EP0085626B1 - Composition and process for treating phosphated metallic surfaces - Google Patents

Composition and process for treating phosphated metallic surfaces Download PDF

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Publication number
EP0085626B1
EP0085626B1 EP83400204A EP83400204A EP0085626B1 EP 0085626 B1 EP0085626 B1 EP 0085626B1 EP 83400204 A EP83400204 A EP 83400204A EP 83400204 A EP83400204 A EP 83400204A EP 0085626 B1 EP0085626 B1 EP 0085626B1
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EP
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Prior art keywords
composition
titanium
trivalent titanium
process according
trivalent
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German (de)
French (fr)
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EP0085626A1 (en
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Joseph Schapira
Victor Ken
Jean-Loup Dauptain
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Compagnie Francaise de Produits Industriels SA
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the subject of the invention is a method for the treatment, more precisely the "post-treatment" of phosphated metal surfaces, in particular when these surfaces must be subsequently coated with a layer of paint.
  • the phosphating, including iron and zinc phosphating, of the metal surfaces in question i.e. surfaces of iron, steel, zinc, iron and galvanized steel substrates, d 'aluminum and alloys of the above metals, cadmium and others, aims to protect these surfaces against corrosion; these surfaces are then optionally covered with a layer of paint which may be based more particularly on lacquers, varnishes and enamels applied for example by immersion, electrophoresis, spraying and the like.
  • These treatments which have the aim of further increasing the effectiveness of the protection against corrosion of previously phosphated metal surfaces, generally employ trivalent and / or hexavalent chromium ions in the form of chromium-based compositions or solutions of chromation. chromate applied in final or passivating rinse.
  • the object of the invention is therefore, above all, to provide a process for the treatment of phosphated metal surfaces with the aid of a composition which, while giving these surfaces protection equivalent to that produced by the chromium plating solutions. 'prior art, no longer has the disadvantages of these.
  • the treatment method according to the invention in which after phosphating of metal surfaces and before possible application of a layer of paint, the phosphated metal surface is treated by bringing said surface into contact with a composition comprising titanium, is characterized in that the composition comprises trivalent titanium at a concentration of 0.01 to 2 g / 1 and has a pH of 2 to 7, the temperature of the composition being less than 90 ° C, preferably included between 18 and 60 ° C.
  • composition used in accordance with the method according to the invention contains trivalent titanium at a concentration of 0.2 to 0.6 g / I.
  • the composition used in accordance with the process according to the invention is obtained by dilution with water from a concentrate which may contain, by way of indication, approximately 10 to 50 g of trivalent titanium per liter, this concentrate which is preferably kept away from oxygen in the air until the time of use, being diluted at that time with the quantity of water, preferably distilled or deionized, chosen to result in the concentration of trivalent titanium which corresponds to that of the composition used.
  • the relatively low stability especially in dilute solution and in contact with the oxygen of the air of the compounds containing trivalent titanium, which rapidly oxidizes to tetravalent titanium, means that the composition used in the process in accordance with invention will generally be prepared at the time of use and regenerated if necessary during operation by reduction of tetravalent titanium formed of trivalent titanium.
  • the process according to the invention is therefore characterized by the fact that the trivalent titanium to be comprised by the composition used is prepared in situ and before the application of the composition to the phosphated metal surfaces, by setting in contact with tetravalent titanium with a reduction means, the composition then being, during the process of treatment of phosphate surfaces, regenerated into. trivalent titanium by bringing into contact in particular a fraction derived from the composition with the abovementioned reduction means in such a way that the concentration of the composition in trivalent titanium compound is maintained in the proportion in particular from 0.2 to 0.6 g of trivalent titanium per liter, mentioned above.
  • the process according to the invention is characterized in that the composition used is prepared from a concentrate and that the concentration of trivalent titanium of the composition thus obtained is maintained at the value effective by regeneration during operation in contact with a means of reducing tetravalent titanium to trivalent titanium.
  • the above regeneration can take place continuously.
  • Proposing therefore, to treat, in order to improve its resistance to corrosion, a phosphated metal surface which may possibly receive one or more layers of paint subsequently, this is done as follows or in an equivalent manner.
  • said metallic surface which may be that of a metallic substrate based on iron, steel, zinc, galvanized iron or steel, aluminum, alloys of these metals, of cadmium and others, to a phosphating treatment comprising, after degreasing with the aid in particular of alkaline detergents, the action of a conventional acid phosphating composition with iron or zinc generally implemented hot and for several minutes by immersion or by sprinkling.
  • the metal surface is treated in accordance with the method according to the invention using a composition which contains a trivalent titanium compound at a concentration of 0, 01 to 2 g, preferably 0.2 to 0.6 g of trivalent titanium per liter and has an acid pH of 2 to 7, preferably 2 to 5.
  • the proportions of 0.2 to 0.6 g of trivalent titanium per liter correspond to a value of 4.17 10-3 to 1.25 - 10-2 gram atoms of trivalent titanium per liter.
  • the pH can be adjusted using soda, ammonia, hydrofluoric acid, nitric acid and other acids or bases.
  • the composition is used at a temperature below 90 ° C. and in particular chosen from the range from 18 to 60 ° C.
  • the treatment preferably takes place by immersing the metal surface in the composition for a period generally between 10 and 60 seconds.
  • composition can also be applied by spraying; this technique is less advantageous because of the sensitivity of trivalent titanium with respect to oxidation.
  • the treatment is followed by rinsing with water and drying, in particular hot, of the metal surface before possible application of a paint which can be chosen from lacquers, varnishes, enamels and the like, applied by any process. suitable.
  • the quality of the anti-corrosion protection conferred can be tested by the salt spray test which will be more particularly discussed in relation to the examples. This test is described in the American standards ASTM B 117 and ASTM D 1654-61. The assessment of the corrosion resistance conferred is made using a scale ranging from 0 (zero resistance) to 10 (very good corrosion resistance).
  • the trivalent titanium compound can be chosen from the group comprising chloride, bromide, fluoride, oxalate and trivalent titanium sulfate which have been found to be particularly active.
  • composition used in accordance with the invention must be regenerated to maintain its concentration of trivalent titanium at an effective value, this which can be achieved by contacting a reduction means, in particular a reducing agent.
  • the treatment enclosure containing the composition can be made to include a bypass pipe in which the reducing agent is placed.
  • the composition can be taken from the bottom of the enclosure, passed through the bypass pipe containing the reducing agent and reintroduced onto the surface of the bath constituting the composition.
  • the immersion treatment is of the dynamic type with translation of the parts comprising the phosphated surfaces to be treated, it will be advantageously arranged so that the direction of the current created within the composition, as a result of the sampling in the bypass line, is contrary to the translational movement of the parts.
  • the reduction means can be either a metallic or chemical reducing agent placed in a column, or an electrolysis cell, the column or cell being traversed by the composition to be regenerated continuously or discontinuously so that the titanium concentration trivalent is maintained at the effective value; the effects of the oxidation of the bath and / or of the regeneration are followed by simple volumetric redox dosing and the regeneration is started or stopped when the proportion of the composition in trivalent titanium goes beyond the limits indicated above.
  • an inert electrode is used, the method being that used in redox batteries.
  • test pieces made up of panels of "cold-rolled steel of current quality, thickness 8/10 mm and -measuring 150 mm x 70 mm, are carefully degreased using trichlorethylene then acetone; they are then subjected to a dip phosphating treatment.
  • a commercial phosphating composition is used, in particular that known under the brand "Duridine 49" ® and the concentration of which is 3% by weight.
  • This composition contains phosphating agents and surfactants.
  • the duration of the quenching of the test pieces in the phosphating composition is 10 minutes.
  • the coating obtained is an iron phosphate coating whose layer weight varies between 0.2 and 0.3 g / m2 .
  • test pieces are divided into three sets of five.
  • test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to this satin fog, the results obtained are examined. using ASTM D 1654-61. These results are shown in Table I below; they represent the means of the results of the three series of tests carried out with the three sets of fifteen test pieces.
  • test specimens consisting of panels of "cold-rolled steel of standard quality, 8/10 mm thick, measuring 150 mm x 70 mm. These test pieces are carefully degreased using trichlorethylene and then acetone before undergoing a phosphating conversion treatment by soaking.
  • This treatment is carried out with the same phosphating composition as in Example 1 and in the conditions described in this example.
  • Curve C shown in FIG. 2 illustrates the variation in the content of the bath in grams of Ti (III) per liter of composition (ordinate axis) as a function of the time T expressed in minutes during which recycling is maintained (abscissa axis) in the conditions which have just been specified.
  • test pieces are dried in an oven at 150 ° C. for 5 minutes, then the water-soluble paint of example 1 is applied to them by dipping while respecting the conditions described in this example.
  • test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to said salt spray, the results obtained are examined in accordance with to ASTM D 1654-61. These results are shown in Table II below; they represent the averages of the results of the tests carried out on three sets of twenty-five test pieces.
  • a zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .
  • the three sets of five test pieces are then treated respectively as the three sets of five test pieces of Example 1.
  • Example 2 After drying and application of the water-soluble paint under the conditions of Example 1, the three series of test pieces are treated as described in standard ASTM B 117. After 384 hours of exposure to salt spray, the results are examined. obtained using ASTM 1654-61. These results are shown in Table III below; they represent the means of the results of three tests, that is to say tests carried out with three sets of three series of five test pieces.
  • a zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .

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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)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a composition and a process for the treatment, more precisely the "post-treatment" of phosphatized metal surfaces, particularly when the surfaces must be subsequently covered with a coat of paint. It relates also to a process for the preparation of the composition and a concentrate useful for this preparation. The composition comprises an effective proportion of trivalent titanium compound and it is presented with an acid pH, the proportion of said compound being sufficient for the corresponding composition to confer on the treated metal surface a protection equivalent to that obtained with known chromatizing solutions. More particularly, the composition contains trivalent titanium at a concentration of 0.01 to 2 g/l, preferably from 0.2 to 0.6 g/l and has a pH of 2 to 7. Reducing means can be arranged to regenerate the trivalent titanium in the treatment solution continuously.

Description

L'invention a pour objet un procédé pour le traitement, plus précisément le « post-traitement » de surfaces métalliques phosphatées, notamment lorsque ces surfaces doivent être subséquemment revêtues d'une couche de peinture.The subject of the invention is a method for the treatment, more precisely the "post-treatment" of phosphated metal surfaces, in particular when these surfaces must be subsequently coated with a layer of paint.

La phosphatation, notamment la phosphatation au fer et au zinc, des surfaces métalliques en question, c'est-à-dire des surfaces de substrats à base de fer, d'acier, de zinc, de fer et d'acier galvanisés, d'aluminium et d'alliages des métaux qui précèdent, de cadmium et d'autres, a pour but de protéger ces surfaces contre la corrosion ; ces surfaces sont éventuellement recouvertes ensuite d'une couche de peinture qui peut être à base plus particulièrement de laques, vernis et émaux appliqués par exemple par immersion, électrophorèse, pistolage et autres.The phosphating, including iron and zinc phosphating, of the metal surfaces in question, i.e. surfaces of iron, steel, zinc, iron and galvanized steel substrates, d 'aluminum and alloys of the above metals, cadmium and others, aims to protect these surfaces against corrosion; these surfaces are then optionally covered with a layer of paint which may be based more particularly on lacquers, varnishes and enamels applied for example by immersion, electrophoresis, spraying and the like.

Il existe déjà des traitements de surfaces métalliques phosphatées, appelés couramment rinçages passivants ou rinçages de post-traitement.Treatments of phosphated metal surfaces already exist, commonly called passivating rinses or post-treatment rinses.

Ces traitements, qui ont pour but d'accroître encore l'efficacité de la protection contre la corrosion des surfaces métalliques préalablement phosphatées, mettent généralement en ceuvre des ions chrome trivalent et/ou hexavalent sous la forme de compositions ou solutions de chromatation à base de chromate appliquées en rinçage final ou passivant.These treatments, which have the aim of further increasing the effectiveness of the protection against corrosion of previously phosphated metal surfaces, generally employ trivalent and / or hexavalent chromium ions in the form of chromium-based compositions or solutions of chromation. chromate applied in final or passivating rinse.

Tout en donnant satisfaction du point de vue de l'amélioration de la protection contre la corrosion ainsi réalisée, ces traitements présentent néanmoins deux inconvénients majeurs résidant, dans l'ordre d'importance,

  • - dans la haute toxicité - due aux ions chrome trivalent et hexavalent - des solutions de chromatation mises en oeuvre et des effluents subséquents dont le traitement visant à éliminer les ions gênants s'impose,
  • - dans la forte coloration se traduisant par des taches jaunes visibles si la couche de peinture subséquemment appliquée est mince.
While giving satisfaction from the point of view of improving the corrosion protection thus produced, these treatments nevertheless have two major drawbacks residing, in order of importance,
  • - in the high toxicity - due to the trivalent and hexavalent chromium ions - chromating solutions used and subsequent effluents whose treatment aimed at removing the troublesome ions is necessary,
  • - in the strong coloration resulting in visible yellow spots if the layer of paint subsequently applied is thin.

De nombreuses tentatives ont visé à remplacer le traitement de chromatage par des traitements à base de compositions exemptes de chrome.Many attempts have been made to replace the chromating treatment with treatments based on chromium-free compositions.

Il a ainsi été proposé d'appliquer aux surfaces préalablement phosphatées, notamment

  • - des compositions renfermant des sels solubles de zirconium (voir FR-A- 2117256),
  • - des compositions renfermant des sels fluorés de calcium, zinc, aluminium, de titane tétravalent, de zirconium, de nickel (voir FR-A- 2 232 615),
  • - des compositions renfermant le titane tétravalent sous la forme de fluotitanate de potassium ou d'ammonium ou d'oxalate de potassium et de titanyle (voir FR-A- 2 339 683).
It has thus been proposed to apply to previously phosphated surfaces, in particular
  • - compositions containing soluble zirconium salts (see FR-A-2117256),
  • - compositions containing fluorinated salts of calcium, zinc, aluminum, tetravalent titanium, zirconium, nickel (see FR-A- 2 232 615),
  • - compositions containing tetravalent titanium in the form of potassium fluotitanate or ammonium or potassium oxalate and titanyl (see FR-A- 2 339 683).

Bien que ces traitements aient permis de supprimer les inconvénients dus à l'ion chrome et inhérents aux compositions qui en renferment, ils n'ont pas donné entièrement satisfaction en raison du fait que la protéction contre la corrosion qu'ils conféraient aux surfaces traitées, était très nettement inférieure à celle réalisée à l'aide des compositions de chromatage.Although these treatments have made it possible to eliminate the drawbacks due to the chromium ion and inherent in the compositions containing it, they have not been entirely satisfactory due to the fact that the protection against corrosion which they confer on the treated surfaces, was very much lower than that produced using the chromating compositions.

