EP0826792B1 - Bath and process for phosphating metal substrates, concentrates for preparing the bath and metal substrates treated according to the process - Google Patents

Bath and process for phosphating metal substrates, concentrates for preparing the bath and metal substrates treated according to the process Download PDF

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Publication number
EP0826792B1
EP0826792B1 EP97402032A EP97402032A EP0826792B1 EP 0826792 B1 EP0826792 B1 EP 0826792B1 EP 97402032 A EP97402032 A EP 97402032A EP 97402032 A EP97402032 A EP 97402032A EP 0826792 B1 EP0826792 B1 EP 0826792B1
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Prior art keywords
ions
phosphatization
ligand
group
aluminum
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EP97402032A
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German (de)
French (fr)
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EP0826792A1 (en
Inventor
Joseph Schapira
Patrick Droniou
Michel Sudour
Michèle Guimon
Daniel Bernard
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Henkel AG and Co KGaA
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Compagnie Francaise de Produits Industriels SA
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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
    • C23C22/12—Orthophosphates containing zinc 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
    • C23C22/10—Orthophosphates containing oxidants

Definitions

  • the subject of the invention is a bath and a method for phosphating of metallic substrates as well as metallic substrates treated using these baths and process.
  • the metallic substrates concerned are those based steel possibly coated with zinc or zinc alloys with other metals like iron, nickel, aluminum, manganese, as well as those based on aluminum possibly ally.
  • Phosphating baths are generally applied by immersion, sprinkling or by combinations of these methods which may include the implementation of applicator rollers.
  • baths consist of aqueous solutions acids containing phosphate ions, fluorides (simple and / or complexed with one or more elements chosen from silicon, boron, zirconium and titanium), nitrates, bivalent cations such as zinc, as well that possibly those of the group comprising Mn, Mg, Ni, Cu, Ca, Fe and monovalent cations such as Na.
  • They may also contain polyoses, derived from sugar, heteropolysaccharides and glucose.
  • the accelerators conventionally used are those from the group comprising nitrites, metal chlorates alkaline, m-nitrobenzene sulfonate, hydrogen peroxide, more recently hydroxylamine and different combinations of these compounds.
  • the nitrites ions have the disadvantage major not to be stable in an acid medium and to decompose into nitrogen oxides; permanent food baths in nitrite ions is therefore necessary even in the absence of consumption linked to the processing of parts; a another disadvantage of nitrite ions lies precisely in the fact that they break down into nitrogen oxides which are known for their dangerous nature, which poses worker safety issues.
  • chlorate ions leads, after reaction to the formation of chloride ions known to be detrimental to the corrosion resistance of layers produced; they also promote the appearance of white dots in these layers when processing certain galvanized substrates, forcing the operator to sand manually treated substrates.
  • Oxygenated water is not stable in a acid conversion containing the metals mentioned above, and its optimal concentration range is very narrow, which makes the bath difficult to control industrially; of more, this bath tends to form large amounts of sludge during use, sludge which should be removed by left at the dump.
  • M-nitrobenzene sulfonate is not easily dosable on the treatment line (this dosage indeed requires the use of chromatographic techniques whose cost and technicality are not compatible with a price of returns acceptable); moreover, its use leads to the generation of significant sludge.
  • Hydroxylamine to work well, must be used at levels leading to relatively low costs high, and especially its degradation can be significant in the presence of metal ions at phosphating temperature high.
  • the object of the invention is, above all, to propose to the user an accelerator for baths and processes phosphating without the disadvantages of those of the prior art.
  • the above-mentioned trivalent cobalt complexes are stable at acidic pH from 1 to 5.5, preferably from 2.5 to 3.5, unlike the simple salts of Cobalt III such as CoF 3 which decomposes into a black oxide insoluble in the phosphating.
  • complexes are most often described in ionic form; in the case of cationic complexes, the associated anion is for example one of the anions of the group comprising Cl, Br, F, I, NO 3 , CN, SCN, PO 4 , SO 4 and acetate; when anionic complexes are involved, the associated cation is for example one of the cations of the group comprising Na, K, Li, Mg, Ca and NH 4 .
  • the phosphating bath according to the invention can contain a conventional accelerator in addition to the accelerator consisting of a trivalent cobalt complex.
  • the invention also relates to a concentrate specific to supply, by a dilution of 1% to 10% with water, the phosphating bath according to the invention.
  • the phosphate coatings obtained through the invention have finesse and homogeneity in less equivalent to those of coatings obtained with placing using accelerators of the prior art.
  • a metal substrate consisting of steel or electro-galvanized steel plates whose dimensions are length 180 mm width 90 mm thickness 0.8mm
  • the free acidity of the phosphating bath is measured by the quantity (in ml) of NaOH N / 10 necessary to bring the pH of 10 ml of this bath at the value of 3.6.
  • Scoring involves measuring the width of the paint peeling perpendicular to the scratch.
  • the acceptance criterion is a separation less than or equal to 8 mm.
  • the adhesion of the paint is evaluated by the test of squaring carried out according to standard ISO 2409.
  • the acceptance limit corresponds to a quote maximum grip of 2.
  • Scoring involves measuring the width of the paint peeling perpendicular to the scratch.
  • the acceptance criterion is less than or equal detachment at 3.5 mm.
  • composition of the baths and the performances recorded appear in Table D.
  • Constituents of the phosphating bath Zn 1025 1025 PO 4 10550 10550 Or 210 210 Mn 730 730 F 1000 935 Fe 20 20 NO 3 2163 2163 SO 4 35 35 Al 1.2 1 accelerator 1 100 - accelerator 11 - 100 substrate steel steel layer weight (g / m 2 ) 2.1 1.6 3C test 3 mm 2.5mm

