EP0180523A1 - Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor - Google Patents

Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor Download PDF

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Publication number
EP0180523A1
EP0180523A1 EP85402096A EP85402096A EP0180523A1 EP 0180523 A1 EP0180523 A1 EP 0180523A1 EP 85402096 A EP85402096 A EP 85402096A EP 85402096 A EP85402096 A EP 85402096A EP 0180523 A1 EP0180523 A1 EP 0180523A1
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Prior art keywords
acid
bath
activation
ppm
refining
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EP85402096A
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German (de)
French (fr)
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EP0180523B1 (en
Inventor
Joseph Schapira
Victor Ken
Denis Thery
Stéphane Jelodin
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CFPI S.A.
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Compagnie Francaise de Produits Industriels SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • step (3) can be omitted, the activating constituents then being introduced directly into the bath used for the step of alkaline degreasing.
  • step (3) becomes essential in order to obtain a sufficiently fine and dense phosphating.
  • the baths intended for carrying out the zinc phosphating step can comprise, in addition to the zinc cation, other metals such as nickel, manganese, calcium or possibly iron, as widely described in the scientific literature.
  • the refining agents used at the time of the activation and refining step or which can be used at the time of the alkaline degreasing step in the case of processes carried out entirely by jet are constituted by compounds of titanium, in particular colloidal titanium salts known under the name of Jernstedt salts; these salts are described in particular in US Patent 2,456,947.
  • Such a Jernstedt salt can be obtained by mixing 95 parts of disodium phosphate with 5 parts of potassium fluotitanate in an amount of water sufficient to dissolve the ingredients. The water is then removed from the mixture by evaporation at a temperature of 80 to 100 ° C.
  • titanium can be used for the production of Jernstedt salt, such as for example titanium sulfate or titanium oxide.
  • polyphosphates containing Jernstedt salts in particular in a proportion of 1 to 300 parts by weight of P207.
  • Jernstedt salts are commonly found on the market and are in particular marketed by the Applicant Company under the trademark "FIXODINE 5".
  • the object of the invention is, above all, to remedy these drawbacks and to ensure that, in the phosphating methods of the genus in question, the activation and refining step can be carried out with industrial water without overflow and supply of refining salts proportional to the quantities of water added while providing a refining and stability effect comparable to that obtained with demineralized water.
  • R representing an alkyl radical or an aryl radical optionally substituted with at least one of the substituents of the group comprising the hydroxyl radical, other phosphonic groups and the amino groups of formula in which R 2 and R 3 which may be identical or different from each other, each represent a hydrogen atom or have the meaning of R 1 .
  • the salts of these acids which can be used are those obtained by partial or total neutralization with alkaline ions such as Na and K or with the NH 4 ion.
  • a bath which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably of 50 to 200 ppm, of at least one alkane-phosphonic acid of formula (I) or one of its salts, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.
  • This bath is also targeted as a new industrial product.
  • constituents of the refining bath used in accordance with the invention may be pyrophosphates or alkali citrates.
  • the activation and refining step according to the invention is carried out at a temperature of 20 to 50 ° C.
  • the stability of the bath used is sufficient for it to be able to operate under normal conditions without regeneration, that is to say without the addition of additional amounts of concentrate other than the normal amounts to be provided by consumption of the product, for approximately 5 15 days.
  • the aim is to study the influence of different activation baths on the morphology of the zinc phosphate crystals deposited in the phosphating step.
  • This morphology is examined using an electronic scanning micro-scape at a magnification of 1500.
  • Two examinations are carried out, the first of which is carried out after treatment in a new bath, 10 minutes after its assembly, and the second of which is carried out after treatment in the same bath, 6 days after the assembly thereof.
  • the activation bath comprises 2 g / l of Jermstedt salt (FIXODINE 5) in demineralized water corresponding to 20 ppm of titanium.
  • FIXODINE 5 Jermstedt salt
  • the other ingredients are sodium phosphates.
  • the pH is 7.
  • Example 2 Same composition and same pH as in Example 1, but the water consists of tap water.
  • the pH 7.9.
  • the bath is identical to that of Example 3, except that the phosphonic acid is present at the rate of 100 ppm.
  • the bath is identical to that of Example 4, but the pH is brought to 9 with trisodium phosphate.
  • the bath is identical to that of Example 6 except that the sodium salt of phosphonic acid is present at the rate of 200 ppm.
  • the bath is identical to that of Example 7, except that the phosphonic acid is present at the rate of 100 ppm and the pH is then 7.
  • test pieces thus treated are examined under the electron microscope, as indicated above.

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  • 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)
  • Detergent Compositions (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Procédé de phosphatation au zinc de substrats essentiellement à base de fer, de zinc ou de leurs alliages, comprenent successivement: 1) une ou plusieurs étapes de dégraissage alcalin, 2) une ou plusieurs étapes de rinçage à l'eau de ville courante, 3) une étape d'activation et d'affinage, 4) une étape de phosphatation au zinc proprement dite, 5) une ou plusieurs étapes de rinçage à l'eau, 6) de préférence, une étape de rinçage final passivant, notamment à l'aide de sels de chrome hexavalent ou de mélanges de chrome hexavalent et de chrome trivalent, caractérisé par le fait que, pour la mise en oeuvre de l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, au moins un acide alcane-phosphonique de formule: <IMAGE> ou d'au moins l'un des sels alcalins ou d'ammonium correspondant aux susdits acides alcane-phosphoniques, le pH du bain étant de 7 à 9,5, de préférence de 7,5 à 9.Process for the phosphating with zinc of substrates essentially based on iron, zinc or their alloys, successively comprise: 1) one or more stages of alkaline degreasing, 2) one or more stages of rinsing with running tap water, 3 ) an activation and refining step, 4) a zinc phosphating step proper, 5) one or more rinsing steps with water, 6) preferably, a passivating final rinsing step, in particular with using hexavalent chromium salts or mixtures of hexavalent chromium and trivalent chromium, characterized in that, for the implementation of the activation and refining step, a bath is used which comprises, in addition to the conventional constituents, in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably from 50 to 200 ppm, at least one alkane-phosphonic acid of formula : <IMAGE> or at least one of the alkali or ammonium salts corresponding to the above alkane-phosphonic acids, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.