L'invention a donc pour but, surtout, de fournir un procédé pour le traitement des surfaces métalliques phosphatées à l'aide d'une composition qui, tout en conférant à ces surfaces une protection équivalente à celle réalisée par les solutions de chromatage de l'art antérieur, ne présente plus les inconvénients de celles-ci.The object of the invention is therefore, above all, to provide a process for the treatment of phosphated metal surfaces with the aid of a composition which, while giving these surfaces protection equivalent to that produced by the chromium plating solutions. 'prior art, no longer has the disadvantages of these.

Or, la Société demanderesse a eu le mérite de trouver que, de façon d'autant plus inattendue que les traitements de l'art antérieur mettant en oeuvre du titane tétravalent n'avaient pas été satisfaisants du point de vue de la protection conférée, le traitement à l'aide d'une composition à base d'un composé du titane trivalent et exempt de chrome conférait aux surfaces métalliques traitées une protection équivalente à celle réalisée avec les solutions de chromatage de l'art antérieur.However, the Applicant Company had the merit of finding that, all the more unexpectedly since the treatments of the prior art using tetravalent titanium had not been satisfactory from the point of view of the protection conferred, the treatment using a composition based on a trivalent titanium compound and free of chromium gave the treated metal surfaces protection equivalent to that achieved with the chromating solutions of the prior art.

Il s'ensuit que le procédé de traitement conforme à l'invention, dans lequel après phosphatation de surfaces métalliques et avant application éventuelle d'une couche de peinture, la surface métallique phosphatée est traitée par mise en contact de ladite surface avec une composition comprenant du titane, est caractérisé par le fait que la composition comprend du titane trivalent à une concentration de 0,01 à 2g/1 et présente un pH de 2 à 7, la température de la composition étant inférieure à 90 °C, de préférence comprise entre 18 et 60 °C.It follows that the treatment method according to the invention, in which after phosphating of metal surfaces and before possible application of a layer of paint, the phosphated metal surface is treated by bringing said surface into contact with a composition comprising titanium, is characterized in that the composition comprises trivalent titanium at a concentration of 0.01 to 2 g / 1 and has a pH of 2 to 7, the temperature of the composition being less than 90 ° C, preferably included between 18 and 60 ° C.

Plus particulièrement, la composition mise en ceuvre conformément au procédé selon l'invention renferme le titane trivalent à une concentration de 0,2 à 0,6 g/I.More particularly, the composition used in accordance with the method according to the invention contains trivalent titanium at a concentration of 0.2 to 0.6 g / I.

Plus particulièrement encore, la composition mise en oeuvre conformément au procédé selon l'invention est obtenue par dilution avec de l'eau à partir d'un concentré pouvant contenir, à titre indicatif, environ 10 à 50 g de titane trivalent par litre, ce concentré qui est maintenu de préférence à l'abri de l'oxygène de l'air jusqu'au moment de l'utilisation étant dilué à ce moment avec la quantité d'eau de préférence distillée ou déionisée, choisie pour aboutir à la concentration en titane trivalent qui correspond à celle de la composition mise en oeuvre.More particularly still, the composition used in accordance with the process according to the invention is obtained by dilution with water from a concentrate which may contain, by way of indication, approximately 10 to 50 g of trivalent titanium per liter, this concentrate which is preferably kept away from oxygen in the air until the time of use, being diluted at that time with the quantity of water, preferably distilled or deionized, chosen to result in the concentration of trivalent titanium which corresponds to that of the composition used.

La stabilité relativement faible, surtout en solution diluée et au contact de l'oxygène de l'air des composés renfermant du titane trivalent, qui s'oxyde rapidement en titane tétravalent, fait que la composition mise en oeuvre dans le procédé conforme à l'invention sera préparée en général au moment de son utilisation et régénérée si nécessaire en cours d'opération par réduction du titane tétravalent formé en titane trivalent.The relatively low stability, especially in dilute solution and in contact with the oxygen of the air of the compounds containing trivalent titanium, which rapidly oxidizes to tetravalent titanium, means that the composition used in the process in accordance with invention will generally be prepared at the time of use and regenerated if necessary during operation by reduction of tetravalent titanium formed of trivalent titanium.

Suivant un aspect particulier, le procédé conforme à l'invention est donc caractérisé par le fait que le titane trivalent devant être comporté par la composition mise en oeuvre est préparé in situ et avant l'application de la composition aux surfaces métalliques phosphatées, par mise en contact du titane tétravalent avec un moyen de réduction, la composition étant ensuite, au cours du procédé de traitement des surfaces phosphatées, régénérée en. titane trivalent par mise en contact notamment d'une fraction dérivée de la composition avec le susdit moyen de réduction de façon telle que la concentration de la composition en composé de titane trivalent soit maintenue à la proportion notamment de 0,2 à 0,6 g de titane trivalent par litre, susmentionnée.According to a particular aspect, the process according to the invention is therefore characterized by the fact that the trivalent titanium to be comprised by the composition used is prepared in situ and before the application of the composition to the phosphated metal surfaces, by setting in contact with tetravalent titanium with a reduction means, the composition then being, during the process of treatment of phosphate surfaces, regenerated into. trivalent titanium by bringing into contact in particular a fraction derived from the composition with the abovementioned reduction means in such a way that the concentration of the composition in trivalent titanium compound is maintained in the proportion in particular from 0.2 to 0.6 g of trivalent titanium per liter, mentioned above.

Suivant un autre aspect, le procédé conforme à l'invention est caractérisé par le fait que la composition mise en oeuvre est préparée à partir d'un concentré et que l'on maintient la concentration en titane trivalent de la composition ainsi obtenue à la valeur efficace par régénération en cours d'opération au contact d'un moyen de réduction du titane tétravalent en titane trivalent.According to another aspect, the process according to the invention is characterized in that the composition used is prepared from a concentrate and that the concentration of trivalent titanium of the composition thus obtained is maintained at the value effective by regeneration during operation in contact with a means of reducing tetravalent titanium to trivalent titanium.

La susdite régénération peut avoir lieu en continu.The above regeneration can take place continuously.

L'invention pourra encore être mieux comprise à l'aide du complément de description et des exemples ci-après, lesquels complément de description et exemples étant donnés en rapport avec des modes de réalisation avantageux.The invention will be able to be understood more clearly with the aid of the additional description and of the examples below, which further description and examples being given in relation to advantageous embodiments.

Se proposant, par conséquent, de traiter, en vue d'améliorer sa résistance à la corrosion, une surface métallique phosphatée devant éventuellement recevoir ultérieurement une ou plusieurs couches de peinture, on s'y prend comme suit ou de façon équivalente.Proposing, therefore, to treat, in order to improve its resistance to corrosion, a phosphated metal surface which may possibly receive one or more layers of paint subsequently, this is done as follows or in an equivalent manner.

On soumet tout d'abord et de façon en soi connue ladite surface métallique qui peut être celle d'un substrat métallique à base de fer, d'acier, de zinc, de fer ou d'acier galvanisés, d'aluminium, d'alliages de ces métaux, de cadmium et autres, à un traitement de phosphatation comportant après dégraissage à l'aide notamment de lessives alcalines, l'action d'une composition classique acide de phosphatation au fer ou au zinc mise en œuvre généralement à chaud et pendant plusieurs minutes par immersion ou par aspersion.First of all, and in a manner known per se, said metallic surface which may be that of a metallic substrate based on iron, steel, zinc, galvanized iron or steel, aluminum, alloys of these metals, of cadmium and others, to a phosphating treatment comprising, after degreasing with the aid in particular of alkaline detergents, the action of a conventional acid phosphating composition with iron or zinc generally implemented hot and for several minutes by immersion or by sprinkling.