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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)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A new composition for a phosphating bath for the treatment of metallic substrates based on steel, possibly coated with Zn or Zn alloyed with Fe, Ni, Al or Mn, or Al-based (possibly alloyed), at a pH of 1 - 5.5.The composition contains classical components comprising :- 0.3 - 25(preferably 0.5 - 10) g/l of Zn ions ; 5 - 50(preferably 8 - 30) g/l of phosphate ions ; and about 0.01 - 10(preferably 0.03 - 3) g/l of a trivalent Co complex represented by one or other of the formulae :- ÄCo(Ligand)nÜc (I) ÄCo(Ligand)nZpÜc (II) -n, p = 1 - 6, with(formula II) n+p ≤ 6 ; -c = charge on the complex, positive or negative according to the charge of the ligand and of Z ; -the Ligand is chosen from the ions of a group comprising NO2, CN, CO3 and SO3, a group comprising oxalate, acetate, citrate, gluconate, tartrate and acetylacetonate, and compounds of formula N (R1, R2, R3), in which R1, R2 and R3 are (independently) H, 1 - 6C alkyl, hydroxyalkyl, hydroxy, alkylamine, hydroxyalkylamine, carboxylic acids or aminocarboxylic acids and their salts ; and -Z is chosen from Cl, Br, F, I, OH, NO3, SCN, PO4, S2O3, MoO4, SeO4 and H2O, given that a given complex may comprise one or more ligands and one or more Z different from one another. Also claimed, is the phosphating process, a concentrate for the preparation of a phosphating bath, the use of the Co complex as an accelerator and metallic substrates treated by the process.

Description

L'invention a pour objet un bain et un procédé de phosphatation de substrats métalliques ainsi que les substrats métalliques traités à l'aide de ces bain et procédé.The subject of the invention is a bath and a method for phosphating of metallic substrates as well as metallic substrates treated using these baths and process.

Elle vise également un concentré pour la préparation de ce bain.It also targets a concentrate for the preparation of this bath.

On connaít déjà des bains et des procédés de phosphatation de substrats métalliques.We already know baths and phosphating processes of metallic substrates.

Ces bains et procédés connus permettent la formation de revêtements de phosphate essentiellement de zinc ou de fer et de zinc à la surface des substrats métalliques traités.These known baths and methods allow the formation phosphate coatings mainly of zinc or iron and zinc on the surface of metallic substrates treated.

L'intérêt des revêtements de phosphate réside dans la bonne résistance à la corrosion qu'ils confèrent à ces surfaces et dans l'amélioration de l'adhérence à ces surfaces des peintures ou des revêtements électrophorétiques appliqués ultérieurement.The interest of phosphate coatings lies in the good corrosion resistance they give to these surfaces and in improving the adhesion to these surfaces electrophoretic paints or coatings applied later.

Les substrats métalliques concernés sont ceux à base d'acier éventuellement revêtu de zinc ou d'alliages du zinc avec d'autres métaux comme le fer, le nickel, l'aluminium, le manganèse, ainsi que ceux à base d'aluminium éventuellement allié.The metallic substrates concerned are those based steel possibly coated with zinc or zinc alloys with other metals like iron, nickel, aluminum, manganese, as well as those based on aluminum possibly ally.

Les bains de phosphatation sont généralement appliqués par immersion, aspersion ou par des combinaisons de ces méthodes qui peuvent comprendre la mise en oeuvre de rouleaux applicateurs.Phosphating baths are generally applied by immersion, sprinkling or by combinations of these methods which may include the implementation of applicator rollers.

Ces bains sont constitués par des solutions aqueuses acides contenant des ions phosphates, fluorures (simples et/ou complexés avec un ou plusieurs éléments choisis parmi le silicium, le bore, le zirconium et le titane), nitrates, des cations bivalents tels que le zinc, ainsi qu'éventuellement ceux du groupe comprenant Mn, Mg, Ni, Cu, Ca, Fe et des cations monovalents tels que Na.These baths consist of aqueous solutions acids containing phosphate ions, fluorides (simple and / or complexed with one or more elements chosen from silicon, boron, zirconium and titanium), nitrates, bivalent cations such as zinc, as well that possibly those of the group comprising Mn, Mg, Ni, Cu, Ca, Fe and monovalent cations such as Na.

Ils peuvent également contenir des polyoses, des dérivés du sucre, des hétéropolysaccharides et du glucose.They may also contain polyoses, derived from sugar, heteropolysaccharides and glucose.

On sait que, dans les bains et procédés du genre en question, la vitesse de formation du dépôt de phosphatation est accrue par l'utilisation d'accélérateurs.We know that in baths and processes of the kind in question, the rate of formation of the phosphate deposit is increased by the use of accelerators.

Les accélérateurs classiquement employés sont ceux du groupe comprenant les nitrites, les chlorates de métaux alcalins, le m-nitrobenzène sulfonate, l'eau oxygénée, plus récemment l'hydroxylamine et différentes combinaisons de ces composés.The accelerators conventionally used are those from the group comprising nitrites, metal chlorates alkaline, m-nitrobenzene sulfonate, hydrogen peroxide, more recently hydroxylamine and different combinations of these compounds.

Il a été proposé d'expliquer leur action par l'oxydation des ions Fe2+, éventuellement présents dans le bain, en ions Fe3+ éliminés sous forme de boues ferriques; en effet, l'augmentation de la proportion d'ions Fe2+ au cours du traitement doit être évitée car elle pourrait inhiber la phosphatation.It has been proposed to explain their action by the oxidation of Fe 2+ ions, possibly present in the bath, into Fe 3+ ions eliminated in the form of ferric sludge; indeed, the increase in the proportion of Fe 2+ ions during treatment should be avoided as it could inhibit phosphating.

Selon une autre explication de leur action, ils permettraient la dépassivation des substrats attaqués par l'acidité de la solution phosphatante, selon la réaction suivante: Métal + Acide H+ ⇄ Ion métal + Hydrogène H2 According to another explanation of their action, they would allow the depassivation of the attacked substrates by the acidity of the phosphate solution, according to the following reaction: Metal + Acid H + ⇄ Metal ion + Hydrogen H 2

Il se trouve que tous les accélérateurs classiquement employés présentent des inconvénients.It turns out that all accelerators conventionally employees have drawbacks.