Description

L'invention a pour objet un procédé perfectionné de phosphatation au zinc du genre de ceux qui comprennent :

  • 1) une ou plusieurs étapes de dégraissage alcalin,
  • 2) une ou plusieurs étapes de rinçage à l'eau de ville courante,
  • 3) une étape d'activation et d'affinage,
  • 4) une étape de phosphatation au zinc proprement dite,
  • 5) une ou plusieurs étapes de rinçage à l'eau,
  • 6) de préférence, une étape de rinçage final passivant, notamment à l'aide de sels de chrome hexavalent ou de mélanges de chrome hexavalent et de chrome trivalent

et qui sont applicables aux surfaces d'objets essentiellement à base de fer, de zinc ou de leurs alliages.The subject of the invention is an improved process for zinc phosphating of the kind which comprises:
  • 1) one or more alkaline degreasing steps,
  • 2) one or more stages of rinsing with running tap water,
  • 3) an activation and refining step,
  • 4) a zinc phosphating step proper,
  • 5) one or more stages of rinsing with water,
  • 6) preferably a passivating final rinsing step, in particular using hexavalent chromium salts or mixtures of hexavalent chromium and trivalent chromium

and which are applicable to the surfaces of objects essentially based on iron, zinc or their alloys.

Elle vise également, et ce à titre de produits industriels nouveaux, le bain d'activation et d'affinage mis en oeuvre dans le cadre de ce procédé et le concentré à partir duquel est obtenu ce bain.It also relates, and this as new industrial products, the activation and refining bath used in the context of this process and the concentrate from which this bath is obtained.

On rappelle que les procédés du genre en question ont pour but de conférer à des surfaces, notamment d'acier, une bonne résistance à la corrosion, notamment après l'application de peintures dont l'adhérence se trouve favorisée.It is recalled that the processes of the kind in question are intended to impart to surfaces, in particular steel, good resistance to corrosion, in particular after the application of paints whose adhesion is favored.

Ces procédés de phosphatation au zinc conduisent à la formation sur les surfaces métalliques en question d'un revêtement cristallin ; ce revêtement cristallin doit être le plus fin et le plus dense possible pour conduire à la meilleure adhérence possible des couches de peinture ultérieures, notamment dans le cas des peintures du type élec- trophorétique.These zinc phosphating processes lead to the formation on the metal surfaces in question of a crystalline coating; this crystalline coating must be as thin and as dense as possible to lead to the best possible adhesion of the subsequent paint layers, in particular in the case of paints of the electrophoretic type.

Les étapes notamment d'activation et de phosphatation proprement dite sont effectuées à l'aide des bains appropriés soit par aspersion, soit par immersion, soit à la fois par aspersion et immersion.The steps in particular of activation and of phosphating proper are carried out using appropriate baths either by spraying, or by immersion, or both by spraying and immersion.

Dans le cas des procédés du genre en question effectués totalement au jet, c'est-à-dire par aspersion, l'étape (3) peut être omise, les constituants activants étant alors introduits directement dans le bain utilisé pour l'étape de dégraissage alcalin.In the case of processes of the kind in question carried out entirely by jet, that is to say by spraying, step (3) can be omitted, the activating constituents then being introduced directly into the bath used for the step of alkaline degreasing.

Par contre, dans le cas des procédés du genre en question qui, de préférence, mettent en oeuvre une immersion totale ou des opérations aspersion/immersion, ce qui est envisagé ici, le maintien de l'étape (3) devient indispensable pour obtenir une phosphatation suffisamment fine et dense.On the other hand, in the case of the processes of the type in question which, preferably, employ total immersion or spraying / immersion operations, which is envisaged here, the maintenance of step (3) becomes essential in order to obtain a sufficiently fine and dense phosphating.

Les bains destinés à la mise en oeuvre de l'étape de phosphatation au zinc peuvent comporter, outre le cation zinc, d'autres métaux comme le nickel, le manganèse, le calcium ou éventuellement le fer, comme largement décrit dans la littérature scientifique.The baths intended for carrying out the zinc phosphating step can comprise, in addition to the zinc cation, other metals such as nickel, manganese, calcium or possibly iron, as widely described in the scientific literature.

Les agents affineurs mis en oeuvre au moment de l'étape d'activation et d'affinage ou qui peuvent être mis en oeuvre au moment de l'étape de dégraissage alcalin dans le cas des procédés effectués totalement au jet sont constitués par des composés de titane, notamment des sels de titane colloidaux connus sous l'appellation de sels de Jernstedt ; ces sels sont décrits notamment dans le brevet US 2.456.947.The refining agents used at the time of the activation and refining step or which can be used at the time of the alkaline degreasing step in the case of processes carried out entirely by jet are constituted by compounds of titanium, in particular colloidal titanium salts known under the name of Jernstedt salts; these salts are described in particular in US Patent 2,456,947.

Un tel sel de Jernstedt peut être obtenu en mélangeant 95 parties de phosphate disodique avec 5 parties de fluotitanate de potassium dans une quantité d'eau suffisante pour dissoudre les ingrédients. L'eau est ensuite chassée du mélange par évaporation à une température de 80 à 100°C.Such a Jernstedt salt can be obtained by mixing 95 parts of disodium phosphate with 5 parts of potassium fluotitanate in an amount of water sufficient to dissolve the ingredients. The water is then removed from the mixture by evaporation at a temperature of 80 to 100 ° C.