Après rinçage, notamment à l'eau du robinet puis à l'eau déionisée, on traite la surface métallique conformément au procédé selon l'invention à l'aide d'une composition qui renferme un composé du titane trivalent à une concentration de 0,01 à 2 g, de préférence de 0,2 à 0,6 g de titane trivalent par litre et présente un pH acide de 2 à 7, de préférence de 2 à 5. After rinsing, in particular with tap water and then with deionized water, the metal surface is treated in accordance with the method according to the invention using a composition which contains a trivalent titanium compound at a concentration of 0, 01 to 2 g, preferably 0.2 to 0.6 g of trivalent titanium per liter and has an acid pH of 2 to 7, preferably 2 to 5.

Les proportions de 0,2 à 0,6 g de titane trivalent par litre correspondent à une valeur de 4,17 10-3 à 1,25 - 10-2 atomes-gramme de titane trivalent par litre.The proportions of 0.2 to 0.6 g of trivalent titanium per liter correspond to a value of 4.17 10-3 to 1.25 - 10-2 gram atoms of trivalent titanium per liter.

Le pH peut être ajusté à l'aide de soude, d'ammoniaque, d'acide fluorhydrique, d'acide nitrique et d'autres acides ou bases.The pH can be adjusted using soda, ammonia, hydrofluoric acid, nitric acid and other acids or bases.

La composition est mise en oeuvre à une température inférieure à 90 °C et notamment choisie dans la gamme de 18 à 60 °C.The composition is used at a temperature below 90 ° C. and in particular chosen from the range from 18 to 60 ° C.

Le traitement a lieu, de préférence, par immersion de la surface métallique dans la composition pendant une durée généralement comprise entre 10 et 60 secondes.The treatment preferably takes place by immersing the metal surface in the composition for a period generally between 10 and 60 seconds.

La composition peut également être appliquée par pulvérisation ; cette technique est moins avantageuse en raison de la sensibilité du titane trivalent à l'égard de l'oxydation.The composition can also be applied by spraying; this technique is less advantageous because of the sensitivity of trivalent titanium with respect to oxidation.

Le traitement est suivi d'un rinçage à l'eau et d'un séchage, notamment à chaud, de la surface métallique avant application éventuelle d'une peinture pouvant être choisie parmi les laques, vernis, émaux et autres, appliqués par tout procédé convenable.The treatment is followed by rinsing with water and drying, in particular hot, of the metal surface before possible application of a paint which can be chosen from lacquers, varnishes, enamels and the like, applied by any process. suitable.

Le rinçage avant application des peintures permet de diminuer le risque de cloquage de ces dernières.Rinsing before application of the paints reduces the risk of blistering of the latter.

La qualité de la protection anti-corrosion conférée peut être testée par l'essai au brouillard salin dont il sera plus particulièrement question en rapport avec les exemples. Ce test est décrit dans les normes américaines ASTM B 117 et ASTM D 1654-61. L'appréciation de la résistance à la corrosion conférée se fait à l'aide d'une échelle allant de 0 (résistance nulle) à 10 (très bonne résistance à la corrosion).The quality of the anti-corrosion protection conferred can be tested by the salt spray test which will be more particularly discussed in relation to the examples. This test is described in the American standards ASTM B 117 and ASTM D 1654-61. The assessment of the corrosion resistance conferred is made using a scale ranging from 0 (zero resistance) to 10 (very good corrosion resistance).

Le composé de titane trivalent peut être choisi dans le groupe comprenant le chlorure, le bromure, le fluorure, l'oxalate et le sulfate de titane trivalent qui se sont révélés particulièrement actifs.The trivalent titanium compound can be chosen from the group comprising chloride, bromide, fluoride, oxalate and trivalent titanium sulfate which have been found to be particularly active.

Avantageusement la composition mise en oeuvre conformément au procédé selon l'invention est préparée au départ à partir d'un concentré qui peut contenir environ 10 à 50 g de titane trivalent par litre et qui conduit à ladite composition par dilution avec la quantité convenable d'eau, de préférence déionisée pour éviter l'introduction d'agents polluants tels que le magnésium et le calcium ; ce concentré contient également les autres constituants éventuels de la composition mise en oeuvre conformément au procédé selon l'invention, à savoir notamment :

  • - une faible quantité, notamment de l'ordre de 0,001 à 0,02 g/l d'agents tensio-actifs, en particulier du type organique tels que les alcoylsulfonates de sodium ou les hydrocarbures éthoxylés,
  • - une faible proportion, notamment de 1 mg/I à 500 mg/I d'agents stabilisants, en particulier tels que le pyrogallol ou l'hydroquinone.
Advantageously, the composition used in accordance with the process according to the invention is prepared at the start from a concentrate which can contain approximately 10 to 50 g of trivalent titanium per liter and which leads to said composition by dilution with the appropriate amount of water, preferably deionized to avoid the introduction of polluting agents such as magnesium and calcium; this concentrate also contains the other optional constituents of the composition used in accordance with the process according to the invention, namely in particular:
  • a small amount, in particular of the order of 0.001 to 0.02 g / l of surface-active agents, in particular of the organic type such as sodium alkyl sulfonates or ethoxylated hydrocarbons,
  • - A small proportion, in particular from 1 mg / I to 500 mg / I of stabilizing agents, in particular such as pyrogallol or hydroquinone.

En raison de la sensibilité du titane trivalent à l'égard de l'oxygène de l'air, le susdit concentré est maintenu à l'abri de l'air jusqu'au moment de son utilisation.Due to the sensitivity of trivalent titanium to oxygen in the air, the above-mentioned concentrate is kept protected from air until it is used.

Cette même sensibilité du titane trivalent fait que la composition mise en oeuvre conformément à l'invention doit être régénérée pour maintenir à une valeur efficace sa concentration en titane trivalent, ce qui peut être réalisé par mise en contact avec un moyen de réduction, notamment un agent réducteur.This same sensitivity of trivalent titanium means that the composition used in accordance with the invention must be regenerated to maintain its concentration of trivalent titanium at an effective value, this which can be achieved by contacting a reduction means, in particular a reducing agent.

Du point de vue pratique, on peut faire comporter à l'enceinte de traitement contenant la composition une conduite de dérivation dans laquelle on dispose l'agent réducteur.From the practical point of view, the treatment enclosure containing the composition can be made to include a bypass pipe in which the reducing agent is placed.

Si le traitement par immersion est du type statique, on peut prélever la composition au fond de l'enceinte, la faire passer par la conduite de dérivation contenant l'agent de réduction et la réintroduire à la surface du bain constituant la composition.If the immersion treatment is of the static type, the composition can be taken from the bottom of the enclosure, passed through the bypass pipe containing the reducing agent and reintroduced onto the surface of the bath constituting the composition.

Si le traitement d'immersion est du type dynamique avec translation des pièces comportant les surfaces phosphatées à traiter, on s'arrangera avantageusement pour que le sens du courant créé au sein de la composition, par suite du prélèvement dans la conduite de dérivation, soit contraire au mouvement de translation des pièces.If the immersion treatment is of the dynamic type with translation of the parts comprising the phosphated surfaces to be treated, it will be advantageously arranged so that the direction of the current created within the composition, as a result of the sampling in the bypass line, is contrary to the translational movement of the parts.