Ainsi, les ions nitrites présentent l'inconvénient majeur de ne pas être stables en milieu acide et de se décomposer en oxydes d'azote; une alimentation permanente des bains en ions nitrites est donc nécessaire même en l'absence de consommation liée au traitement de pièces; un autre inconvénient des ions nitrites réside précisément dans le fait qu'ils se décomposent en oxyde d'azote qui sont connus pour leur caractère dangereux, ce qui pose des problèmes liés à la sécurité des travailleurs.So, the nitrites ions have the disadvantage major not to be stable in an acid medium and to decompose into nitrogen oxides; permanent food baths in nitrite ions is therefore necessary even in the absence of consumption linked to the processing of parts; a another disadvantage of nitrite ions lies precisely in the fact that they break down into nitrogen oxides which are known for their dangerous nature, which poses worker safety issues.

La mise en oeuvre des ions chlorates conduit, après réaction, à la formation d'ions chlorures connus pour être néfastes vis-à-vis de la résistance à la corrosion des couches produites; ils favorisent également l'apparition de points blancs dans ces couches lors du traitement de certains substrats zingués, obligeant l'opérateur à poncer manuellement les substrats traités.The use of chlorate ions leads, after reaction to the formation of chloride ions known to be detrimental to the corrosion resistance of layers produced; they also promote the appearance of white dots in these layers when processing certain galvanized substrates, forcing the operator to sand manually treated substrates.

L'eau oxygénée n'est pas stable dans un bain de conversion acide contenant les métaux évoqués plus haut, et son domaine de concentration optimal est très étroit, ce qui rend le bain difficile à contrôler industriellement; de plus, ce bain tend à former de grandes quantités de boues lors de l'utilisation, boues qu'il convient d'éliminer par mise en décharge.Oxygenated water is not stable in a acid conversion containing the metals mentioned above, and its optimal concentration range is very narrow, which makes the bath difficult to control industrially; of more, this bath tends to form large amounts of sludge during use, sludge which should be removed by left at the dump.

Le m-nitrobenzène sulfonate n'est pas facilement dosable sur ligne de traitement (ce dosage nécessite en effet le recours à des techniques chromatographiques dont le coût et la technicité ne sont pas compatibles avec un prix de revient acceptable); de plus, son utilisation conduit à la génération de boues importantes.M-nitrobenzene sulfonate is not easily dosable on the treatment line (this dosage indeed requires the use of chromatographic techniques whose cost and technicality are not compatible with a price of returns acceptable); moreover, its use leads to the generation of significant sludge.

L'hydroxylamine, pour donner de bons résultats, doit être utilisée à des teneurs conduisant à des coûts relativement élevés, et surtout sa dégradation peut être importante en présence d'ions métalliques à température de phosphatation élevée.Hydroxylamine, to work well, must be used at levels leading to relatively low costs high, and especially its degradation can be significant in the presence of metal ions at phosphating temperature high.

Par ailleurs, le document GB-A-599 784 décrit l'utilisation de complexes de cobalt divalent en milieu phosphatant.Furthermore, the document GB-A-599,784 describes the use of divalent cobalt complexes in the environment phosphating.

L'invention a pour but, surtout, de proposer à l'utilisateur un accélérateur pour des bains et des procédés de phosphatation ne présentant pas les inconvénients de ceux de l'art antérieur.The object of the invention is, above all, to propose to the user an accelerator for baths and processes phosphating without the disadvantages of those of the prior art.

Et la Société Demanderesse a eu le mérite de trouver que, de façon surprenante et inattendue, ce but était atteint dès lors que l'on utilise comme accélérateur pour des bains et des procédés de phosphatation un complexe de cobalt trivalent.And the Applicant Company had the merit of finding that, surprisingly and unexpectedly, this goal was achieved when we use as an accelerator for baths and phosphating processes a complex of trivalent cobalt.

Il s'ensuit que le bain de phosphatation conforme à l'invention, dont le pH est d'environ 1 à environ 5,5 et dans la constitution duquel entrent les composants classiques des bains de phosphatation, est caractérisé par le fait qu'il comporte:

  • de 0,3 à 25 g/l d'ion zinc, de préférence de 0,5 à 10 g/l,
  • de 5 à 50 g/l d'ion phosphate, de préférence de 8 à 30 g/l, et
  • de 0,01 à 10 g/l, de préférence de 0,03 à 3 g/l d'un complexe de cobalt trivalent représenté par l'une des formules: [ Co(Ligand)n ]c [ Co(Ligand)n Zp ]c dans lesquelles
    • n et p sont des nombres entiers de 1 à 6 avec, dans le cas de la formule (II), n+p ≤ 6,
    • c représente la charge du complexe et peut donc être positif ou négatif selon la charge du Ligand et de Z,
    • le Ligand est choisi parmi les ions du groupe comprenant NO2, CN, CO3 et SO3, parmi les ions du groupe comprenant les ions oxalate, acétate, citrate, gluconate, tartrate et acétylacétonate, et parmi les composés de formule N(R1, R2, R3) dans laquelle R1, R2 et R3 sont choisis, indépendamment les uns des autres, dans le groupe comprenant H, les groupements carbonés en C1 à C6 dont notamment les groupements alkyle, hydroxyalkyle, hydroxy, alkylamine, hydroxyalkylamine ainsi que les acides carboxyliques ou aminocarboxyliques et leurs sels, et
    • Z est choisi dans le groupe comprenant Cl, Br, F, I, OH, NO3, SCN, PO4, SO4, S2O3, MoO4, SeO4 et H20, étant donné qu'un complexe donné peut comporter un ou plusieurs Ligands et un ou plusieurs Z différents les uns des autres.
It follows that the phosphating bath according to the invention, the pH of which is from about 1 to about 5.5 and in the constitution of which the conventional components of the phosphating baths are included, is characterized in that it includes:
  • from 0.3 to 25 g / l of zinc ion, preferably from 0.5 to 10 g / l,
  • from 5 to 50 g / l of phosphate ion, preferably from 8 to 30 g / l, and
  • from 0.01 to 10 g / l, preferably from 0.03 to 3 g / l of a trivalent cobalt complex represented by one of the formulas: [Co (Ligand) n ] c [Co (Ligand) n Z p ] c in which
    • n and p are whole numbers from 1 to 6 with, in the case of formula (II), n + p ≤ 6,
    • c represents the charge of the complex and can therefore be positive or negative depending on the charge of Ligand and Z,
    • the Ligand is chosen from the ions of the group comprising NO 2 , CN, CO 3 and SO 3 , from the ions of the group comprising the oxalate, acetate, citrate, gluconate, tartrate and acetylacetonate ions, and from the compounds of formula N (R 1 , R 2 , R 3 ) in which R 1 , R 2 and R 3 are chosen, independently of one another, from the group comprising H, carbon groups from C 1 to C 6 , in particular alkyl, hydroxyalkyl groups, hydroxy, alkylamine, hydroxyalkylamine as well as the carboxylic or aminocarboxylic acids and their salts, and
    • Z is chosen from the group comprising Cl, Br, F, I, OH, NO 3 , SCN, PO 4 , SO 4 , S 2 O 3 , MoO 4 , SeO 4 and H 2 0, since a given complex can have one or more Ligands and one or more different Z's from each other.

