH of 2 to 6 and an additional content of at least one pyrazole of the formula where X, Y and Z are identical or different functional groups, such as hydrogen, hydroxyl, alkyl, acyl, amino or nitro groups.
  • the solutions to be used to carry out the method according to the invention have considerable stability and lead to coatings of low porosity and good gloss properties.
  • the mixed organic / inorganic coatings obtained impart excellent paint adhesion and are themselves and in connection with a subsequent painting of high corrosion resistance.
  • the phosphate ions can be introduced via phosphoric acid or phosphates, such as alkali or ammonium phosphates.
  • the surfaces are preferably brought into contact with a solution which contains 0.1 to 20 g / l of phosphate ions.
  • a further advantageous embodiment of the invention consists in bringing the surface into contact with a solution which contains 0.05 to 10 g / 1 pyrazole compound. If the concentration is less than 0.05 g / l, the corrosion resistance of the coating decreases, possibly due to insufficient complex formation between titanium and / or zirconium and the pyrazole compound, and the stability of the coating solution is reduced. A concentration higher than 10 g / I is practically not associated with any further increase in corrosion resistance and is therefore not very economical.
  • Particularly suitable pyrazole compounds are 3,5-dimethylpyrazole, 3-methyl-5-hydroxypyrazole and 3-methyl-4-amino-5-hydroxypyrazole.
  • Another preferred embodiment of the invention consists in bringing the metal surface into contact with a solution containing 0.05 to 10 g / l of di-bis-hexaphosphoric ester of the inositol or whose salts contain.
  • esters are essentially obtained by hydrolysis of the hexaphosphoric ester of inositol (phytic acid).
  • Phytic acid is a substance commonly found in cereals, is obtained on an industrial scale and is therefore most suitable for carrying out the process according to the invention. Like its salt (phytin), phytic acid is harmless.
  • the salts of the 2- to 6-fold phosphoric acid ester of inositol are usually the sodium, potassium, lithium, magnesium, calcium, strontium and barium salts. They are water-soluble and therefore particularly suitable for the process according to the invention.
  • concentrations of the esters or the salts to be used it should be taken into account that, at contents below 0.05 g / l, the corrosion resistance of the coating obtained decreases, and in particular the resistance to discoloration in boiling water also decreases.
  • the coating solution can also become unstable.
  • a concentration higher than 10 g / l leads to practically no improvement in the corrosion resistance or the other advantages of the coating obtained.
  • Titanium hydrofluoric acid H 2 TiF 6
  • Suitable zirconium compounds are e.g. B. zirconium hydrofluoric acid (H 2 ZrF 6 ) and its alkali metal salts, the ammonium salt, zirconium sulfate, zirconyl sulfate, zirconium hydroxide and zirconium oxalate.
  • hydrofluoric acid In order to easily detach these titanium or zirconium compounds, it is advisable to use hydrofluoric acid.
  • boron fluorides such as borofluorohydric acid or water-soluble salts thereof.
  • a suitable salt of borofluoric acid is e.g. B. ammonium borofluoride.
  • the addition of the boron fluoride accelerates the formation of the coating.
  • An additional preferred embodiment of the invention consists in bringing the surfaces into contact with a solution which additionally contains sulfate and / or fluoride ions.
  • the sulfate ions can be introduced using sulfuric acid, sodium sulfate, ammonium sulfate. Sulphate ions suppress corrosion during coating formation. They also give the coating even better gloss properties.
  • the fluoride addition serves in particular to stabilize aluminum that has gone into solution.
  • Suitable cleaning agents are e.g. B. organic solvents such as trichlorethylene, or alkaline or acidic aqueous degreasing agents.
