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EP0215041B1 - Procede de phosphatation de surfaces metalliques - Google Patents

Procede de phosphatation de surfaces metalliques Download PDF

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Publication number
EP0215041B1
EP0215041B1 EP86901388A EP86901388A EP0215041B1 EP 0215041 B1 EP0215041 B1 EP 0215041B1 EP 86901388 A EP86901388 A EP 86901388A EP 86901388 A EP86901388 A EP 86901388A EP 0215041 B1 EP0215041 B1 EP 0215041B1
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EP
European Patent Office
Prior art keywords
phosphating
zinc
bromate
phosphate
phosphating solutions
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
EP86901388A
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German (de)
English (en)
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EP0215041A1 (fr
Inventor
Ramon Bacardit Cabado
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0215041A1 publication Critical patent/EP0215041A1/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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids

Definitions

  • the invention relates to a process for phosphating metal surfaces, in particular iron and steel, with aqueous, acidic phosphating solutions which, in addition to zinc and phosphate ions, contain an accelerator combination of alkali metal bromate and m-nitrobenzenesulfonate.
  • the new process is particularly suitable as a pretreatment of the metal surfaces for a subsequent cathodic electrocoating.
  • Chlorate serves as an accelerator for these phosphating baths, optionally in combination with nitrite or nitrate.
  • the thin and uniform phosphate coatings obtained in this way are particularly suitable as the basis for a subsequent electrocoating.
  • such low-zinc phosphating processes are much more sensitive to changes in the process parameters due to the accelerators mentioned. This means that although high-quality phosphate layers result with fresh phosphating solutions, the corrosion protection deteriorates due to the irregularity of phosphate layers after the throughput of a large amount of metal surfaces, and in some cases no more useful protective layers are formed.
  • DE-PS 1072055 describes a method for increasing the layer weight in the production of phosphate coatings. This increase in layer weight is achieved by adding a chelating agent, in particular based on polycarboxy-a-amino acids, to the phosphating solutions based on zinc phosphate.
  • a chelating agent in particular based on polycarboxy-a-amino acids
  • nitrate, nitrite and chlorate, bromate or nitrobenzenesulfonate can also be used as accelerators.
  • this is not a so-called “low zinc process”.
  • the process described in DE-PS 10 96152 also uses zinc phosphating solutions which have the conventional ratios of zinc to phosphate. These phosphating solutions additionally contain a certain amount of calcium and an oxidizing agent as an accelerator, bromate or m-nitrobenzenesulfonate being mentioned, among others. This process, which operates at relatively high temperatures, results in phosphating layers with layer weights in the range from 102 to 117 mg / dm 2 .
  • DE-OS 2418 118 also describes a process for the preparation of phosphate coatings on iron and steel in which phosphating solutions based on alkali metal and / or ammonium orthophosphate are used. These phosphating baths additionally contain short-chain alkanolamines, nonionic wetting agents and an accelerating agent, bromate or m-nitrobenzenesulfonate being also mentioned, among others. However, this does not result in zinc phosphate layers on the metal surfaces.
  • a major disadvantage of the conventional phosphating processes based on zinc phosphate or alkali metal phosphate discussed above - in comparison to the low-zinc phosphating process mentioned at the outset - is the fact that the phosphate layers formed here for subsequent cathodic electrocoating are less - due to the different chemical layer structure are suitable.
  • thicker phosphate layers usually result, ie with a " higher layer weight, with relatively high bath temperatures being used.
  • the present invention is based on the object of providing a phosphating process based on zinc phosphate solutions which ensures the formation of high-quality zinc phosphate layers which - with a low layer weight - are distinguished by a comparatively high iron content and are therefore particularly suitable for subsequent cathodic electrocoating .
  • the temperatures of the phosphating baths used should be relatively low and these phosphating baths should remain “stable” even with a higher throughput on metal surfaces, ie. H. Ensure phosphate layers of consistent quality.
  • the invention accordingly relates to a process for phosphating metal surfaces, in particular iron and steel, as pretreatment for a subsequent cathodic electrodeposition coating, by treating them with aqueous acid phosphating solutions which, in addition to zinc and phosphate ions, contain an alkali metal bromate as accelerator.
  • the comparatively low bath temperature which is in the range from 35 to 40 ° C., preferably from 38 to 40 ° C.
  • Another important point is the - compared to the known low-zinc processes - the relatively high content of free acid. This necessitates a stronger pickling reaction of the phosphating solutions on the metal surfaces to be treated, at the same time an increased incorporation of iron into the phosphate layer that forms and thus an improved layer formation overall.
  • the phosphate layers formed in the process according to the invention have layer weights in the range from 1 to 1.65 g / m 2 .