Le moyen de réduction peut être soit un agent réducteur métallique ou chimique disposé dans une colonne, soit une cellule d'électrolyse, la colonne ou la cellule étant traversée par la composition à régénérer en continu ou en discontinu de façon telle que la concentration en titane trivalent soit maintenue à la valeur efficace ; on suit les effets de l'oxydation du bain et/ou de la régénération par simple dosage volumétrique oxydo-réducteur et on met en route ou on stoppe la régénération lorsque la proportion de la composition en titane trivalent sort des limites indiquées plus haut.The reduction means can be either a metallic or chemical reducing agent placed in a column, or an electrolysis cell, the column or cell being traversed by the composition to be regenerated continuously or discontinuously so that the titanium concentration trivalent is maintained at the effective value; the effects of the oxidation of the bath and / or of the regeneration are followed by simple volumetric redox dosing and the regeneration is started or stopped when the proportion of the composition in trivalent titanium goes beyond the limits indicated above.

Les agents réducteurs utilisés peuvent être constitués :

  • - lorsqu'il s'agit de réducteurs métalliques, par de l'amalgame solide de zinc, par des grains de cadmium, par des métaux de Raney, la réduction s'effectuant bien en milieu acide chlorhydrique ou sulfurique (0,5 à 2 N),
  • - lorsqu'il s'agit de réducteurs chimiques, par des borohydrures ou hypophosphites de métaux alcalins du groupe comprenant NaBH4, KBH4, NaH2P02, H,0 ; l'emploi de ces agents se fait à chaud et nécessite la présence d'un catalyseur ; il permet notamment d'amener le fluotitanate de potassium (K2TiFe) en TiF3.
The reducing agents used can consist of:
  • - in the case of metallic reducing agents, with solid zinc amalgam, with cadmium grains, with Raney metals, the reduction taking place well in hydrochloric or sulfuric acid medium (0.5 to 2 NOT),
  • - in the case of chemical reducers, with borohydrides or hypophosphites of alkali metals from the group comprising NaBH 4 , KBH 4 , NaH 2 P0 2 , H, 0; the use of these agents is done hot and requires the presence of a catalyst; it makes it possible in particular to bring potassium fluotitanate (K 2 TiF e ) to TiF 3 .

Quand la réduction est réalisée au moyen d'une électrolyse, on utilise une électrode inerte, le procédé étant celui utilisé dans les batteries redox.When the reduction is carried out by means of electrolysis, an inert electrode is used, the method being that used in redox batteries.

Compte tenu de l'exposé qui précède, il sera avantageux pour l'utilisateur de disposer simultanément de la composition de traitement mise en oeuvre dans le procédé selon l'invention et des moyens de réduction permettant de régénérer et évehtuellement de préparer ladite composition.In view of the foregoing description, it will be advantageous for the user to have simultaneously the treatment composition used in the process according to the invention and reduction means making it possible to regenerate and optionally to prepare said composition.

Les exemples qui suivent sont relatifs à des modes de réalisation préférés de l'invention et montrent, de par les résultats réunis, les avantages de cellemci.The examples which follow relate to preferred embodiments of the invention and show, by the results gathered, the advantages of cellemci.

Exemple 1Example 1

Quinze éprouvettes constituées par des panneaux en « acier laminé à froid de qualité courante d'épaisseur 8/10 mm et-mesurant 150 mm x 70 mm, sont soigneusement dégraissées à l'aide de trichloréthylène puis d'acétone ; elles sont ensuite soumises à un traitement de phosphatation au trempé.Fifteen test pieces made up of panels of "cold-rolled steel of current quality, thickness 8/10 mm and -measuring 150 mm x 70 mm, are carefully degreased using trichlorethylene then acetone; they are then subjected to a dip phosphating treatment.

Pour ce traitement, on utilise une composition de phosphatation du commerce, notamment celle connue sous la marque « Duridine 49 » ® et dont la concentration est de 3 % en poids.For this treatment, a commercial phosphating composition is used, in particular that known under the brand "Duridine 49" ® and the concentration of which is 3% by weight.

Cette composition contient des agents phosphatants et des tensio-actifs.This composition contains phosphating agents and surfactants.

Son pH est de 4,8 à 4,9.Its pH is 4.8 to 4.9.

Elle est mise en oeuvre à 60 °C.It is implemented at 60 ° C.

La durée de la trempe des éprouvettes dans la composition de phosphatation est de 10 minutes.The duration of the quenching of the test pieces in the phosphating composition is 10 minutes.

Le revêtement obtenu est un revêtement de phosphate de fer dont le poids de couche varie entre 0,2 et 0,3 g/m2.The coating obtained is an iron phosphate coating whose layer weight varies between 0.2 and 0.3 g / m2 .

On divise les quinze éprouvettes dont la surface est ainsi phosphatée en trois séries de cinq.The fifteen test pieces, the surface of which is thus phosphated, are divided into three sets of five.

La première série ou Série (1) n'est soumise à aucun traitement destiné à accroître la protection contre la corrosion ; elle est simplement soumise à deux rinçages successifs, à savoir :

  • - un rinçage à l'eau du robinet :
    • - temps : 10 secondes au trempé
    • - température : ambiante,
  • - un rinçage à l'eau déionisée :
    • - temps : 30 secondes au trempé
    • - température : ambiante.
The first series or Series (1) is not subjected to any treatment intended to increase protection against corrosion; it is simply subjected to two successive rinses, namely:
  • - rinsing with tap water:
    • - time: 10 seconds by soaking
    • - ambient temperature,
  • - rinsing with deionized water:
    • - time: 30 seconds by soaking
    • - ambient temperature.

La deuxième série ou Série (2) est soumise à un traitement de chromatage. On procède successivement à :

  • - un rinçage à l'eau du robinet :
    • - temps : 10 secondes au trempé
    • - température : ambiante,
  • - un rinçage final dans une solution chromique de pH égal à 3,4, qui est préparée avec de l'eau déionisée et qui contient 0,25 g/l de chrome hexavalent ainsi que 0,06 g/l de chrome trivalent :
    • - temps : 30 secondes au trempé
    • - température : ambiante,
  • - un rinçage à l'eau déionisée :
    • - temps : 5 secondes au trempé
    • - température : ambiante.
The second series or Series (2) is subjected to a chromating treatment. We proceed successively to:
  • - rinsing with tap water:
    • - time: 10 seconds by soaking
    • - ambient temperature,
  • - a final rinse in a chromic solution with a pH equal to 3.4, which is prepared with deionized water and which contains 0.25 g / l of hexavalent chromium as well as 0.06 g / l of trivalent chromium:
    • - time: 30 seconds by soaking
    • - ambient temperature,
  • - rinsing with deionized water:
    • - time: 5 seconds by soaking
    • - ambient temperature.

La troisième série ou Série (3) est soumise au traitement conforme à l'invention. On procède successivement à :

  • - un rinçage à l'eau du robinet :
    • - temps : 10 secondes au trempé
    • - température : ambiante,
  • - un rinçage final dans une solution de chlorure de titane trivalent préparée à l'aide d'eau déionisée contenant 0,33 g/l de titane trivalent et dont le pH est ajusté avec de la soude à 3,4 :
    • - temps : 30 secondes au trempé
    • - température : ambiante,
  • - un rinçage à l'eau déionisée :
    • - temps : 5 secondes au trempé
    • - température : ambiante.
The third series or Series (3) is subjected to the treatment in accordance with the invention. We proceed successively to:
  • - rinsing with tap water:
    • - time: 10 seconds by soaking
    • - ambient temperature,
  • - a final rinse in a solution of trivalent titanium chloride prepared using deionized water containing 0.33 g / l of trivalent titanium and whose pH is adjusted with sodium hydroxide to 3.4:
    • - time: 30 seconds by soaking
    • - ambient temperature,
  • - rinsing with deionized water:
    • - time: 5 seconds by soaking
    • - ambient temperature.