  • the surfaces to be treated can be brought into contact with the coating solutions in any way. Suitable forms of application are spraying, dipping, flooding and rolling up.
  • the duration of the application of the solution to the workpieces varies depending on the type of aluminum surface or the nature of the alloy or the shape of the workpiece, etc.
  • the treatment time is generally between 1 sec. And 10 minutes.
  • the workpiece is then rinsed with water in the usual way and finally dried with hot air at 50 to 200 ° C. It is also possible to omit the water rinse and to dry the coating solution directly.
  • the coating solution can be applied at normal temperature. However, it is particularly advantageous if, according to a further embodiment of the invention, the surface is brought into contact with a solution heated to 40 to 90 ° C. This further improves corrosion resistance, adhesive strength and adhesion for a well-applied varnish.
  • the pH range of the coating solution used is between 2 and 6 in order to achieve a coating with excellent tightness and corrosion resistance with very good adhesive properties. If the pH value exceeds 6, insoluble titanium hydroxide and / or zirconium hydroxide are formed in the coating solution. If the pH is below 2, there is a strong pickling attack on the metal to be treated and a coating with very good corrosion resistance is practically impossible to achieve.
  • the pH can be adjusted with alkaline substances, e.g. B. caustic alkali, such as caustic soda, with ammonia water, sodium carbonate, and optionally acids, such as phosphoric acid, hydrofluoric acid, sulfuric acid.
  • the coating solutions used in the process according to the invention contain - as explained above - no toxic metals, such as. As chrome and the like., And cause little or practically no sewage or sludge problems.
  • the solution is stable. Thankss to its contact with the surface of aluminum or aluminum alloys, an organic-inorganic complex coating containing titanium / aluminum phosphate and / or zircon / aluminum phosphate is formed, which, even after the workpiece has been deformed, has a high salt water spray and moisture resistance as well as color stability in boiling Has water and in high temperature steam.
  • Aluminum plates (A 5052) measuring 0.4 x 70 x 150 mm were cleaned with an aqueous 1.5% alkaline degreasing agent, for 7 seconds with a coating solution which contained and had a pH of 4.0 and a temperature of 60 ° C, sprayed, then rinsed with tap water and finally with deionized water. Drying was carried out in a hot air oven at 200 ° C within 2 minutes.
  • Aluminum plates (A 5082) with the dimensions 0.4 x 70 x 150 mm were cleaned as in Example 1 and for 10 seconds with a coating solution which contained and had a pH of 4.5 and a temperature of 65 ° C, sprayed. The coating was then rinsed with water, again with deionized water, and dried in a hot air oven at 200 ° C for 2 minutes.
  • Plates treated in this way were subjected to the pasteurization test, i. H. Exposed to high pressure steam in a pressure vessel at 125 ° C for 30 minutes and checked for a color change on its surface.
  • the test results were subjected to the same evaluation procedure as the cooking water test of Example 1.
  • treated plates were coated with a commercially available epoxy paint for hollow vessels (XJ-K 190 A) for 3 to 4 J.Lm, baked for 8 minutes at 205 ° C, 1 hour in a boiling aqueous solution of 3% citric acid and 3% table salt dipped and at up to 80 ° C dried. Then, with a sharp knife, crosses were scratched into the paint surface down to the metal surface, cellophane adhesive strips were pressed on firmly, these were torn off violently and the detachment of the paint layer was checked.
  • the adhesive strength of the paint layer was evaluated in accordance with:
  • Example 2 A comparison test was carried out, which was carried out under the conditions of Example 1.
  • the coating was formed using a solution that contained a pH of 3.8 and a temperature of 40 ° C.
  • the coating quality was assessed by boiling water test, salt spray test and moisture test. The results were as follows:

