EP0055881B1 - Procédé pour le traitement de surfaces métalliques - Google Patents

Procédé pour le traitement de surfaces métalliques Download PDF

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Publication number
EP0055881B1
EP0055881B1 EP81201403A EP81201403A EP0055881B1 EP 0055881 B1 EP0055881 B1 EP 0055881B1 EP 81201403 A EP81201403 A EP 81201403A EP 81201403 A EP81201403 A EP 81201403A EP 0055881 B1 EP0055881 B1 EP 0055881B1
Authority
EP
European Patent Office
Prior art keywords
metal surfaces
brought
contact
treating solution
treatment
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
EP81201403A
Other languages
German (de)
English (en)
Other versions
EP0055881A1 (fr
Inventor
Raymond Lee Wetzel
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
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22831357&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0055881(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Publication of EP0055881A1 publication Critical patent/EP0055881A1/fr
Application granted granted Critical
Publication of EP0055881B1 publication Critical patent/EP0055881B1/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
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • 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
    • C23C22/368—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 magnesium cations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate

Definitions

  • the invention relates to a method for applying conversion coatings on metal surfaces, in particular those made of aluminum and aluminum alloys, with treatment liquids containing magnesium and phosphate ions.
  • Metal surfaces e.g. B. made of steel, galvanized steel, aluminum, aluminum alloys and the like. Are usually surface-treated to preserve their usability and to improve their appearance and thus to increase their commercial value.
  • Typical treatment sequences are cleaning, forming a conversion coating, post-treatment, drying and applying organic layer material, e.g. B. colorants, paint, varnish, plastic coatings and the like., Individual process steps are separated by water rinsing.
  • the metal surface is cleaned in the first stage in order to free it from oil, dirt and corrosion products.
  • the second stage is a rinse with water, chemical residues from the first stage being removed from the metal surface.
  • the metal surface is wetted with an aqueous chemical reaction solution and the liquid film z. B. dried up.
  • DE-AS 17 69 582 describes, for example, a process in which an aqueous solution which contains hexavalent chromium, trivalent chromium, alkali ions and silicon dioxide in certain proportions is dried on the metal.
  • the coatings formed are e.g. B .. well suited as electrical insulation, as corrosion protection and as a primer for paints and the like.
  • the object of the invention is to provide a method which avoids the known, in particular the aforementioned disadvantages, and yet can be carried out simply and without additional effort.
  • 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 metal surfaces are brought into contact with a treatment liquid which additionally contains tannin, is chromium-free and has a pH of 2 to less than 7.
  • Tannin whose suitability for forming conversion coatings is also known in the absence of phosphate ions, significantly improves the corrosion protection effect and the paint adhesion, especially in the case of treatment liquids containing magnesium and phosphate ions.
  • I tannins are gallic acid derivatives with a molecular weight of approx. 400 to 3,000. They are classified as hydrolyzable or condensed tannins.
  • the hydrolyzable tannins are made soluble in mineral acid by boiling, whereas the condensed tannins are insoluble under the same conditions.
  • Many tannins occur naturally, for example in the bark or in Lichen mangroves, oaks, eucalyptus, various firs, such as hemlock, pine, larch and willow.
  • Suitable tannins or tannic acids are e.g. B.
  • the metals such as. B. chrome or zirconium.
  • the vegetable tannins either the hydrolyzable or condensed or mixtures thereof, are preferably used in the process according to the invention.
  • the metal surfaces are brought into contact with a treatment liquid, the magnesium in amounts of 0.01 to 50 g / l, preferably 0.095 to 10 g / l, and phosphate in amounts of 0.01 to 50 g / l , preferably 0.05 to 3.0 g / l, or tannin in amounts of 0.01 to 10 g / l, preferably up to 3 g / l.
  • nitrate content should be 0.01 to 10 g / l, preferably 0.05 to 2 g / l.
  • Another preferred embodiment of the invention consists in bringing the metal surfaces into contact with a treatment liquid which additionally contains fluoride.