Les quinze éprouvettes ainsi traitées sont séchées dans une étuve à 150 °C pendant 5 minutes, puis on leur applique au trempé une peinture hydrosoluble (notamment celle de marque BOUVET, référence : Primaire A6 noir satiné n° 63 04 44) en respectant les conditions stipulées par le fournisseur, à savoir :

  • - viscosité : 25 à 30 secondes, mesurée à la coupe Ford n° 4,
  • - pH : 8,8 à 9,2
  • - temps d'égouttage : 10 minutes
  • - temps et température de cuisson : 15 minutes à 160 °C.
The fifteen test pieces thus treated are dried in an oven at 150 ° C for 5 minutes, then a water-soluble paint is applied to them by dipping (in particular that of the BOUVET brand, reference: Primer A6 satin black n ° 63 04 44) respecting the conditions. stipulated by the supplier, namely:
  • - viscosity: 25 to 30 seconds, measured with the Ford n ° 4 cut,
  • - pH: 8.8 to 9.2
  • - draining time: 10 minutes
  • - cooking time and temperature: 15 minutes at 160 ° C.

On traite trois autres jeux de quinze éprouvettes dans les mêmes conditions.Three other sets of fifteen test pieces are treated under the same conditions.

Les éprouvettes sont ensuite soumises à un essai de corrosion au brouillard salin à 5% à une température de 35 °C dans les conditions spécifiées dans la norme ASTM B 117. Après 96 heures d'exposition à ce brouillard satin, on examine les résultats obtenus en utilisant la norme ASTM D 1654-61. Ces résultats sont indiqués dans le tableau I ci-dessous ; ils représentent les moyennes des résultats des trois séries d'essais effectués avec les trois jeux de quinze éprouvettes.

Figure imgb0001
The test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to this satin fog, the results obtained are examined. using ASTM D 1654-61. These results are shown in Table I below; they represent the means of the results of the three series of tests carried out with the three sets of fifteen test pieces.
Figure imgb0001

Ces résultats montrent que les éprouvettes traitées avec une composition à base de titane trivalent manifestent une résistance à la corrosion équivalente à un traitement de chromatage classique. Cette performance est d'autant plus remarquable que la présence d'ion chlorure apporté par le chlorure de titane (III) est bien connue pour son effet néfaste dans ce type de bain sur la tenue à la corrosion.These results show that the specimens treated with a composition based on trivalent titanium exhibit a corrosion resistance equivalent to a conventional chromating treatment. This performance is all the more remarkable since the presence of chloride ion provided by titanium chloride (III) is well known for its harmful effect in this type of bath on the resistance to corrosion.

Exemple 2Example 2

On utilise vingt-cinq éprouvettes constituées par des panneaux en « acier laminé à froid de qualité courante d'épaisseur 8/10 mm et mesurant 150 mm x 70 mm. Ces éprouvettes sont soigneusement dégraissées à l'aide de trichloréthylène puis d'acétone avant de subir un traitement de conversion phosphatante au trempé.Twenty-five test specimens are used, consisting of panels of "cold-rolled steel of standard quality, 8/10 mm thick, measuring 150 mm x 70 mm. These test pieces are carefully degreased using trichlorethylene and then acetone before undergoing a phosphating conversion treatment by soaking.

Ce traitement est réalisé avec la même composition de phosphatation qu'à l'exemple 1 et dans les conditions décrites à cet exemple.This treatment is carried out with the same phosphating composition as in Example 1 and in the conditions described in this example.

Le revêtement obtenu est un revêtement de phosphate de fer dont le poids de couche varie entre 0,2 et 0,3 g/m2. On forme cinq séries de cinq éprouvettes qui sont traitées comme suit.

  • Série (1) :
    • - rinçage à l'eau du robinet :
      • - temps : 10 secondes au trempé
      • - température : ambiante,
      • - rinçage à l'eau déionisée :
      • - temps : 30 secondes au trempé
      • - température : 60 °C.
  • Série (2) :
    • - rinçage à l'eau du robinet :
      • - temps : 10 secondes au trempé
      • - température : ambiante,
    • - chromatage dans une solution chromique préparée à partir d'eau déionisée qui contient 0,25 g/I de chrome hexavalent et 0,06 g/l de chrome trivalent et dont le pH est 3,4 :
      • - temps : 30 secondes au trempé
      • ― température : 60 °C,
    • - rinçage à l'eau déionisée :
      • - temps : 5 secondes au trempé
      • - température : ambiante.
  • Série (3) :
    • - rinçage à l'eau du robinet :
      • - temps : 10 secondes au trempé
      • - température: ambiante,
    • - traitement par rinçage final dans une solution de fluotitanate de potassium préparée à partir d'eau déionisée qui contient 5 g/I de fluotitanate de potassium (soit environ 1 g/l de titane tétravalent) et dont le pH est ajusté à 4,5 avec de la soude :
      • - temps : 30 secondes au trempé
      • - température : 60 °C,
    • - rinçage à l'eau déionisée :
      • ― temps : 5 secondes au trempé
      • - température : ambiante.
  • Série (4) :
    • - rinçage à l'eau du robinet :
      • - temps : 10 secondes au trempé
      • - température : ambiante,
    • - traitement par rinçage final dans une solution de fluotitanate de potassium et d'hypophosphite de sodium préparée à partir d'eau déionisée contenant 5 g/l de titane tétravalent et 10 g/I d'hypophosphite de sodium avec un pH ajusté à 4,5 avec de la soude :
      • - temps : 30 secondes au trempé
      • - température : 60 °C,
    • - rinçage à l'eau déionisée :
      • - temps : 5 secondes au trempé
      • - température : ambiante.
  • Série (5) :
    • - rinçage à l'eau du robinet :
      • - temps : 10 secondes au trempé
      • - température : ambiante,
    • - traitement selon l'invention par rinçage final dans une solution de fluorure de titane trivalent contenant 0,3 g/I de titane trivalent. Cette solution est préparée par dissolution de 5 g de fluotitanate de potassium et 10 g d'hypophosphite de sodium (NaH2PO2, H20) dans un litre d'eau déionisée, chauffage de ce mélange à 60 °C et circulation en circuit fermé à l'aide d'une pompe péristaltique sur une colonne contenant 30 g de poudre de zinc.
The coating obtained is an iron phosphate coating whose layer weight varies between 0.2 and 0.3 g / m 2 . Five sets of five test pieces are formed which are treated as follows.
  • Series (1):
    • - rinsing with tap water:
      • - time: 10 seconds by soaking
      • - ambient temperature,
      • - rinsing with deionized water:
      • - time: 30 seconds by soaking
      • - temperature: 60 ° C.
  • Series (2):
    • - rinsing with tap water:
      • - time: 10 seconds by soaking
      • - ambient temperature,
    • - chromating in a chromic solution prepared from deionized water which contains 0.25 g / I of hexavalent chromium and 0.06 g / l of trivalent chromium and whose pH is 3.4:
      • - time: 30 seconds by soaking
      • - temperature: 60 ° C,
    • - rinsing with deionized water:
      • - time: 5 seconds by soaking
      • - ambient temperature.
  • Series (3):
    • - rinsing with tap water:
      • - time: 10 seconds by soaking
      • - ambient temperature,
    • - treatment by final rinsing in a potassium fluotitanate solution prepared from deionized water which contains 5 g / l of potassium fluotitanate (i.e. approximately 1 g / l of tetravalent titanium) and whose pH is adjusted to 4.5 with soda:
      • - time: 30 seconds by soaking
      • - temperature: 60 ° C,
    • - rinsing with deionized water:
      • - time: 5 seconds by soaking
      • - ambient temperature.
  • Series (4):
    • - rinsing with tap water:
      • - time: 10 seconds by soaking
      • - ambient temperature,
    • - treatment by final rinsing in a solution of potassium fluotitanate and sodium hypophosphite prepared from deionized water containing 5 g / l of tetravalent titanium and 10 g / I of sodium hypophosphite with a pH adjusted to 4, 5 with soda:
      • - time: 30 seconds by soaking
      • - temperature: 60 ° C,
    • - rinsing with deionized water:
      • - time: 5 seconds by soaking
      • - ambient temperature.
  • Series (5):
    • - rinsing with tap water:
      • - time: 10 seconds by soaking
      • - ambient temperature,
    • treatment according to the invention by final rinsing in a solution of trivalent titanium fluoride containing 0.3 g / l of trivalent titanium. This solution is prepared by dissolving 5 g of potassium fluotitanate and 10 g of sodium hypophosphite (NaH 2 PO 2 , H 2 0) in one liter of deionized water, heating this mixture to 60 ° C and circulating in closed circuit using a peristaltic pump on a column containing 30 g of zinc powder.