D'autres sources de titane peuvent être utilisées pour la fabrication du sel de Jernstedt, comme par exemple le sulfate de titane ou l'oxyde de titane.Other sources of titanium can be used for the production of Jernstedt salt, such as for example titanium sulfate or titanium oxide.

On peut également aouter des polyphosphates aux sels de Jernstedt, notamment en une proportion de 1 à 300 parties en poids de P207.It is also possible to add polyphosphates containing Jernstedt salts, in particular in a proportion of 1 to 300 parts by weight of P207.

Les sels de Jernstedt se trouvent couramment sur le marché et sont en particulier commercialisés par la Société Demanderesse sous la marque de fabrique "FIXODINE 5".Jernstedt salts are commonly found on the market and are in particular marketed by the Applicant Company under the trademark "FIXODINE 5".

Etant donné la sensibilité des sels de Jernstedt à la dureté de l'eau utilisée pour monter le bain d'affinage, on a jusqu'à ce jour, dans les procédés du genre en question, utilisé soit de l'eau déminéralisée pour monter les bains d'activation, soit dans le cas d'utilisation d'eau industrielle fait fonctionner le bain par débordement avec apport de sels affineurs proportionnel aux quantités d'eau ajoutées.Given the sensitivity of the Jernstedt salts to the hardness of the water used to mount the refining bath, it has hitherto been used in processes of the kind in question, either demineralized water to mount the activation baths, that is to say in the case of the use of industrial water, operates the bath by overflow with the addition of refining salts proportional to the quantities of water added.

Une telle façon de procéder est coûteuse en eau et en produit actif, notamment lorsque le procédé de phosphatation est appliqué au traitement d'objets de grande surface par immersion tels que rencontrés dans l'industrie automobile pour les carrosseries, les bains de traitement étant alors très volumineux et pouvant atteindre couramment des volumes de 100 à 200 m .Such a procedure is costly in water and in active product, in particular when the phosphating process is applied to the treatment of large surface objects by immersion such as encountered in the automobile industry for bodywork, the treatment baths then being very bulky and can commonly reach volumes of 100 to 200 m.

L'invention a pour but, surtout, de remédier à ces inconvénients et de faire en sorte que, dans les procédés de phosphatation du genre en question, l'étape d'activation et d'affinage puisse être mise en oeuvre avec de l'eau industrielle sans débordement et apport de sels affineurs proportionnel aux quantités d'eau ajoutées tout en fournissant un effet d'affinage et de stabilité comparable à celui obtenu avec de l'eau déminéralisée.The object of the invention is, above all, to remedy these drawbacks and to ensure that, in the phosphating methods of the genus in question, the activation and refining step can be carried out with industrial water without overflow and supply of refining salts proportional to the quantities of water added while providing a refining and stability effect comparable to that obtained with demineralized water.

Or, la Société Demanderesse a trouvé que ce but pouvait être atteint par l'addition aux bains d'affinage et d'activation des procédés du genre en question d'une quantité efficace d'au moins un acide alcane phosphonique de formule (I) définie ci-dessous ou d'un sel correspondant.However, the Applicant Company has found that this object could be achieved by adding to the refining and activation baths of the processes of the type in question an effective amount of at least one alkane phosphonic acid of formula (I) defined below or a corresponding salt.

La susdite formule I, à laquelle répond l'acide alcane-phosphonique mis en oeuvre conformément à l'invention, est comme suit :

Figure imgb0001
avec R représentant un radical alcoyle ou un radical aryle éventuellement substitué par au moins l'un des substituants du groupe comprenant le radical hydroxyle, d'autres groupements phosphoniques et les groupements amino de formule
Figure imgb0002
dans laquelle R2 et R3 qui peuvent être identiques ou différents l'un de l'autre, représentent chacun un atome d'hydrogène ou ont la signification de R1.The above-mentioned formula I, to which the alkane-phosphonic acid used in accordance with the invention corresponds, is as follows:
Figure imgb0001
 with R representing an alkyl radical or an aryl radical optionally substituted with at least one of the substituents of the group comprising the hydroxyl radical, other phosphonic groups and the amino groups of formula
Figure imgb0002
 in which R 2 and R 3 which may be identical or different from each other, each represent a hydrogen atom or have the meaning of R 1 .

Les sels de ces acides qui sont utilisables sont ceux obtenus par neutralisation partielle ou totale par des ions alcalins tels que Na et K ou par l'ion NH4 .The salts of these acids which can be used are those obtained by partial or total neutralization with alkaline ions such as Na and K or with the NH 4 ion.

A titre d'exemple d'un tel sel, on indique celui de la formule (Ia) ci-après :

Figure imgb0003
By way of example of such a salt, that of the formula (Ia) below is indicated:
Figure imgb0003

Parmi les acides alcane-phosphoniques de formule (I), on préfère plus particulièrement ceux du groupe comprenant :

  • - l'acide hydroxyméthylphosphonique
  • - l'acide hydroxypropylphosphonique
  • - l'acide octylphosphonique
  • - l'acide éthyl- et l'acide butylphosphonique
  • - l'acide 1-hydroxyéthylidène-1.1-diphosphonique
  • - l'acide amino-tri(méthylènephosphonique)
  • - l'acide éthylène-diamine-tétra(méthylènephospho- nique) et
  • - l'acide 2-phosphono-butane-1,2,4-tricarboxylique.
Among the alkane-phosphonic acids of formula (I), more particularly preferred are those of the group comprising:
  • - hydroxymethylphosphonic acid
  • - hydroxypropylphosphonic acid
  • - octylphosphonic acid
  • - ethyl acid and butylphosphonic acid
  • - 1-hydroxyethylidene-1.1-diphosphonic acid
  • - amino-tri acid (methylenephosphonic)
  • - ethylene-diamine-tetra (methylenephosphonic) acid and
  • - 2-phosphono-butane-1,2,4-tricarboxylic acid.