Le mérite de la Société Demanderesse est d'autant plus grand que les utilisations connues des complexes de cobalt trivalent ne permettent nullement de prévoir l'applicabilité de ces produits comme accélérateurs dans les bains et procédés de phosphatation.The merit of the Applicant Company is all the more greater than the known uses of the complexes of trivalent cobalt in no way predict the applicability of these products as accelerators in baths and phosphating processes.

En effet, on ne connaissait jusqu'à présent (voir le document EP-A-0 458 020) que la mise en oeuvre des complexes de cobalt trivalent en remplacement des dérivés, cancérogènes, de chrome hexavalents, dans les traitements des surfaces de substrats essentiellement à base d'aluminium en vue de la formation sur ces surfaces de couches de conversion; les traitements de phosphatation n'étaient pas envisagés; les couches de conversion ainsi obtenues contiennent de l'oxyde d'aluminium comme constituant majeur, du moins en pourcentage volumique, et des oxydes de cobalt CoO, Co3O4 et Co2O3; en raison de l'utilisation d'ammoniaque dans les procédés décrits dans le document EP-A-0 458 020, la réaction de conversion a lieu à un pH compris entre 5 et 9,5.In fact, until now, we only knew (see document EP-A-0 458 020) that the use of trivalent cobalt complexes to replace carcinogenic, hexavalent chromium derivatives in the treatment of substrate surfaces essentially based on aluminum for the purpose of forming conversion layers on these surfaces; phosphating treatments were not considered; the conversion layers thus obtained contain aluminum oxide as the major constituent, at least in volume percentage, and cobalt oxides CoO, Co 3 O 4 and Co 2 O 3 ; due to the use of ammonia in the processes described in document EP-A-0 458 020, the conversion reaction takes place at a pH of between 5 and 9.5.

Les susdits complexes de cobalt trivalent sont stables à pH acide de 1 à 5,5, préférentiellement de 2,5 à 3,5, contrairement aux sels simples de Cobalt III tel CoF3 qui se décompose en un oxyde noir insoluble dans les bains de phosphatation.The above-mentioned trivalent cobalt complexes are stable at acidic pH from 1 to 5.5, preferably from 2.5 to 3.5, unlike the simple salts of Cobalt III such as CoF 3 which decomposes into a black oxide insoluble in the phosphating.

Ces complexes sont le plus souvent décrits sous forme ionique; lorsqu'il s'agit de complexes cationiques, l'anion associé est par exemple l'un des anions du groupe comprenant Cl, Br, F, I, NO3, CN, SCN, PO4, SO4 et l'acétate; lorsqu'il s'agit de complexes anioniques, le cation associé est par exemple l'un des cations du groupe comprenant Na, K, Li, Mg, Ca et NH4.These complexes are most often described in ionic form; in the case of cationic complexes, the associated anion is for example one of the anions of the group comprising Cl, Br, F, I, NO 3 , CN, SCN, PO 4 , SO 4 and acetate; when anionic complexes are involved, the associated cation is for example one of the cations of the group comprising Na, K, Li, Mg, Ca and NH 4 .

Dans un mode de réalisation préféré du bain de phosphatation conforme à l'invention, le complexe de cobalt trivalent est choisi dans le groupe comprenant:
   [Co(NH3)6]Cl3
   [Co(NO2)6]Na3
   [Co(en)3](NO3)3   avec en = éthylènediamine
   [Co(pn)3](NO3)3   avec pn = diamino 1-2 propane
   [Co(oxalate)en2]NO3
   [Co(citrate)(CO3)]Na2
   [CoF(NH3)5](NO3)2
   [Co(NO3)(NH3)5](NO3)2.In a preferred embodiment of the phosphating bath according to the invention, the trivalent cobalt complex is chosen from the group comprising:
[Co (NH 3 ) 6 ] Cl 3
[Co (NO 2 ) 6 ] Na 3
[Co (en) 3 ] (NO 3 ) 3 with en = ethylenediamine
[Co (pn) 3 ] (NO 3 ) 3 with pn = diamino 1-2 propane
[Co (oxalate) in 2 ] NO 3
[Co (citrate) (CO 3 )] Na 2
[CoF (NH 3 ) 5 ] (NO 3 ) 2
[Co (NO 3 ) (NH 3 ) 5 ] (NO 3 ) 2 .

Le bain de phosphatation conforme à l'invention peut contenir un accélérateur classique en plus de l'accélérateur constitué par un complexe de cobalt trivalent.The phosphating bath according to the invention can contain a conventional accelerator in addition to the accelerator consisting of a trivalent cobalt complex.

Le procédé de phosphatation conforme à l'invention, qui comprend les étapes successives des procédés de phosphatation classiques, dont notamment:

  • une étape de dégraissage,
  • une étape de rinçage,
  • l'étape de phosphatation proprement dite,
  • une étape de rinçage et
  • une étape de séchage,
est caractérisé par le fait que, dans l'étape de phosphatation proprement dite, on met en oeuvre le bain de phosphatation conforme à l'invention.The phosphating process according to the invention, which comprises the successive stages of the conventional phosphating processes, including in particular:
  • a degreasing step,
  • a rinsing step,
  • the actual phosphating step,
  • a rinsing step and
  • a drying step,
is characterized in that, in the actual phosphating step, the phosphating bath according to the invention is used.