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

Claims (8)

1. Procédé pour la formation de revêtements sur des surfaces d'aluminium ou d'alliages d'aluminium au moyen de solutions aqueuses acides qui contiennent des ions phosphate, au moins un ester di- jusqu'à hexaphosphorique de l'inositol ou des sels alcalins ou alcalino-terreux de celui-ci ainsi qu'au moins un composé de titane et/ou de zirconium, caractérisé par le fait que l'on met la surface en contact avec une solution qui a un pH compris entre 2 et 6 et qui a une teneur additionnelle d'au moins un pyrazole de formule
Figure imgb0012
X, Y et Z étant des groupes fonctionnels identiques ou différents tels que des atomes d'hydrogène, des groupes hydroxy, alkyÍe, acyle, amino ou nitro.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on met les surfaces en contact avec une solution qui contient de 0,1 à 20 g/I d'ions phosphate.
3. Procédé selon la revendication 1 ou 2, caractérisé par le fait que l'on met les surfaces en contact avec une solution qui contient de 0,05 à 10 g/I de composé pyrazolique.
4. Procédé selon la revendication 1, 2 ou 3, caractérisé par le fait que l'on met les surfaces métalliques en contact avec une solution qui contient de 0,05 à 10 g/I d'ester di- jusqu'à hexaphosphorique de l'inositol ou de sels de celui-ci.
5. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé par le fait que l'on met les surfaces métalliques en contact avec une solution qui contient de 0,005 à 10 g/I de composé de titane et/ou de zirconium (calculé en tant que titane ou zirconium métallique).
6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé par le fait que l'on met les surfaces en contact avec une solution qui contient des borofluorures tels qu'acide borofluorhydrique ou sels solubles de celui-ci.
7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé par le fait que l'on met les surfaces en contact avec une solution qui contient en outre des ions sulfate et/ou fluorure.
8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé par le fait que l'on met les surfaces en contact avec une solution portée à une température de 40 à 90 °C.
EP81201255A 1980-05-12 1981-11-10 Formation de revêtements sur des surfaces d'aluminium Expired EP0078866B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP55062539A JPS5839232B2 (ja) 1980-05-12 1980-05-12 アルミニウム及びアルミニウム合金表面の皮膜化成処理液
EP81201255A EP0078866B1 (fr) 1980-05-12 1981-11-10 Formation de revêtements sur des surfaces d'aluminium
DE8181201255T DE3172781D1 (en) 1981-11-10 1981-11-10 Formation of coatings on aluminium surfaces

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP55062539A JPS5839232B2 (ja) 1980-05-12 1980-05-12 アルミニウム及びアルミニウム合金表面の皮膜化成処理液
EP81201255A EP0078866B1 (fr) 1980-05-12 1981-11-10 Formation de revêtements sur des surfaces d'aluminium

Publications (2)

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EP0078866A1 EP0078866A1 (fr) 1983-05-18
EP0078866B1 true EP0078866B1 (fr) 1985-10-30

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EP81201255A Expired EP0078866B1 (fr) 1980-05-12 1981-11-10 Formation de revêtements sur des surfaces d'aluminium

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JP (1) JPS5839232B2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3236247A1 (de) * 1982-09-30 1984-04-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur oberflaechenbehandlung von aluminium
US4992116A (en) * 1989-04-21 1991-02-12 Henkel Corporation Method and composition for coating aluminum
US5209788A (en) * 1990-11-21 1993-05-11 Ppg Industries, Inc. Non-chrome final rinse for phosphated metal
US5147472A (en) * 1991-01-29 1992-09-15 Betz Laboratories, Inc. Method for sealing conversion coated metal components
US5226976A (en) * 1991-04-15 1993-07-13 Henkel Corporation Metal treatment
US5514478A (en) * 1993-09-29 1996-05-07 Alcan International Limited Nonabrasive, corrosion resistant, hydrophilic coatings for aluminum surfaces, methods of application, and articles coated therewith
EP1221497A3 (fr) * 1998-06-19 2003-12-03 Alcoa Inc. Procédé d'inhibition de tâches à la surface de produits en aluminium
AU4695799A (en) * 1998-06-19 2000-01-05 Alcoa Inc. Method for inhibiting stains on aluminum product surfaces
EP1115800A1 (fr) * 1998-08-24 2001-07-18 Akzo Nobel N.V. Agent anti-usure par abrasion pour des compositions de revetement
US10329674B2 (en) * 2016-12-01 2019-06-25 Vitech International, Inc. Fluorinated acid compounds, compositions and methods of use

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076734A (en) * 1960-07-01 1963-02-05 Acme Steel Co Protective coatings on metals
US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
JPS535622B2 (fr) * 1973-02-12 1978-03-01
CA1083335A (fr) * 1976-05-10 1980-08-12 Chemed Corporation Compose inhibiteur de corrosion et methode d'utilisation

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Publication number Publication date
EP0078866A1 (fr) 1983-05-18
JPS5839232B2 (ja) 1983-08-29
JPS56163280A (en) 1981-12-15

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