Il s'ensuit que le procédé conforme à l'invention est caractérisé par le fait que, pour l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, d'au moins un acide alcane- phosphonique de formule (I) ou d'un de ses sels, le pH du bain étant de 7 à 9,5, de préférence de 7,5 à 9.It follows that the method according to the invention is characterized in that, for the activation step and refining, a bath is used which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably of 50 to 200 ppm, of at least one alkane-phosphonic acid of formula (I) or one of its salts, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9.

Ce bain est visé, par ailleurs, à titre de produit industriel nouveau.This bath is also targeted as a new industrial product.

Pour régler le pH à la valeur recherchée, on peut avoir recours à des proportions appropriées de tartrates, phosphates, polyphosphates et carbonates alcalins.To adjust the pH to the desired value, use may be made of appropriate proportions of tartrates, phosphates, polyphosphates and alkali carbonates.

D'autres constituants du bain d'affinage mis en oeuvre conformément à l'invention peuvent être des pyrophosphates ou des citrates alcalins.Other constituents of the refining bath used in accordance with the invention may be pyrophosphates or alkali citrates.

Des bains d'affinage dont la mise en oeuvre est particulièrement avantageuse sont ceux dont la composition est indiquée ci-après :Refining baths whose implementation is particularly advantageous are those whose composition is indicated below:

Bain A :Bath A:

  • - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
  • - 60 ppm du sel de sodium de l'acide aminotri-(méthylène-phosphonique)- 60 ppm of the sodium salt of aminotri- (methylene-phosphonic acid)
  • - eau q.s.- water q.s.
Bain B :Bath B:

  • - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
  • - 200 ppm du sel de sodium de l'acide phosphonique- 200 ppm of the sodium salt of phosphonic acid
  • - eau q.s.- water q.s.
Bain C :Bath C:

  • - 2 g/1 de sel de Jernstedt (FIXODINE 5)- 2 g / 1 Jernstedt salt (FIXODINE 5)
  • - 50 ppm d'acide 1-hydroxyéthylidène-1,1-diphospho- nique,- 50 ppm of 1-hydroxyethylidene-1,1-diphosphonic acid,
  • - eau q.s.- water q.s.

Pour préparer ces bains, on introduit successivement dans la quantité d'eau appropriée le sel de Jernstedt et l'acide phosphonique.To prepare these baths, successively introduce the appropriate amount of Jernstedt salt and phosphonic acid.

Plus généralement et notamment dans la pratique, on prépare ces bains à partir de concentrés contenant l'acide de formule (I) ou son sel et le sel de Jernstedt en des proportions telles que son mélange avec une quantité appropriée d'eau fournit le bain d'activation et d'affinage mise en oeuvre conformément à l'invention.More generally and in particular in practice, we prepare these baths from concentrates containing the acid of formula (I) or its salt and Jernstedt salt in proportions such that mixing it with an appropriate amount of water provides the activation and refining bath works in accordance with the invention.

Avantageusement, le concentré en question se présente sous forme de deux récipients séparés contenant respectivement, d'une part, le sel de Jernstedt et, d'autre part, une solution aqueuse de l'acide phosphonique de formule (I) ou de son sel, ces deux récipients pouvant être réunis de préférence sous la forme de ce qu'on appelle généralement un "kit" de traitement ; ce concentré peut également se présenter sous forme d'une poudre comprenant:

  • - de 1 à 5 2 en poids de titane exprimé en titane (IV) sous forme de phosphate de titane
  • - de 2,5 à 10 2 en poids d'acide phosphonique de formule (I)
  • - de 89 à 92,5 X en poids de phosphate de sodium et de potassium.
Advantageously, the concentrate in question is in the form of two separate containers containing respectively, on the one hand, Jernstedt salt and, on the other hand, an aqueous solution of the phosphonic acid of formula (I) or its salt , these two containers being able to be combined preferably in the form of what is generally called a "kit" for treatment; this concentrate can also be in the form of a powder comprising:
  • - from 1 to 5 2 by weight of titanium expressed as titanium (IV) in the form of titanium phosphate
  • - from 2.5 to 10 2 by weight of phosphonic acid of formula (I)
  • - from 89 to 92.5 X by weight of sodium and potassium phosphate.

Un exemple avantageux dudit concentré conforme à l'invention est celui de formule :

  • - titane exprimé en titane (IV) sous forme de phosphate de titane ...... 2 % en poids
  • - phosphate trisodique ............. 93 % en poids
  • - acide 1-hydroxyéthylidène-1,1- diphosphonique ................... 5 % en poids.
An advantageous example of said concentrate according to the invention is that of formula:
  • - titanium expressed as titanium (IV) in the form of titanium phosphate ...... 2% by weight
  • - trisodium phosphate ............. 93% by weight
  • - 1-hydroxyethylidene-1,1-diphosphonic acid ................... 5% by weight.

L'étape d'activation et d'affinage conforme à l'invention est effectuée à une température de 20 à 50°C.The activation and refining step according to the invention is carried out at a temperature of 20 to 50 ° C.

La stabilité du bain mis en oeuvre est suffisante pour qu'il puisse fonctionner en régime normal sans régénération, c'est-à-dire sans apport de quantités supplémentaires de concentré autres que les quantités normales à apporter par consommation du produit, pendant environ 5 à 15 jours.The stability of the bath used is sufficient for it to be able to operate under normal conditions without regeneration, that is to say without the addition of additional amounts of concentrate other than the normal amounts to be provided by consumption of the product, for approximately 5 15 days.