  • the advantages achieved with the method according to the invention also include significantly reduced sludge formation in the phosphating bath and increased stability thereof. This is to be understood to mean that even with a greater throughput of metal surfaces in the phosphating bath, the quality of the layers formed does not suffer any losses.
  • the phosphating solutions used in the process according to the invention have a free acid score in the range from 0.5 to 1, preferably from 0.6 to 0.8.
  • the total acid score is in the range from 18 to 25, preferably from 20 to 22.
  • the free acid content is determined according to the score and the total acid score is determined according to the methods known here - cf. for example, “The Phosphating of Metals •, Leuze Verlag / Saulgau, 1974, pages 274 to 277:
  • the free acid score corresponds to the consumption of ml n / 10 NaOH in the titration of 10 ml bath solution until the change in the first H 3 P0 4 stage (indicator methyl orange or bromophenol blue).
  • the total acid score corresponds to the consumption of ml n / 10 NaOh when titrating 10 ml bath solution against phenolphthalein as an indicator.
  • a combination of an alkali metal bromate and an m-nitrobenzenesulfonate is used as the accelerator, the amounts to be used and the weight ratio of bromate to m-nitrobenzenesulfonate to be within the limits given above.
  • Alkali metal bromates which are suitable for this purpose are the sodium or potassium salts, preferably the sodium bromate.
  • the sodium salt is preferably used as the m-nitrobenzenesulfonate.
  • the content of zinc in the phosphating solutions according to the invention should be in the range of the above-mentioned limits; likewise the weight ratio of phosphate to zinc and the weight ratios of zinc or phosphate to bromate.
  • metal cations can also be used in the process according to the invention. These are nickel or cobalt or manganese ions, with an additional content of nickel ions in the phosphating bath being preferred.
  • concentration ranges of these metal cations to be used are:
  • the phosphating solutions according to the invention can also contain 2 or 3 of these additional ion types, the total amount of these additional metal cations, however, not exceeding a total of 1.5 g / l.
  • the method according to the invention is particularly suitable for phosphating metal surfaces made of iron and steel. However, it can also be used to advantage for phosphating metal surfaces made of zinc, aluminum, galvanized or aluminized steel.
  • the phosphating solutions used in the process according to the invention can be prepared by dissolving the individual components in water. However, the phosphating solutions are preferably obtained by diluting concentrates which contain the active components in the same ratio as in the bath solutions. If necessary, is another Addition of alkali metal ions, preferably sodium, is necessary in order to bind the proportion of phosphate which exceeds the free acid content to be set.
  • the phosphating solutions can be applied to the metal surfaces in the process according to the invention in a manner known per se, ie. H. by spraying, dipping or in a combined spraying / dipping process.
  • the treatment times to be observed here depend on the respective application process: they are approximately 90 to 120 seconds in the spraying process; with the immersion process approx. 180 seconds and with the combined spray / immersion process approx. 20 to 30 seconds for spraying and approx. 150 to 180 seconds for diving.
  • the usual, known treatment measures can be taken before and after the actual phosphating step.
  • the metal surfaces to be phosphated are previously subjected to a cleaning treatment to remove grease and dirt, for example with the aid of alkaline cleaners. It can also be expedient - but is by no means necessary - to activate the metal surfaces in a manner known per se before the actual phosphating treatment.
  • Corresponding activating agents based on titanium phosphate are suitable, for example.
  • the metal surfaces are usually rinsed thoroughly with water. Rinsing with water and, if appropriate, aftertreatment with customary passivating agents, for example with chromium (VI) / chromium (III) solutions, also take place after the phosphating.
  • the final treatment is then cathodic electrocoating, likewise in a manner known per se.
  • the zinc phosphate layers with a high iron content obtained by the process according to the invention are generally suitable for all types of use of phosphate layers known to date, but they have particular advantages for subsequent cathodic electrocoating. Here they show a high resistance of the paint film against paint infiltration under corrosive stress as well as an excellent paint adhesion to the metallic surface.
  • the phosphate layers obtained were finely crystalline and closed.
  • Table 1 below are for the individual examples in each case the temperature of the phosphating solution, the type and duration - refer to the application layer as well as the weights of the phosphate layer produced.
  • Sheets of electrolytically galvanized steel (7.5 ⁇ m thick) and sheets of aluminum (Al 99.5, semi-hard) were treated in the same way.
  • the phosphate layers produced on electrolytically galvanized steel showed a slightly increased layer weight.
  • the phosphated sheets were then cathodically electrocoated with different paint qualities and dried at elevated temperature.
  • the dry film thickness of the paints was approx. 20 ⁇ m in each case.
  • the painted sheets were then each provided with a parallel cut and subjected to a salt spray test in accordance with SS DIN 50021. After completion of the spray test, the infiltration of paint was determined and the formation of bubbles (blister) was assessed optically. Tables 2 and 3 below show the results obtained:

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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)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

Procédé de phosphatation de surfaces métalliques, en particulier du fer et de l'acier, avec des solutions de phosphatation aqueuses acides. Outre des ions zinc et des ions phosphate, les solutions contiennent une combinaison activatrice d'un bromate de métal alcalin et du m-nitrobenzolsulfonate. Ce nouveau procédé est particulièrement approprié au prétraitement de surfaces métalliques avant de procéder à un laquage cathodique en bain électrolytique. Les solutions acides de phosphatation satisfont les conditions suivantes: a) teneur en zinc: 1, 2 à 2g/l; b) teneur en bromate: 0,5 à 1g/l; c) teneur en m-nitrobenzolsulfonate: 0,2 à 0,5 g/l; d) rapport pondéral phosphate : zinc = (7 à 20) : 1; e) rapport pondéral phosphate : bromate = (14 à 48) : 1; f) rapport pondéral zinc : bromate = (1,2 à 4) : 1; g) rapport pondéral bromate : m-nitrobenzolsulfonate = (1 à 5) : 1; h) nombre total de points acides : 18 à 25; i) nombre de points sans acide : 0,5 à 1; g) température: 35 à 40oC.

Claims (7)

1. Procédé de phosphatation de surfaces métalliques, en particulier de fer et d'acier, en tant que traitement préalable pour un laquage cathodique par immersion électrique, ultérieur, au moyen de leur traitement avec des solutions aqueuses acides de phosphatation qui contiennent, à côté d'ions zinc et d'ions phosphates un bromate de métal alcalin comme accélérateur, caractérisé en ce que l'on travaille avec des solutions de phosphatation acides qui correspondent aux conditions suivantes :
Figure imgb0020
2. Procédé selon la revendication 1, caractérisé en ce que le bromate et le m-nitrophénylsulfonate sont mis en oeuvre sous la forme de leurs sels de sodium.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que les solutions de phosphatation possèdent un indice d'acidité totale de 20 à 22 et un indice d'acidité libre de 0,6 à 0,8.
4..Procédé selon les revendications 1 à 3, caractérisé en ce que les solutions de phosphatation sont à une température de 38 à 40 °C.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que les solutions de phosphatation contiennent, en addition :
Figure imgb0021
6. Procédé selon la revendication 5, caractérisé en ce que les solutions de phosphatation contiennent deux ou trois de ces types d'ions additionnels pour lesquels la quantité totale de ces cations métalliques additionnels ne dépasse pas au total 1,5 g/I.
7. Procédé selon les revendications 1 à 6, caractérisé en ce que les solutions de phosphatation sont appliquées sur les surfaces métalliques par pulvérisation, immersion ou selon un procédé mixte pulvérisation/immersion.