L'invention vise également un concentré propre à fournir, par une dilution de 1% à 10% avec de l'eau, le bain de phosphatation conforme à l'invention.The invention also relates to a concentrate specific to supply, by a dilution of 1% to 10% with water, the phosphating bath according to the invention.

Les revêtements de phosphate obtenus grâce à l'invention présentent une finesse et une homogénéité au moins équivalente à celles des revêtements obtenus avec mise en oeuvre des accélérateurs de l'art antérieur.The phosphate coatings obtained through the invention have finesse and homogeneity in less equivalent to those of coatings obtained with placing using accelerators of the prior art.

De plus, leur stabilité est excellente.In addition, their stability is excellent.

Les performances enregistrées grâce à l'invention, en utilisant un complexe de cobalt trivalent comme accélérateur, apparaissent clairement à la lecture des exemples comparatifs non limitatifs suivants.The performances recorded thanks to the invention, using a trivalent cobalt complex as an accelerator, appear clearly on reading the examples following non-limiting comparisons.

Dans ces exemples, on a appliqué à un substrat métallique, constitué par des plaques d'acier ou d'acier électrozingué dont les dimensions sont longueur 180 mm largeur 90 mm épaisseur 0,8 mm In these examples, we applied to a metal substrate, consisting of steel or electro-galvanized steel plates whose dimensions are length 180 mm width 90 mm thickness 0.8mm

la séquence de traitements résultant du tableau A. Etape Type de traitement Produits T (°C) et durée (min) dégraissage immersion Ridoline 1550 CF / 4 2% p/p 60°C + Ridosol 550 CF 0,2% p/p 5 minutes rinçage immersion eau de ville 20°C 1 minute affinage immersion Fixodine 50 CF 0,05% p/p 20°C en eau déminéralisée 1 minute phosphatation immersion selon compositions indiquées 55°C aux tableaux B, C et D 3 minutes rinçage immersion eau déminéralisée 20°C 1 minute séchage air chaud

Ridoline 1550 CF / 4 =
produit alcalin à base de potasse et de silicates commercialisé par la Société Demanderesse
Ridosol 550 CF =
produit acide à base de tensioactifs non-ioniques commercialisé par la Société Demanderesse
Fixodine 50 CF =
produit neutre à base de phosphates de Na et de Ti commercialisé par la Société Demanderesse
the processing sequence resulting from Table A. Step Type of treatment Products T (° C) and duration (min) degreasing immersion Ridoline 1550 CF / 4 2% w / w 60 ° C + Ridosol 550 CF 0.2% w / w 5 minutes rinsing immersion city water 20 ° C 1 minute ripening immersion Fixodine 50 CF 0.05% w / w 20 ° C in demineralized water 1 minute phosphating immersion according to the compositions indicated 55 ° C in Tables B, C and D 3 minutes rinsing immersion Demineralized Water 20 ° C 1 minute drying hot air
Ridoline 1550 CF / 4 =
alkaline product based on potash and silicates marketed by the Applicant Company
Ridosol 550 CF =
acid product based on nonionic surfactants marketed by the Applicant Company
Fixodine 50 CF =
neutral product based on Na and Ti phosphates sold by the Applicant Company

L'acidité libre du bain de phosphatation est mesurée par la quantité (en ml) de NaOH N/10 nécessaire pour amener le pH de 10 ml de ce bain à la valeur de 3,6. The free acidity of the phosphating bath is measured by the quantity (in ml) of NaOH N / 10 necessary to bring the pH of 10 ml of this bath at the value of 3.6.

Sur les plaques traitées, on a déterminé:

  • la structure de la couche cristalline par observation au microscope électronique à balayage (MEB) en vue d'obtenir la taille des cristaux et le taux de recouvrement,
  • le poids de couche par mesure selon la norme ISO 3892,
  • la résistance au brouillard salin (BS) selon la norme ISO 9227.
On the treated plates, it was determined:
  • the structure of the crystal layer by observation with a scanning electron microscope (SEM) in order to obtain the size of the crystals and the recovery rate,
  • the layer weight per measurement according to ISO 3892,
  • resistance to salt spray (BS) according to ISO 9227.

Pour des substrats métalliques revêtus de peinture type polyester laque blanche Saultain de la Société PPG, référence Y 143 W 408, la durée du test au brouillard salin est de 96 heures, cette peinture ayant des performances très nettement inférieures à une peinture cataphorétique.For metallic substrates coated with paint Saultain white lacquer polyester type from PPG, reference Y 143 W 408, the duration of the salt spray test is 96 hours, this paint having very good performances significantly lower than a cataphoretic painting.

La cotation consiste à mesurer la largeur du décollement de peinture perpendiculairement à la rayure.Scoring involves measuring the width of the paint peeling perpendicular to the scratch.

Le critère d'acceptation est un décollement inférieur ou égal à 8 mm.The acceptance criterion is a separation less than or equal to 8 mm.

L'adhérence de la peinture est évaluée par le test de quadrillage effectué selon la norme ISO 2409.The adhesion of the paint is evaluated by the test of squaring carried out according to standard ISO 2409.

La limite d'acceptation correspond à une cotation d'adhérence au maximum égale à 2.The acceptance limit corresponds to a quote maximum grip of 2.

Pour les substrats phosphatés revêtus d'une peinture cataphorétique commercialisée par la Société PPG sous la référence W 742/962, on a effectué le test de "Corrosion par Changement Climatique" (ou test "3C") selon la norme Renault D17 1686/D.For phosphated substrates coated with paint cataphoretic marketed by the PPG Company under the reference W 742/962, the "Corrosion by Climate Change "(or" 3C "test) according to Renault standard D17 1686 / D.