  • the conversion coatings produced by the process according to the invention consist essentially of magnesium phosphate, generally also of phosphates of the treated metals and tannin compounds. If fluoride is also used, fluoride compounds can also be incorporated. In any case, a fluoride content of the treatment liquid increases the reaction of the tannin with the metal surface, especially with aluminum, thereby facilitating the formation of the conversion coating and improving its quality.
  • nitrate ions also favors the coating formation and the favorable properties of the conversion coating itself.
  • the active components magnesium, fluoride, phosphate and nitrate can be used as salts, magnesium z. B. in the form of magnesium nitrate, or - as far as possible and taking into account the pH to be set - as an acid.
  • the treatment liquid is applied in a manner known per se, e.g. B. by diving, spraying, rolling up. Spray and roll up methods are preferred.
  • the temperature of the metals to be treated can be at ambient temperature or higher. Higher temperatures, e.g. B. of about 38 ° C, are often due to the heat transfer in upstream cleaning and rinsing.
  • the treatment liquid can be used at ambient temperature or at a temperature above 38 ° C.
  • the metal surfaces are preferably brought into contact with a treatment liquid which has a temperature in the range from 49 to 60 ° C. Higher temperatures accelerate the volatilization of the water.
  • the contact time between the metal surface and the treatment liquid can vary greatly depending on the application. When spraying extruded aluminum or aluminum alloys, a contact time of 1 minute is preferred. In contrast, a spray duration of 10 seconds is preferred in the treatment of aluminum coils. In the case of roll-up methods, the contact time is generally short. The general rule is: the hotter and more concentrated the treatment liquid; the shorter the contact time can be. !
  • Another extremely advantageous embodiment of the invention consists in drying the treatment liquid and in this case preferably dimensioning the film of the treatment liquid in such a way that a layer weight of max. 4.3 g / m 2 is obtained. This procedure avoids the occurrence of rinsing water.
  • the use of the treatment liquid with a pH in the range from 2.5 to 4.5 is particularly expedient with regard to rapid and good layer formation.
  • the treatment liquid used by the method according to the invention can have other additives known in the technology of producing conversion coatings.
  • Examples are accelerators, chelating agents, dyes, stabilizers and the commonly used metal cations, such as zinc, manganese, cobalt, nickel, iron and the like, insofar as they have no disadvantageous effect on the subsequently applied coatings with regard to corrosion protection and adhesion.
  • the coatings obtained by the process according to the invention are of excellent corrosion resistance and improve the adhesion of subsequently applied organic coatings in a similar manner to the industrially customary processes.
  • corrosion protection and adhesion promotion are similar to the conversion coatings obtained with chromium-containing treatment liquids.
  • the invention therefore represents an alternative to the use of chromium-containing treatment liquids, their disadvantages with regard to toxicity and environmental pollution being avoided.
  • the treated metal surfaces have essentially the same color and Surface characteristics on untreated metal surfaces, in particular discoloration is avoided.
  • treatment liquid 4 was applied by spraying with subsequent water rinsing and drying.
  • Treatment liquid 5 was applied by roller application. It was then dried.
  • the sheet metal samples obtained by treatment with the 5 different treatment liquids were each divided into 3 lots, each lot being provided with one of the 3 lacquers.
  • VF stands for very little
  • F for little
  • M for medium
  • D dense blistering
  • the size of the bubbles is rated from 9 (very small bubble) to 1 (very large bubble). 10 means no blistering.
  • G or C concentration effects expresses that the sheets have a rating of 10, except for local blistering due to the handling (G) of the sheets or of concentration effects (C), e.g. B. caused by descending solution.
  • the elasticity and thus the adhesive strength of the paint layer is determined in the event of sudden deformation.
  • a falling body is allowed to hit the unpainted sheet metal side with its spherically shaped striking part (ball diameter 15.9 mm).
  • the standard test is carried out shortly after the paint has hardened and at ambient temperature.
  • One variant is the “cold deepening”, in which the test is carried out on a painted sheet that is cooled to or below - 9.44 ° C.
  • Another test method is the "delayed cold impact”, whereby the test is carried out at least 5 days after painting.
  • Table I contains the test results of the sheets provided with the acrylic varnish, Table 11 the test results of the sheets provided with the alkyd resin varnish and Table 111 the test results of the sheets provided with the varnish based on polyester.