Les autres étapes du procédé de phosphatation au zinc conforme à l'invention, sont effectuées de manière conventionnelle.The other steps of the zinc phosphating process according to the invention are carried out in a conventional manner.

On en trouve la description détaillée notamment dans la demande de brevet français N* 80 03185.The detailed description is found in particular in French patent application N * 80 03185.

L'invention pourra être encore mieux comprise à l'aide des exemples décrits ci-après et dont les deux premiers sont des exemples comparatifs faisant ressortir les avantages inhérents à l'invention par rapport à l'état antérieur de la technique.The invention can be understood even better with the aid of the examples described below and the first two of which are comparative examples highlighting the advantages inherent in the invention compared with the prior art.

Dans ces exemples, seule l'étape d'activation et d'affinage est décrite, les autres étapes étant toujours les mêmes, la succession d'étapes étant la suivante :

  • - étape de dégraissage alcalin par immersion dans un bain aqueux comportant une composition à base de sels alcalins, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "RIDOLINE 1501" à 1,5 / en poids/volume ainsi qu'une composition tensioactive, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "RIDOSOL 502 R" à 0,15 % en volume, la température étant de 60°C et la durée de 5 minutes ;
  • - étape de rinçage à l'eau de ville courante à température ambiante ;
  • - étape d'affinage conforme à l'invention par immersion pendant 1 minute à la température ambiante ;
  • - étape de phosphatation au zinc à l'aide d'un bain aqueux comportant une composition à base de phosphates acides de zinc, à savoir celle commercialisée par la Société Demanderesse sous la marque de fabrique "GRANODINE 908". en procédant par immersion, pendant 3 minutes, à 55°C ;
  • - une étape de rinçage à l'eau de ville courante,
  • - une étape de séchage pendant 5 minutes sous courant d'air chaud à 80°C.
In these examples, only the activation and refining step is described, the other steps being always the same, the succession of steps being as follows:
  • - alkaline degreasing step by immersion in an aqueous bath comprising a composition based on alkaline salts, namely that marketed by the Applicant Company under the trademark "RIDOLINE 1501" at 1.5 / by weight / volume as well as a surfactant composition, namely that marketed by the Applicant Company under the trademark "RIDOSOL 502 R" at 0.15% by volume, the temperature being 60 ° C and the duration of 5 minutes;
  • - rinsing step with running tap water at room temperature;
  • - refining step according to the invention by immersion for 1 minute at room temperature;
  • - Zinc phosphating step using an aqueous bath comprising a composition based on zinc acid phosphates, namely that marketed by the Applicant Company under the trademark "GRANODINE 908". by immersion, for 3 minutes, at 55 ° C;
  • - a rinsing step with running tap water,
  • - a drying step for 5 minutes under a stream of hot air at 80 ° C.

On s'attache à étudier dans ces exemples l'influence de différents bains d'activation sur la morphologie des cristaux de phosphate de zinc déposés dans l'étape de phosphatation.In these examples, the aim is to study the influence of different activation baths on the morphology of the zinc phosphate crystals deposited in the phosphating step.

Cette morphologie est examinée à l'aide d'un micro- scape électronique à balayage à un grossissement de 1500.This morphology is examined using an electronic scanning micro-scape at a magnification of 1500.

On pratique deux examens dont le premier est effectué après traitement dans un bain neuf, 10 minutes après ses montage, et dont le deuxième est effectué après trai- tellement dans le même bain, 6 jours après le montage de celui-ci.Two examinations are carried out, the first of which is carried out after treatment in a new bath, 10 minutes after its assembly, and the second of which is carried out after treatment in the same bath, 6 days after the assembly thereof.

EXEMPLE 1 (Comparatif)EXAMPLE 1 (Comparative)

Le bain d'activation comprend 2 g/l de sel de Jermstedt (FIXODINE 5) en eau déminéralisée correspondant à 20 ppm de titane.The activation bath comprises 2 g / l of Jermstedt salt (FIXODINE 5) in demineralized water corresponding to 20 ppm of titanium.

Les autres constituants sont des phosphates de sodium.The other ingredients are sodium phosphates.

Le pH est de 7.The pH is 7.

EXEMPLE 2 (Comparatif)EXAMPLE 2 (Comparative)

Même composition et même pH que dans l'exemple 1 mais l'eau est constituée par de l'eau du robinet.Same composition and same pH as in Example 1, but the water consists of tap water.

Le pH est de 7,9.The pH is 7.9.

EXEMPLE 3EXAMPLE 3

Le bain d'activation comprend, dans de l'eau du robinet :

  • - 2 g/1 de sel de Jernstedt (FIXODINE 5)
  • - 50 ppm d'acide 1-hydroxyéthylidène-1,1-diphospho- nique,
The activation bath includes, in tap water:
  • - 2 g / 1 Jernstedt salt (FIXODINE 5)
  • - 50 ppm of 1-hydroxyethylidene-1,1-diphosphonic acid,

le pH résutant étant de 7,8.the resulting pH being 7.8.

EXEMPLE 4EXAMPLE 4

Le bain est identique à celui de l'exemple 3, à la différence près que l'acide phosphonique est présent à raison de 100 ppm.The bath is identical to that of Example 3, except that the phosphonic acid is present at the rate of 100 ppm.

EXEMPLE 5EXAMPLE 5

Le bain est identique à celui de l'exemple 4, mais le pH est amené à 9 avec du phosphate trisodique.The bath is identical to that of Example 4, but the pH is brought to 9 with trisodium phosphate.