Ce test consiste en une succession de 9 cycles d'une semaine comportant chacun les phases suivantes:

  • 24 heures de brouillard salin selon la norme ISO 9227,
  • 4 fois un cycle de 8 heures à 40°C et sous 95 à 100% d'humidité relative (HR), et de 16 heures à 20°C et sous 70 à 75% HR,
  • 48 heures à 20°C et sous 60 à 65% HR.
This test consists of a succession of 9 one-week cycles each comprising the following phases:
  • 24 hours of salt spray according to ISO 9227,
  • 4 times a cycle of 8 hours at 40 ° C and under 95 to 100% relative humidity (RH), and 16 hours at 20 ° C and under 70 to 75% RH,
  • 48 hours at 20 ° C and under 60 to 65% RH.

La cotation consiste à mesurer la largeur du décollement de peinture perpendiculairement à la rayure. Le critère d'acceptation est un décollement inférieur ou égal à 3,5 mm.Scoring involves measuring the width of the paint peeling perpendicular to the scratch. The acceptance criterion is less than or equal detachment at 3.5 mm.

EXEMPLE 1EXAMPLE 1

On a effectué 16 essais (A à P) en utilisant

  • huit accélérateurs conformes à l'invention, à savoir: Accélérateur 1 [Co(NH3)6]Cl3 Accélérateur 2 [Co(NO2)6]Na3 Accélérateur 3 [Co(en)3](NO3)3
    avec en = éthylènediamine         Accélérateur 4 [Co(pn)3] (NO3)3
    avec pn = diamino 1-2 propane         Accélérateur 5 [Co(oxalate)en2]NO3 Accélérateur 6 [Co(citrate)(CO3)]Na2 Accélérateur 7 [CoF(NH3)5] (NO3)2 Accélérateur 8 [Co(NO3) (NH3)5] (NO3)2
  • un accélérateur constitué par un sel de cobalt et qui n'est pas selon l'invention :
       Accélérateur 9 CoF3 sel de Cobalt III
  • un accélérateur constitué par un complexe de cobalt divalent et qui n'est pas selon l'invention :
       Accélérateur 10 [Co(NH3)6]Cl2 complexe de Cobalt II
  • et un accélérateur selon l'art antérieur, à savoir l'accélérateur 11 qui est du nitrite de sodium NaNO2.
16 tests (A to P) were carried out using
  • eight accelerators in accordance with the invention, namely: Accelerator 1 [Co (NH 3 ) 6 ] Cl 3 Accelerator 2 [Co (NO 2 ) 6 ] Na 3 Accelerator 3 [Co (en) 3 ] (NO 3 ) 3
    with en = ethylenediamine     Accelerator 4 [Co (pn) 3 ] (NO 3 ) 3
    with pn = diamino 1-2 propane     Accelerator 5 [Co (oxalate) in 2 ] NO 3 Accelerator 6 [Co (citrate) (CO 3 )] Na 2 Accelerator 7 [CoF (NH 3 ) 5 ] (NO 3 ) 2 Accelerator 8 [Co (NO 3 ) (NH 3 ) 5 ] (NO 3 ) 2
  • an accelerator consisting of a cobalt salt and which is not according to the invention:
    Accelerator 9 CoF 3 Cobalt III salt
  • an accelerator constituted by a divalent cobalt complex and which is not according to the invention:
    Accelerator 10 [Co (NH 3 ) 6 ] Cl 2 Cobalt II complex
  • and an accelerator according to the prior art, namely the accelerator 11 which is sodium nitrite NaNO 2 .

Les compositions des bains correspondant aux onze essais, la nature des substrats (acier ou acier électrozingué EZ), la taille des cristaux et le pourcentage de recouvrement résultent du tableau B.

Figure 00100001
Figure 00110001
The compositions of the baths corresponding to the eleven tests, the nature of the substrates (steel or electro-galvanized steel EZ), the size of the crystals and the percentage of covering result from Table B.
Figure 00100001
Figure 00110001

L'examen des données réunies dans le tableau B montre

  • que la structure cristalline obtenue avec des complexes de Cobalt III comme accélérateurs est aussi fine et homogène qu'une phosphatation cristalline classique accélérée aux nitrites (essai P) et
  • que les sels de Cobalt III ou les complexes de Cobalt II (essais N et O) ne jouent aucun rôle d'accélérateurs, comme le montrent aussi bien le taux de recouvrement que la taille du peu de cristaux formés.
Examination of the data collected in Table B shows
  • that the crystal structure obtained with Cobalt III complexes as accelerators is as fine and homogeneous as a conventional crystalline phosphating accelerated with nitrites (test P) and
  • that the Cobalt III salts or the Cobalt II complexes (tests N and O) do not play any role of accelerators, as shown by the recovery rate as well as the size of the few crystals formed.

EXEMPLE 2EXAMPLE 2

On a effectué cinq essais (Q à U) en utilisant les accélérateurs 3, 7, 8 et 11 et on a déterminé sur des plaques traitées et recouvertes de la peinture type polyester laque blanche identifiée plus haut les performances anti-corrosion et d'adhérence peinture. Les compositions des bains dans les cinq essais et les résultats des mesures effectuées sont réunis dans le tableau C. Teneur (ppm) des bains de phosphatation dans les bains Q R S T U Constituants du bain de phosphatation Zn 1025 1025 1025 1025 1025 PO4 10550 9860 9860 9860 10550 Ni 210 0 0 0 210 Mn 730 1460 1460 730 730 F 1000 365 365 365 1000 Fe 20 20 20 20 20 NO3 2163 3770 3770 2020 2163 SO4 35 35 35 35 35 Al 0,87 0,75 0,65 0,75 0,85 accélérateur 3 200 400 - - - accélérateur 7 - - 400 - - accélérateur 8 - - - 400 - accélérateur 11 - - - - 100 substrat acier acier acier acier acier poids de couche (g/m2) 2,96 2,16 1,74 0,94 2,8 adhérence 1 0 2 0 1 BS 96 h (mm) 3 5 6 6 7 Five tests (Q to U) were carried out using accelerators 3, 7, 8 and 11 and anti-corrosion and adhesion performance were determined on plates treated and covered with polyester white lacquer paint identified above. painting. The compositions of the baths in the five tests and the results of the measurements carried out are collated in Table C. Content (ppm) of phosphating baths in baths Q R S T U Constituents of the phosphating bath Zn 1025 1025 1025 1025 1025 PO 4 10550 9860 9860 9860 10550 Or 210 0 0 0 210 Mn 730 1460 1460 730 730 F 1000 365 365 365 1000 Fe 20 20 20 20 20 NO 3 2163 3770 3770 2020 2163 SO 4 35 35 35 35 35 Al 0.87 0.75 0.65 0.75 0.85 accelerator 3 200 400 - - - accelerator 7 - - 400 - - accelerator 8 - - - 400 - accelerator 11 - - - - 100 substrate steel steel steel steel steel layer weight (g / m 2 ) 2.96 2.16 1.74 0.94 2.8 grip 1 0 2 0 1 BS 96 h (mm) 3 5 6 6 7