En respectant un débit de circulation de 0,7 I/heure, on obtient au bout d'une heure une solution de pH = 4,5 contenant 0,3 g/l de titane trivalent que l'on peut utiliser tel que (le schéma du montage utilisé est montré en figure 1 et la courbe d'obtention du titane trivalent en figure 2).By respecting a circulation rate of 0.7 I / hour, a solution of pH = 4.5 containing 0.3 g / l of trivalent titanium which can be used such as ( Diagram of the assembly used is shown in FIG. 1 and the curve for obtaining trivalent titanium in FIG. 2).

Le montage montré figure 1 comporte :

  • - une enceinte 1 contenant des moyens de chauffage, par exemple une résistance chauffante 1a, ainsi que la composition 1b dans laquelle est effectué le traitement,
  • - des moyens de réduction du titane tétravalent en titane trivalent comprenant un réducteur métallique R disposé à l'intérieur d'une colonne 2 fixée sur un support 3 de façon à déboucher au-dessus de la composition 1b,
  • - une pompe 4 reliée par une canalisation 5 au fond de l'enceinte 1 et par une canalisation 6 au sommet de la colonne 2 et propre à prélever dans l'enceinte 1 une fraction de la composition 1 b et de la faire passer par la colonne 2.
The assembly shown in Figure 1 includes:
  • an enclosure 1 containing heating means, for example a heating resistance 1a, as well as composition 1b in which the treatment is carried out,
  • means for reducing tetravalent titanium to trivalent titanium comprising a metallic reducing agent R placed inside a column 2 fixed on a support 3 so as to open out above composition 1b,
  • a pump 4 connected by a pipe 5 to the bottom of the enclosure 1 and by a pipe 6 at the top of the column 2 and suitable for taking from the enclosure 1 a fraction of the composition 1b and of the pass through column 2.

La courbe C montrée figure 2 illustre la variation de la teneur du bain en grammes de Ti(III) par litre de composition (axe des ordonnées) en fonction du temps T exprimé en minutes pendant lequel est maintenu le recyclage (axe des abscisses) dans les conditions qui viennent d'être précisées.Curve C shown in FIG. 2 illustrates the variation in the content of the bath in grams of Ti (III) per liter of composition (ordinate axis) as a function of the time T expressed in minutes during which recycling is maintained (abscissa axis) in the conditions which have just been specified.

Le traitement dans cette solution est comme suit :

  • - temps : 30 secondes au trempé
  • - température : 60 °C,
  • - rinçage à l'eau déionisée :
  • - temps : 5 secondes au trempé
  • - température : ambiante.
The treatment in this solution is as follows:
  • - time: 30 seconds by soaking
  • - temperature: 60 ° C,
  • - rinsing with deionized water:
  • - time: 5 seconds by soaking
  • - ambient temperature.

Les éprouvettes ainsi préparées sont séchées dans une étuve à 150°C pendant 5 minutes, puis on leur applique au trempé la peinture hydrosoluble de l'exemple 1 en respectant les conditions décrites à cet exemple.The thus prepared test pieces are dried in an oven at 150 ° C. for 5 minutes, then the water-soluble paint of example 1 is applied to them by dipping while respecting the conditions described in this example.

Les éprouvettes sont ensuite soumises à un essai de corrosion au brouillard salin à 5 % à une température de 35 °C dans les conditions spécifiées dans la norme ASTM B 117. Après 96 heures d'exposition audit brouillard salin, on examine les résultats obtenus conformément à la norme ASTM D 1654-61. Ces résultats sont indiqués dans le tableau Il ci-dessous ; ils représentent les moyennes des résultats des essais réalisés sur trois jeux de vingt-cinq éprouvettes.

Figure imgb0002
The test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to said salt spray, the results obtained are examined in accordance with to ASTM D 1654-61. These results are shown in Table II below; they represent the averages of the results of the tests carried out on three sets of twenty-five test pieces.
Figure imgb0002

Ces résultats montrent que, dès que la composition contient une quantité suffisante de titane trivalent, les performances anticorrosion deviennent équivalentes à celles d'un rinçage chromique classique.These results show that, as soon as the composition contains a sufficient amount of trivalent titanium, the anticorrosion performance becomes equivalent to that of a conventional chromic rinse.

Exemple 3Example 3

Trois séries de cinq éprouvettes constituées par des panneaux en « acier laminé à froid de qualité courante d'épaisseur 8/10 mm et mesurant 150 x 70 mm, sont soigneusement dégraissées au trichloréthylène puis à l'acétone avant d'être soumises aux traitements suivants :

  • - dégraissage au jet à l'aide d'une composition de dégraissage alcalin, notamment celle qui est commercialisée sous la marque « Ridoline 910 et dont
    • - la concentration d'utilisation est de 1 % en poids,
    • - la température d'application 60 °C et
    • - la durée du traitement de 90 secondes,
    • - la pression d'application étant de 1,5 bar,
  • - rinçage à l'eau du robinet :
    • - temps : 10 secondes au trempé
    • - température : ambiante,
  • - conversion phosphatante au jet à l'aide d'une solution de phosphatation, notamment celle commercialisée sous la marque « Granodine 16 dont
    • - la concentration en agents phosphatants et tensio-actifs est de 1,6 % en volume,
    • - la température d'application de 55 °C,
    • - la durée d'application de 1 minute et
    • - la pression de 0,8 bar.
Three series of five test pieces made up of panels of "cold-rolled steel of current quality of thickness 8/10 mm and measuring 150 x 70 mm, are carefully degreased with trichlorethylene and then with acetone before being subjected to the following treatments :
  • - jet degreasing using an alkaline degreasing composition, in particular that which is marketed under the brand "Ridoline 910 and of which
    • - the use concentration is 1% by weight,
    • - the application temperature 60 ° C and
    • - the duration of the treatment of 90 seconds,
    • - the application pressure being 1.5 bar,
  • - rinsing with tap water:
    • - time: 10 seconds by soaking
    • - ambient temperature,
  • - phosphating jet conversion using a phosphating solution, in particular that sold under the brand name “Granodine 16 including
    • - the concentration of phosphating agents and surfactants is 1.6% by volume,
    • - the application temperature of 55 ° C,
    • - the duration of application of 1 minute and
    • - the pressure of 0.8 bar.

On obtient un revêtement de phosphate de zinc dont le poids de couche varie entre 2 et 3 g/m2.A zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .

Les trois séries de cinq éprouvettes sont alors traitées respectivement comme les trois séries de cinq éprouvettes de l'exemple 1.The three sets of five test pieces are then treated respectively as the three sets of five test pieces of Example 1.