EXEMPLE 6EXAMPLE 6

Le bain d'activation comprend, dans de l'eau du robinet :

  • - 2 g/l de sel de Jernstedt (FIXODINE 5)
  • - 60 ppm du sel de sodium de l'acide aminotri(méthylène-phosphonique),
The activation bath includes, in tap water:
  • - 2 g / l Jernstedt salt (FIXODINE 5)
  • - 60 ppm of the sodium salt of aminotri acid (methylene-phosphonic),

le pH étant de 8.the pH being 8.

EXEMPLE 7EXAMPLE 7

Le bain est identique à celui de l'exemple 6 à la différence près que le sel de sodium de l'acide phosphonique est présent à raison de 200 ppm.The bath is identical to that of Example 6 except that the sodium salt of phosphonic acid is present at the rate of 200 ppm.

EXEMPLE 8EXAMPLE 8

Le bain est identique à celui de l'exemple 7, à la différence près que l'acide phosphonique est présent à raison de 100 ppm et le pH est alors de 7.The bath is identical to that of Example 7, except that the phosphonic acid is present at the rate of 100 ppm and the pH is then 7.

EXEMPLE 9EXAMPLE 9

Le bain d'activation comprend, dans de l'eau du robinet :

  • - 2 g/1 de sel de Jernstedt (FIXODINE 5)
  • - 600 ppm d'acide 2-phosphono-butane-1,2,4-tricar- boxylique,
The activation bath includes, in tap water:
  • - 2 g / 1 Jernstedt salt (FIXODINE 5)
  • - 600 ppm of 2-phosphono-butane-1,2,4-tricarboxylic acid,

le pH étant réglé à 9 avec du phosphate trisodique.the pH being adjusted to 9 with trisodium phosphate.

Dans tous les exemples, on traite deux éprouvettes en acier qualité automobile d'une dimension de 25 x 20 cm.In all the examples, two automotive quality steel specimens with a dimension of 25 x 20 cm are treated.

Les éprouvettes ainsi traitées sont examinées au microscope électronique, comme indiqué précédemment.The test pieces thus treated are examined under the electron microscope, as indicated above.

Suivant la grosseur relative des cristaux, on attribue une note de 1 à 5, à savoir :

  • 1 : note correspondant à la finesse maximum (cristaux très fins)
  • 2 : note correspondant à des cristaux fins
  • 3 : note correspondant à des cristaux moyens
  • 4 : note correspondant à des cristaux grossiers
  • 5 : note correspondant à des cristaux très grossiers.
Depending on the relative size of the crystals, a score of 1 to 5 is assigned, namely:
  • 1: note corresponding to maximum finesse (very fine crystals)
  • 2: note corresponding to fine crystals
  • 3: note corresponding to medium crystals
  • 4: note corresponding to coarse crystals
  • 5: note corresponding to very coarse crystals.

On a réuni dans le tableau suivant les résultats trouvés.

Figure imgb0004
The results found are collated in the following table.
Figure imgb0004

De l'ensemble de ces résultats, on déduit :

  • - que les acides phosphoniques mis en oeuvre selon l'invention ou leurs sels améliorent notablement la densité et la finesse des cristaux,
  • - que les résultats obtenus sont supérieurs ou équivalents aux résultats obtenus avec un montage en eau déminéralisée.
From all these results, we deduce:
  • - that the phosphonic acids used according to the invention or their salts notably improve the density and the fineness of the crystals,
  • - that the results obtained are superior or equivalent to the results obtained with an assembly in demineralized water.

Comme il va de soi et comme il résulte d'ailleurs déjà de ce qui précède, l'invention ne se limite nullement à ceux de ses modes d'application et de réalisation qui ont été plus spécialement envisagés ; elle en embrasse, au contraire, toutes les variantes.As goes without saying and as it already follows from the above, the invention is in no way limited to those of its modes of application and embodiments which have been more especially envisaged; on the contrary, it embraces all its variants.

Claims (10)