L'examen des données réunies au tableau C montre que les performances anti-corrosion et d'adhérence peinture sont équivalentes pour des substrats ayant subi des phosphatations accélérées avec des complexes de Cobalt III, ou avec des nitrites.Examination of the data collected in Table C shows that anti-corrosion and paint adhesion performance are equivalent for substrates that have undergone accelerated phosphating with Cobalt complexes III, or with nitrites.

EXEMPLE 3EXAMPLE 3

On a effectué deux essais (V et W) en utilisant les accélérateurs 1 et 11.Two tests (V and W) were carried out using the accelerators 1 and 11.

On a traité des plaques revêtues de la peinture cataphorétique identifiée plus haut et on a déterminé le poids de couche et les performances dans le test "3C" (corrosion par changement climatique). We treated plates coated with paint cataphoretic identified above and we determined the layer weight and performance in the "3C" test (corrosion by climate change).

La composition des bains et les performances enregistrées apparaissent dans le tableau D. Teneur (ppm) des bains de phosphatation dans les bains V W Constituants du bain de phosphatation Zn 1025 1025 PO4 10550 10550 Ni 210 210 Mn 730 730 F 1000 935 Fe 20 20 NO3 2163 2163 SO4 35 35 Al 1,2 1 accélérateur 1 100 - accélérateur 11 - 100 substrat acier acier poids de couche (g/m2) 2,1 1,6 Test 3C 3 mm 2,5 mm The composition of the baths and the performances recorded appear in Table D. Content (ppm) of phosphating baths in baths V W Constituents of the phosphating bath Zn 1025 1025 PO 4 10550 10550 Or 210 210 Mn 730 730 F 1000 935 Fe 20 20 NO 3 2163 2163 SO 4 35 35 Al 1.2 1 accelerator 1 100 - accelerator 11 - 100 substrate steel steel layer weight (g / m 2 ) 2.1 1.6 3C test 3 mm 2.5mm

De l'examen des données réunies dans le tableau D, il apparaít que l'utilisation des complexes de Cobalt III comme accélérateurs permet d'obtenir d'une manière comparable à une phosphatation classique accélérée avec du nitrite, une couche de phosphatation fine et homogène qui offre une excellente résistance à la corrosion.From the examination of the data gathered in table D, it appears that the use of Cobalt III complexes as accelerators provides a comparable way to conventional accelerated phosphating with nitrite, a thin and homogeneous layer of phosphating which offers excellent resistance to corrosion.

EXEMPLE 4EXAMPLE 4

Dans cet exemple, on a comparé la stabilité dans le temps du bain conforme à l'invention à celle d'un bain comportant l'accélérateur classique constitué par le nitrite de Na. In this example, we compared the stability in the bath time according to the invention to that of a bath comprising the conventional accelerator constituted by the Na nitrite.

Dans cet ordre d'idées, on a examiné le bain selon l'essai E (exemple 1) après une semaine de vieillissement.In this connection, we examined the bath according to test E (example 1) after one week of aging.

Par dosage, on a déterminé qu'il contient toujours environ 90% du complexe de cobalt III.By assay, it was determined that it still contains about 90% of the cobalt III complex.

Par ailleurs, une expérience de phosphatation réalisée avec ce bain fournit des plaques qui sont phosphatées de manière significativement comparable à celles traitées avec ce bain au moment de sa constitution.In addition, a phosphating experience made with this bath provides plates which are phosphates significantly comparable to those treated with this bath at the time of its constitution.

A titre de comparaison, on a examiné le bain selon l'essai P (exemple 1).For comparison, the bath was examined according to test P (example 1).

Par dosage, on a déterminé que ce bain ne contient plus d'accélérateur après 4 heures de vieillissement; par ailleurs, une plaque traitée par ce bain après ce vieillissement n'est pas phosphatée.By assay, it was determined that this bath does not contain more accelerator after 4 hours of aging; through elsewhere, a plate treated by this bath after this aging is not phosphated.

Claims (9)