EP86901388A 1985-02-22 1986-02-20 Procede de phosphatation de surfaces metalliques Expired EP0215041B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES541129 1985-02-22
ES541129A ES8606528A1 (es) 1985-02-22 1985-02-22 Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas

Publications (2)

Publication Number Publication Date
EP0215041A1 EP0215041A1 (fr) 1987-03-25
EP0215041B1 true EP0215041B1 (fr) 1988-08-17

Family

ID=8488822

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86901388A Expired EP0215041B1 (fr) 1985-02-22 1986-02-20 Procede de phosphatation de surfaces metalliques

Country Status (9)

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US (1) US4708744A (fr)
EP (1) EP0215041B1 (fr)
JP (1) JPS62501919A (fr)
BR (1) BR8605484A (fr)
DE (1) DE3660553D1 (fr)
ES (1) ES8606528A1 (fr)
PL (1) PL254554A1 (fr)
SU (1) SU1560060A3 (fr)
WO (1) WO1986004931A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1333683C (fr) * 1987-12-18 1994-12-27 Masahiro Jo Procede de phosphatation de surfaces metalliques
US5525431A (en) * 1989-12-12 1996-06-11 Nippon Steel Corporation Zinc-base galvanized sheet steel excellent in press-formability, phosphatability, etc. and process for producing the same
DE4330002C1 (de) * 1993-09-04 1995-03-23 Herberts Gmbh Verfahren zur Lackierung von metallischen Substraten und Anwendung des Verfahrens
AU678284B2 (en) * 1993-09-06 1997-05-22 Henkel Kommanditgesellschaft Auf Aktien Nickel-free phosphatization process
DE19540085A1 (de) * 1995-10-27 1997-04-30 Henkel Kgaa Nitratarme, manganfreie Zinkphosphatierung
US6530999B2 (en) * 2000-10-10 2003-03-11 Henkel Corporation Phosphate conversion coating
WO2009017535A2 (fr) * 2007-06-07 2009-02-05 Henkel Ag & Co. Kgaa Phosphatation au manganèse, zinc et modifiée au cobalt

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE522392A (fr) * 1952-08-28
US2884351A (en) * 1956-01-25 1959-04-28 Parker Rust Proof Co Method of cold rolling ferrous strip stock
BE635606A (fr) * 1962-08-01
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
GB1591039A (en) * 1977-05-03 1981-06-10 Pyrene Chemical Services Ltd Processes and compositions for coating metal surfaces
JPS5811513B2 (ja) * 1979-02-13 1983-03-03 日本ペイント株式会社 金属表面の保護方法
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
US4498935A (en) * 1981-07-13 1985-02-12 Parker Chemical Company Zinc phosphate conversion coating composition

Also Published As

Publication number Publication date
JPS62501919A (ja) 1987-07-30
ES8606528A1 (es) 1986-04-01
EP0215041A1 (fr) 1987-03-25
DE3660553D1 (en) 1988-09-22
BR8605484A (pt) 1987-04-22
WO1986004931A1 (fr) 1986-08-28
US4708744A (en) 1987-11-24
PL254554A1 (en) 1986-08-26
ES541129A0 (es) 1986-04-01
SU1560060A3 (ru) 1990-04-23

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