1. Procédé de phosphatation au zinc de substrats essentiellement à base de fer, de zinc ou de leurs alliages, comprenant successivement : 1) une ou plusieurs étapes de dégraissage alcalin, 2) une ou plusieurs étapes de rinçage à l'eau de ville courante, 3) une étape d'activation et d'affinage, 4) une étape de phosphatation au zinc proprement dite, 5) une ou plusieurs étapes de rinçage à l'eau, 6) de préférence, une étape de rinçage final passivant, notamment à l'aide de sels de chrome hexavalent ou de mélanges de chrome hexavalent et de chrome trivalent
caractérisé par le fait que, pour la mise en oeuvre de l'étape d'activation et d'affinage, on a recours à un bain qui comporte, outre les constituants classiques dont notamment au moins un sel de Jernstedt en une proportion correspondant à environ 1 à 100 ppm de titane, une proportion de 10 à 700 ppm, de préférence de 50 à 200 ppm, d'au moins un acide alcane-phosphonique de formule :
Figure imgb0005
dans laquelle R1 représente un radical alcoyle ou un radical aryle éventuellement substitué par au moins l'un des substituants du groupe comprenant le radical hydroxyle, d'autres groupements phosphoniques et les groupements amino de formule
Figure imgb0006
dans laquelle R et R3 qui peuvent être identiques ou différents l'un de l'autre, représentant chacun un atome d'hydrogène ou ayant la signification de R 1, ou d'au moins l'un des sels alcalins ou d'ammonium correspondant aux susdits acides alcane-phosphoniques, le pH du bain étant de 7 à 9,5, de préférence de 7,5 à 9.1. A method of phosphating zinc of substrates essentially based on iron, zinc or their alloys, successively comprising: 1) one or more alkaline degreasing steps, 2) one or more stages of rinsing with running tap water, 3) an activation and refining step, 4) a zinc phosphating step proper, 5) one or more stages of rinsing with water, 6) preferably a passivating final rinsing step, in particular using hexavalent chromium salts or mixtures of hexavalent chromium and trivalent chromium
characterized in that, for the implementation of the activation and refining step, use is made of a bath which comprises, in addition to the conventional constituents including in particular at least one Jernstedt salt in a proportion corresponding to approximately 1 to 100 ppm of titanium, a proportion of 10 to 700 ppm, preferably from 50 to 200 ppm, of at least one alkane-phosphonic acid of formula:
Figure imgb0005
 in which R 1 represents an alkyl radical or an aryl radical optionally substituted with at least one of the substituents of the group comprising the hydroxyl radical, other phosphonic groups and the amino groups of formula
Figure imgb0006
 wherein R and R 3 which may be the same or different from each other, each representing a hydrogen atom or having the meaning of R 1, or at least one of the alkali or ammonium salts corresponding to the above alkane-phosphonic acids, the pH of the bath being from 7 to 9.5, preferably from 7.5 to 9. 2. Procédé selon la revendication 1, caractérisé par le fait que l'acide alcane-phosphonique comporté par le bain d'activation et d'affinage est choisi dans le groupe comprenant : - l'acide hydroxyméthylphosphonique - l'acide hydroxypropylphosphonique - l'acide octylphosphonique - l'acide éthyl- et l'acide butylphosphonique - l'acide 1-hydroxyéthylidène-1,1-diphosphonique - l'acide amino-tri(méthylènephosphonique) - l'acide éthylène-diamine-tétra(méthylènephospho- nique) et - l'acide 2-phosphono-butane-1,2,4-tricarboxylique. 2. Method according to claim 1, characterized in that the alkane-phosphonic acid comprised by the activation and refining bath is chosen from the group comprising: - hydroxymethylphosphonic acid - hydroxypropylphosphonic acid - octylphosphonic acid - ethyl acid and butylphosphonic acid - 1-hydroxyethylidene-1,1-diphosphonic acid - amino-tri acid (methylenephosphonic) - ethylene-diamine-tetra (methylenephosphonic) acid and - 2-phosphono-butane-1,2,4-tricarboxylic acid. 3. Procédé selon l'une des revendications 1 et 2, caractérisé par le fait que le bain d'activation et d'affinage mis en oeuvre présente la composition suivante : - 2 g/1 de sel de Jernstedt (FIXODINE 5) - 60 ppm du sel de sodium de l'acide aminotri-(méthylène-phosphonique) - eau q.s. 3. Method according to one of claims 1 and 2, characterized in that the activation and refining bath used has the following composition: - 2 g / 1 Jernstedt salt (FIXODINE 5) - 60 ppm of the sodium salt of aminotri- (methylene-phosphonic acid) - water qs 4. Procédé selon l'une des revendications 1 et 2, caractérisé par le fait le bain d'activation et d'affinage mis en oeuvre présente la composition suivante : - 2 g/1 de sel de Jernstedt (FIXODINE 5) - 200 ppm du sel de sodium de l'acide phosphonique - eau q.s. 4. Method according to one of claims 1 and 2, characterized in that the activation and refining bath used has the following composition: - 2 g / 1 Jernstedt salt (FIXODINE 5) - 200 ppm of the sodium salt of phosphonic acid - water qs 5. Procédé selon l'une des revendications 1 et 2, caractérisé par le fait le bain d'activation et d'affinage mis en oeuvre présente la composition suivante : - 2 g/1 de sel de Jernstedt (FIXOIYINE 5) - 50 ppm d'acide 1-hydroxyéthylidène-1,1-disphos- phonique, - eau q.s. 5. Method according to one of claims 1 and 2, characterized in that the activation and refining bath used has the following composition: - 2 g / 1 Jernstedt salt (FIXOIYINE 5) - 50 ppm of 1-hydroxyethylidene-1,1-disphosphonic acid, - water qs 6. Bain tel que mis en oeuvre dans le procédé selon l'une des revendications 1 à 5.6. Bath as used in the method according to one of claims 1 to 5. 7. Concentré pour la préparation du bain d'activation et d'affinage selon la revendication 6, caractérisé par le fait qu'il comporte les constituants dudit bain en des proportions telles que ce bain est obtenu par mélange du concentré avec une proportion appropriée d'eau.7. Concentrate for the preparation of the activation and refining bath according to claim 6, characterized in that it comprises the constituents of said bath in proportions such that this bath is obtained by mixing the concentrate with an appropriate proportion d 'water. 8. Concentré selon la revendication 7, caractérisé par le fait qu'il se présente sous la forme d'une poudre comprenant : - de 1 à 5 % en poids de titane exprimé en titane(IV) sous forme de phosphate de titane, - de 2,5 à 10 % en poids d'acide phosphonique, - de 89 à 92,5 % en poids de phosphate de sodium et de potassium. 8. Concentrate according to claim 7, characterized in that it is in the form of a powder comprising: from 1 to 5% by weight of titanium expressed as titanium (IV) in the form of titanium phosphate, - from 2.5 to 10% by weight of phosphonic acid, - from 89 to 92.5% by weight of sodium and potassium phosphate. 9. Concentré selon la revendication 7, caractérisé par le fait qu'il présente la constitution suivante :
Figure imgb0007
 9. Concentrate according to claim 7, characterized in that it has the following constitution:
Figure imgb0007
 10. Concentré selon la revendication 7, caractérisé par le fait qu'il se présente sous la forme de deux récipients séparés réunis dans ce qu'on appelle un "kit" de traitement et contenant respectivement, d'une part, le sel de Jernstedt et, d'autre part, une solution aqueuse de l'acide phosphonique de formule (I) ou de son sel.10. Concentrate according to claim 7, characterized in that it is in the form of two separate containers joined in what is called a "kit" treatment and containing respectively, on the one hand, Jernstedt salt and, on the other hand, an aqueous solution of the phosphonic acid of formula (I) or its salt.
EP85402096A 1984-10-31 1985-10-30 Process for zinc phosphate coating, activation and grain refining bath used in this process and concentrate therefor Expired EP0180523B1 (en)