  1. Phosphatization bath for metallic substrates based on steel possibly coated with zinc or with alloys of zinc with other metals like iron, nickel, aluminum, manganese, or still based on aluminum or aluminum alloys, whose pH is from 1 to 5.5 and in the constitution of which the classical components of the phosphatization baths go into, said bath being characterized by the fact that it comprises
    from 0.3 to 25 g/l of zinc ion,
    from 5 to 50 g/l of phosphate ion and
    from 0.01 to 10 g/l of a trivalent cobalt complex represented by one or another of the formulae: [Co(Ligand)n]c [Co(Ligand)nZp]c in which
    n and p are integers from 1 to 6 with the proviso that, in case of formula (II), n+p ≤ 6,
    c represents the charge of the complex and can consequently be positive or negative according to the charge of the Ligand and of Z,
    the Ligand is selected among the ions of the group comprising NO2, CN, CO3 and SO3, among the ions of the group comprising oxalate ions, acetate ions, citrate ions, gluconate ions, tartrate ions et acetylacetonate ions, and among the compounds of formula N(R1, R2, R3) wherein R1, R2 and R3 are selected, independently from one another, in the group comprising H, the carbonated groups in C1 to C6 among which especially alkyl, hydroxyalkyl, hydroxy, alkylamine, hydroxyalkylamine groups as well as carboxylic or aminocarboxylic acids and their salts, and
    Z is selected in the group comprising Cl, Br, F, I, OH, NO3, SCN, PO4, SO4, S2O3, MoO4, SeO4 and H2O,
    it being understood that the given complex can comprise one or several Ligands and one or several Z, different from each other.
  2. Phosphatization bath according to claim 1, characterized by the fact that it comprises from 0.5 to 10 g of zinc ion.
  3. Phosphatization bath according to claim 2, characterized by the fact that it comprises from 8 to 30 g of phosphate ion.
  4. Phosphatization bath according to claim 2, characterized by the fact that it comprises from 0.03 to 3 g of a trivalent cobalt complex represented by one or another of the formulae (I) and (II).
  5. Phosphatization bath according to one of claims 1 to 4, characterized by the fact that the trivalent cobalt complex is selected from the group comprising:
       [Co(NH3)6]Cl3
       [Co(NO2)6]Na3
       [Co(en)3](NO3)3 with en = ethylenediamine
       [Co(pn)3]NO3)3 with pn = diamino 1-2 propane
       [Co(oxalate)en2]NO3
       [Co(citrate)(CO3)]Na2
       [CoF(NH3)5](NO3)2
       [Co(NO3)(NH3)5](NO3)2.
  6. Process for the phosphatization of metallic substrates based on steel possibly coated with zinc or with alloys of zinc with other metals like iron, nickel, aluminum, manganese, or still based on aluminum or aluminum alloys, comprising the successive stages of classical phosphatization processes, among which especially:
    a degreasing step,
    a rinsing step,
    the phosphatization step proper,
    a rinsing step and
    a drying step,
    characterized by the fact that, during the phosphatization step proper, the phosphatization bath according to one of claims 1 to 5 is used.
  7. Concentrate adapted to provide, by dilution from 1% to 10% with water, the phosphatization bath according to one of claims 1 to 5.
  8. Use as accelerator in the phosphatization baths for metallic substrates based on steel possibly coated with zinc or with alloys of zinc with other metals like iron, nickel, aluminum, manganese, or still based on aluminum or aluminum alloys, of a trivalent cobalt complex represented by one or another of the formulae: [CO(Ligand)n]c [Co(Ligand)nZp]c in which
    n and p are integers from 1 to 6 with the proviso that, in case of formula (II), n+p ≤ 6,
    c represents the charge of the complex and can consequently be positive or negative according to the charge of the Ligand and of Z,
    the Ligand is selected among the ions of the group comprising NO2, CN, CO3 and SO3, among the ions of the group comprising oxalate ions, acetate ions, citrate ions, gluconate ions, tartrate ions et acetylacetonate ions, and among the compounds of formula N(R1, R2, R3) wherein R1, R2 and R3 are selected, independently from one another, in the group comprising H, the carbonated groups in C1 to C6 among which especially alkyl, hydroxyalkyl, hydroxy, alkylamine, hydroxyalkylamine groups as well as carboxylic or aminocarboxylic acids and their salts, and
    Z is selected in the group comprising Cl, Br, F, I, OH, NO3, SCN, PO4, SO4, S2O3, MoO4, SeO4 and H2O,
    it being understood that the given complex can comprise one or several Ligands and one or several Z, different from each other.
  9. Use as accelerator in the phosphatization baths for metallic substrates based on steel possibly coated with zinc or with alloys of zinc with other metals like iron, nickel, aluminum, manganese, or still based on aluminum or aluminum alloys, of a trivalent cobalt complex selected from the group comprising:
       [Co(NH3)6]Cl3
       [Co(NO2)6]Na3
       [Co(en)3](NO3)3 with en = ethylenediamine
       [Co(pn)3]NO3)3 with pn = diamino 1-2 propane
       [Co(oxalate)en2]NO3
       [Co(citrate)(CO3)]Na2
       [CoF(NH3)5](NO3)2
       [Co(NO3)(NH3)5](NO3)2.
EP97402032A 1996-09-02 1997-09-01 Bath and process for phosphating metal substrates, concentrates for preparing the bath and metal substrates treated according to the process Expired - Lifetime EP0826792B1 (en)

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FR9610684A FR2752851B1 (en) 1996-09-02 1996-09-02 BATH AND METHOD FOR PHOSPHATION OF METAL SUBSTRATES, CONCENTRATE FOR THE PREPARATION OF THIS BATH AND METAL SUBSTRATES TREATED WITH THE BATH AND METHOD
FR9610684 1996-09-02

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US8062435B2 (en) * 2001-06-18 2011-11-22 Henkel Kommanditgesellschaft Auf Aktien Phosphating operation
US7294211B2 (en) * 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
US7235142B2 (en) * 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
WO2003060019A1 (en) * 2002-01-04 2003-07-24 University Of Dayton Non-toxic corrosion protection pigments based on cobalt
US6818313B2 (en) * 2002-07-24 2004-11-16 University Of Dayton Corrosion-inhibiting coating
US20040011252A1 (en) * 2003-01-13 2004-01-22 Sturgill Jeffrey A. Non-toxic corrosion-protection pigments based on manganese
CN100443632C (en) * 2006-11-20 2008-12-17 中国重型汽车集团有限公司 Low-temperature zinc-based phosphatization liquid

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GB599728A (en) * 1944-10-09 1948-03-19 Sunil Coomar Mukhopadhyay Shar Improvements in or relating to processes for increasing the resistance of metals to corrosion
GB599784A (en) * 1946-05-13 1948-03-19 Royston Fraser Drysdale Improvements in or relating to processes for the production of protective coatings on metal surfaces
US3420715A (en) * 1965-06-04 1969-01-07 Cons Foods Corp Additive for phosphate coating solution
US4540494A (en) * 1983-03-10 1985-09-10 Veb Leuna Werke "Walter Ulbricht" Method for the removal of oxygen dissolved in water
US4722753A (en) * 1985-05-16 1988-02-02 Parker Chemical Company Alkaline resistant phosphate conversion coatings
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
US5298092A (en) * 1990-05-17 1994-03-29 The Boeing Company Non-chromated oxide coating for aluminum substrates
EP0488430B1 (en) * 1990-11-30 1997-06-11 The Boeing Company Non-chromated cobalt conversion coating
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