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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Claims (10)

1. Procédé d'application de revêtements de conversion sur des surfaces métalliques, en particulier d'aluminium et d'alliages d'aluminium, avec des liquides de traitement contenant des ions magnésium et des ions phosphate, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient en outre du tanin, est exempt de chrome et présente un pH de 2 à moins de 7.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient du magnésium en des quantités de 0,01 à 50 g/I, de préférence de 0,095 à 10 g/l, et du phosphate en des quantités de 0,01 à 50 g/i, de préférence de 0,05 à 3,0 g/I.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient du tanin en des quantités de 0,01 à 10 g/l, de préférence jusqu'à 3 g/I.
4. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient en outre du nitrate.
5. Procédé suivant la revendication 4, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient du nitrate en des quantités de 0,01 à 10 g/l, de préférence de 0,05 et 2 g/I.
6. Procédé suivant une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient en outre du fluorure.
7. Procédé suivant la revendication 6, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui contient du fluorure en des quantités de 0,01 à 10 g/I, de préférence de 0,05 à 3 g/l.
8. Procédé suivant une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui présente une température dans le domaine de 49 à 60 °C.
9. Procédé suivant l'une quelconque des revendications 1 à 8, caractérisé en ce qu'on sèche le liquide de traitement et on dose dans ce cas de préférence la pellicule de liquide de traitement de telle sorte qu'on obtienne après séchage un poids de couche de 4,3 g/m2 au maximum.
10. Procédé suivant une ou plusieurs des revendications 1 à 9, caractérisé en ce qu'on met les surfaces métalliques en contact avec un liquide de traitement qui présente un pH de 2,5 à 4,5.
EP81201403A 1981-01-02 1981-12-29 Procédé pour le traitement de surfaces métalliques Expired EP0055881B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/222,218 US4385096A (en) 1981-01-02 1981-01-02 Aqueous magnesium treatment composition for metals
US222218 1981-01-02

Publications (2)

Publication Number Publication Date
EP0055881A1 EP0055881A1 (fr) 1982-07-14
EP0055881B1 true EP0055881B1 (fr) 1985-04-24

Family

ID=22831357

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81201403A Expired EP0055881B1 (fr) 1981-01-02 1981-12-29 Procédé pour le traitement de surfaces métalliques

Country Status (6)

Country Link
US (1) US4385096A (fr)
EP (1) EP0055881B1 (fr)
JP (1) JPS5934234B2 (fr)
AU (1) AU535455B2 (fr)
DE (1) DE3170216D1 (fr)
GB (1) GB2093074B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672084B2 (fr) * 1992-11-30 2007-03-07 Bulk Chemicals, Inc. Procede et composition de traitement de surfaces metalliques
US5804652A (en) * 1993-08-27 1998-09-08 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US6459848B1 (en) 1997-08-06 2002-10-01 Victor Company Of Japan, Ltd. Magnetic recording apparatus and method, and magnetic recording medium
US6749953B1 (en) * 2000-11-21 2004-06-15 Sambix Corporation Whiskerless galvanized product having multi-layer rust prevention film and manufacturing method of whiskerless galvanized product having multi-layer rust prevention film
DE10116501A1 (de) * 2001-04-03 2002-10-17 Bosch Gmbh Robert Stutzen zum Anschluß eines Absaugschlauchs an eine Handwerkzeugmaschine
US8277870B2 (en) * 2008-11-25 2012-10-02 GM Global Technology Operations LLC Method of controlling corrosion at an interface formed between metal components

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3975214A (en) * 1972-04-24 1976-08-17 Oxy Metal Industries Corporation Tannin containing compositions
BE798243A (fr) * 1972-04-24 1973-07-31 Parker Ste Continentale Procede pour appliquer un revetement resistant a la corrosion et a l'humidite sur une surface metallique
US4017334A (en) * 1973-10-04 1977-04-12 Oxy Metal Industries Corporation Process for treating aluminum cans
US4054466A (en) * 1975-09-10 1977-10-18 Oxy Metal Industries Corporation Tannin treatment of aluminum
US4063969A (en) * 1976-02-09 1977-12-20 Oxy Metal Industries Corporation Treating aluminum with tannin and lithium
US4094801A (en) * 1976-04-29 1978-06-13 The Lubrizol Corporation Magnesium-containing complexes, method for their preparation, and compositions containing the same
JPS53120644A (en) * 1977-03-31 1978-10-21 Nippon Packaging Kk Surface treatment method of aluminium and its alloy

Also Published As

Publication number Publication date
GB2093074B (en) 1985-03-06
DE3170216D1 (en) 1985-05-30
EP0055881A1 (fr) 1982-07-14
AU535455B2 (en) 1984-03-22
JPS5934234B2 (ja) 1984-08-21
JPS57134569A (en) 1982-08-19
GB2093074A (en) 1982-08-25
US4385096A (en) 1983-05-24
AU7922482A (en) 1982-07-08

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