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FR8416725 1984-10-31

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339452A2 (en) * 1988-04-28 1989-11-02 Henkel Kommanditgesellschaft auf Aktien Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating
EP0340530A1 (en) * 1988-04-28 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Titanium-free activating agents, process for preparing them and their use in activating a metal surface before zinc phosphating
FR2686622A1 (en) * 1992-01-29 1993-07-30 Francais Prod Ind Cfpi CONCENTRATE FOR ACTIVATION AND REFINING BATH AND BATH OBTAINED FROM THIS CONCENTRATE.
EP0707664A4 (en) * 1993-06-15 1996-02-09 Henkel Corp Rapidly dissolving and storage stable titanium phosphate containing activating composition
WO1996008588A1 (en) * 1994-09-12 1996-03-21 Ppg Industries, Inc. Liquid rinse conditioner for phosphate conversion coatings

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793867A (en) * 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
CA1309315C (en) * 1987-07-14 1992-10-27 Toan Manh Ngo Compositions and process for metal treatment
US5003986A (en) * 1988-11-17 1991-04-02 Kenneth D. Pool, Jr. Hierarchial analysis for processing brain stem signals to define a prominent wave
US4917737A (en) * 1989-03-13 1990-04-17 Betz Laboratories, Inc. Sealing composition and method for iron and zinc phosphating process
DE4131950A1 (en) * 1991-09-25 1993-04-01 Boehme Chem Fab Kg Fluxes and remelting fluids for circuit board mfr. - comprising alkane phosphonic acids and/or their salts, half ester(s) di:ester(s) and half ester salts
US5628838A (en) * 1992-01-29 1997-05-13 C.F.P.I Societe Anonyme Concentrate for activating and defining bath and bath obtained from this concentrate
US20050268991A1 (en) * 2004-06-03 2005-12-08 Enthone Inc. Corrosion resistance enhancement of tin surfaces
CN111534815A (en) * 2020-05-22 2020-08-14 山东大学 Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864139A (en) * 1970-12-04 1975-02-04 Amchem Prod Pretreatment compositions and use thereof in treating metal surfaces
EP0031103A1 (en) * 1979-12-21 1981-07-01 Gerhard Collardin GmbH Method for the pretreatment of metal surfaces prior to phosphatizing
EP0091627A2 (en) * 1982-04-14 1983-10-19 Gerhard Collardin GmbH Process for cleaning, degreasing and activating metallic surfaces
DE3217145A1 (en) * 1982-05-07 1983-11-10 Gerhard Collardin GmbH, 5000 Köln Method for cleaning, degreasing and activating metal surfaces

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427459A (en) * 1982-01-25 1984-01-24 Pennwalt Corporation Phosphate conversion coatings for metals with reduced coating weights and crystal sizes
US4497667A (en) * 1983-07-11 1985-02-05 Amchem Products, Inc. Pretreatment compositions for metals

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864139A (en) * 1970-12-04 1975-02-04 Amchem Prod Pretreatment compositions and use thereof in treating metal surfaces
EP0031103A1 (en) * 1979-12-21 1981-07-01 Gerhard Collardin GmbH Method for the pretreatment of metal surfaces prior to phosphatizing
EP0091627A2 (en) * 1982-04-14 1983-10-19 Gerhard Collardin GmbH Process for cleaning, degreasing and activating metallic surfaces
DE3217145A1 (en) * 1982-05-07 1983-11-10 Gerhard Collardin GmbH, 5000 Köln Method for cleaning, degreasing and activating metal surfaces

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0339452A2 (en) * 1988-04-28 1989-11-02 Henkel Kommanditgesellschaft auf Aktien Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating
EP0340530A1 (en) * 1988-04-28 1989-11-08 Henkel Kommanditgesellschaft auf Aktien Titanium-free activating agents, process for preparing them and their use in activating a metal surface before zinc phosphating
EP0339452A3 (en) * 1988-04-28 1991-06-12 Henkel Kommanditgesellschaft auf Aktien Polymer titanium phosphates, process for their preparaton and their use in the activation of metal surfaces before zinc phosphating
FR2686622A1 (en) * 1992-01-29 1993-07-30 Francais Prod Ind Cfpi CONCENTRATE FOR ACTIVATION AND REFINING BATH AND BATH OBTAINED FROM THIS CONCENTRATE.
EP0554179A1 (en) * 1992-01-29 1993-08-04 C F P I Concentrate for activating and refining bath and bath obtained
EP0707664A4 (en) * 1993-06-15 1996-02-09 Henkel Corp Rapidly dissolving and storage stable titanium phosphate containing activating composition
EP0707664A1 (en) * 1993-06-15 1996-04-24 Henkel Corporation Rapidly dissolving and storage stable titanium phosphate containing activating composition
WO1996008588A1 (en) * 1994-09-12 1996-03-21 Ppg Industries, Inc. Liquid rinse conditioner for phosphate conversion coatings

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JPS61124582A (en) 1986-06-12
US4678519A (en) 1987-07-07
ATE44051T1 (en) 1989-06-15
EP0180523B1 (en) 1989-06-14
FR2572422B1 (en) 1993-03-05
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DE3571050D1 (en) 1989-07-20
CA1260809A (en) 1989-09-26

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