Après séchage et application de la peinture hydrosoluble dans les conditions de l'exemple 1, les trois séries d'éprouvettes sont traitées de la façon décrite dans la norme ASTM B 117. Après 384 heures d'exposition au brouillard salin, on examine les résultats obtenus en utilisant la norme ASTM 1654-61. Ces résultats sont indiqués dans le tableau III ci-dessous ; ils représentent les moyennes des résultats de trois essais, c'est-à-dire des essais effectués avec trois jeux de trois séries de cinq éprouvettes.

Figure imgb0003
After drying and application of the water-soluble paint under the conditions of Example 1, the three series of test pieces are treated as described in standard ASTM B 117. After 384 hours of exposure to salt spray, the results are examined. obtained using ASTM 1654-61. These results are shown in Table III below; they represent the means of the results of three tests, that is to say tests carried out with three sets of three series of five test pieces.
Figure imgb0003

Ces résultats confirment les conclusions formulées à l'exemple 1.These results confirm the conclusions made in Example 1.

Exemple 4Example 4

On utilise toujours des éprouvettes constituées par des panneaux en « acier laminé à froid de qualité courante d'épaisseur 8/10 mm et mesurant 150 x 70 mm. Ces éprouvettes sont soigneusement dégraissées au trichloréthylène puis à l'acétone avant d'être traitées comme suit :

  • - dégraissage au jet au moyen d'une composition de dégraissage alcalin dans les conditions de l'exemple 3,
  • - rinçage à l'eau du robinet :
    • - temps : 10 secondes au trempé
    • - température : ambiante,
  • - conversion phosphatante au jet dans les conditions de l'exemple 3.
Always use test pieces made up of panels of "cold rolled steel of current quality, thickness 8/10 mm and measuring 150 x 70 mm. These test pieces are carefully degreased with trichlorethylene and then with acetone before being treated as follows:
  • - degreasing with a jet using an alkaline degreasing composition under the conditions of Example 3,
  • - rinsing with tap water:
    • - time: 10 seconds by soaking
    • - ambient temperature,
  • - phosphating jet conversion under the conditions of Example 3.

On obtient un revêtement de phosphate de zinc dont le poids de couche varie entre 2 et 3 g/m2.A zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .

On traite trois jeux de cinq séries de cinq éprouvettes dans les conditions de l'exemple 2.Three sets of five sets of five test pieces are treated under the conditions of Example 2.

On soumet toutes les éprouvettes au test du brouillard salin (norme ASTM B 117). Après 384 heures de brouillard salin, on examine les résultats obtenus, en utilisant les données de la norme ASTM D 1654-61. Ces résultats sont indiqués dans le tableau IV ci-dessous ; ils représentent les moyennes des résultats obtenus avec les trois jeux.
(Voir tableau IV page 9)All the test pieces are subjected to the salt spray test (standard ASTM B 117). After 384 hours of salt spray, the results obtained are examined, using data from standard ASTM D 1654-61. These results are shown in Table IV below; they represent the averages of the results obtained with the three games.
(See table IV page 9)

Figure imgb0004
Ces résultats confirment les conclusions formulées à l'exemple 2.
Figure imgb0004
 These results confirm the conclusions made in Example 2.

On dispose ainsi, et ce quel que soit le mode de réalisation adopté, d'une composition et d'un procédé de traitement des surfaces métalliques phosphatées dont les caractéristiques et les avantages résultent clairement de ce qui précède.Whatever the embodiment adopted, there is thus a composition and a method for treating phosphated metal surfaces, the characteristics and advantages of which are clearly apparent from the above.

Claims (9)

1. A process for the treatment of phosphatised metallic surfaces in which, before the application of any paint layer, the phosphatised metallic surfaces is treated by being brought into contact with a composition containing titanium, characterised in that the composition contains trivalent titanium of a concentration of 0,01 to 2 g per litre and exhibits a pH of 2 to 7, the temperature of the composition being lower than 90 °C.
2. A process according to claim 1, characterised in that the surface is brought into contact with the composition by immersion and that this contact lasts from 10 to 60 seconds.
3. A process according to one of claims 1 and 2, characterised in that the composition used contains trivalent titanium of a concentration of 0.2 to 0.6 g per litre.
- 4. A process according to one of claims 1 to 3, characterised in that the temperature of the composition used is between 18 and 60 °C.
5. A process according to one of claims 1 to 4, characterised in that the composition used is prepared by dilution with water, from a concentrate containing from 10 to 50 g trivalent titanium per litre.
6. A process according to one of claims 1 to 5, characterised in that the composition used is prepared by dilution with water, from a concentrate containing at least one surface-active agent and at least one stabilizing agent.
7. A process according to claim 6, characterised in that the composition used is prepared by dilution with water, from a concentrate containing :
- from 0.001 to 0.02 g per litre of surface-active agents chosen from the sodium alkylsulphonates and ethoxylated hydrocarbons,
- from 1 to 500 mg per litre of stabilizing agent chosen from pyrogallol and hydroquinone.
8. A process according to one of claims 1 to 7, characterised in that the trivalent titanium which must be included in the composition used is prepared in situ and before the application of the composition to the phosphatised metallic surfaces by bringing the tetravalent titanium into contact with a reducing agent, the composition then being regenerated into trivalent titanium during the process of-the treatment of the phosphatised surfaces, by bringing a fraction obtained from the composition into contact with the above reducing means in such a way that the concentration of the composition in trivalent titatium compounds is maintained in a proportion of 0.2 to 0.6 g trivalent titanium per litre.
9. A process according to claim 8, characterised in that the means of reducing the tetravalent titanium into trivalent titanium is either a metal reducing agent or a chemical reducing agent which is placed in a column, or an electrolysis cell.
EP83400204A 1982-01-29 1983-01-28 Composition and process for treating phosphated metallic surfaces Expired EP0085626B1 (en)

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Application Number Priority Date Filing Date Title
AT83400204T ATE23574T1 (en) 1982-01-29 1983-01-28 COMPOSITION AND METHOD OF TREATMENT OF PHOSPHATEATED METAL SURFACES.

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FR8201476A FR2520758A1 (en) 1982-01-29 1982-01-29 COMPOSITION AND METHOD FOR THE TREATMENT OF PHOSPHATE METAL SURFACES
FR8201476 1982-01-29

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AU2448684A (en) * 1983-03-02 1984-09-06 Parker Chemical Company Metal treatment before phosphate coating
DE3400339A1 (en) * 1984-01-07 1985-08-29 Gerhard Collardin GmbH, 5000 Köln METHOD FOR REPASSIVATING PHOSPHATED METAL SURFACES USING SOLUTIONS CONTAINING NICKEL AND / OR COPPER CATIONS
US5073196A (en) * 1989-05-18 1991-12-17 Henkel Corporation Non-accelerated iron phosphating
DE4031817A1 (en) * 1990-10-08 1992-04-09 Henkel Kgaa METHOD FOR PASSIVATING POST-TREATMENT OF PHOSPHATED METAL SURFACES
US5128211A (en) * 1991-02-28 1992-07-07 Diversey Corporation Aluminum based phosphate final rinse

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FR1388662A (en) * 1962-10-15 1965-02-12 Parker Ste Continentale Method and solution for the treatment of metal surfaces provided with a chemical coating
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US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
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EP0085626A1 (en) 1983-08-10
DE3367630D1 (en) 1987-01-02
ATE23574T1 (en) 1986-11-15
CA1197674A (en) 1985-12-10
US4497666A (en) 1985-02-05
JPS58136781A (en) 1983-08-13
FR2520758B1 (en) 1984-04-27

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