EP0433118B1 - Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath - Google Patents

Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath Download PDF

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Publication number
EP0433118B1
EP0433118B1 EP90403233A EP90403233A EP0433118B1 EP 0433118 B1 EP0433118 B1 EP 0433118B1 EP 90403233 A EP90403233 A EP 90403233A EP 90403233 A EP90403233 A EP 90403233A EP 0433118 B1 EP0433118 B1 EP 0433118B1
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EP
European Patent Office
Prior art keywords
bath
ions
acid
ion
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP90403233A
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German (de)
French (fr)
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EP0433118A1 (en
Inventor
Joseph Schapira
Patrick Droniou
Patrice Adrien Jules Pelletier
Man Tik Ho
Didier Raimond Charles Pernes
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Compagnie Francaise de Produits Industriels SA
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Compagnie Francaise de Produits Industriels SA
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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • C23C22/182Orthophosphates containing manganese cations containing also zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/17Orthophosphates containing zinc cations containing also organic acids
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/46Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
    • C23C22/47Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates containing also phosphates

Definitions

  • the subject of the invention is a process for the chemical conversion of metallic substrates, in particular based on iron or zinc-plated steel, with a view to increasing their resistance to corrosion, their ability to deformation or simultaneously both.
  • These treatments can be carried out on the substrates to be treated by spraying or by immersion.
  • the substrates thus treated can be used as they are or else receive a subsequent application of lubricant, protective oil or paint.
  • a phosphating bath it is possible for a phosphating bath to contain from 2 to 50 g / l of aliphatic polyhydroxymonocarboxylic acid, such as gluconic acid.
  • the layer weight can be increased by adding an organic polyacid in an accelerated chlorate phosphating bath and practically free of ferrous ions.
  • the object of the invention is, above all, to remedy this drawback and to provide a chemical conversion bath which, while providing performance equivalent to that of the process described in patent FR-A-2,531,457, can be regenerated by continued.
  • the chemical conversion process is characterized in that it comprises the implementation, at the time of the phosphating step proper, of a zinc conversion bath free of chlorate ions and of a temperature from 70 to 99 ° C, containing from 0.5 to 25 g / l of zinc ion, from 5 to 40 g / l of phosphate ions, from 2 to 40 g / l of nitrate ions as well as from 0 , 1 to 15 g / l of iron ions and 21 to 100 g / l of at least one organic chelating agent consisting of a polycarboxylic acid chosen from the group comprising oxalic, malic, glutamic, tartaric, aspartic, malonic acids and citric acid, or a salt thereof.
  • the salts of the above polycarboxylic acids are chosen from those of alkali metals, alkaline earth metals, ammonium, iron, zinc, manganese, molybdenum, cobalt and nickel.
  • the zinc ion present in an amount of 0.5 to 25 g / l, can be introduced in any suitable way, and in particular in the form of its salts with nitric, phosphoric, carbonic, gluconic, citric acids. , or in the form of its oxide. It can be combined with all the metals commonly used in a phosphating bath such as, for example, manganese, nickel, cobalt, calcium, magnesium.
  • the iron ions present in a proportion of 0.1 to 15 g / l, can be introduced either by dissolving iron in the solid state, such as for example iron wool, massive pieces or scrap steel parts, either thanks to iron salts with sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids; it can be the ferrous ion, the ferric ion or a mixture of the two.
  • the phosphate ions on the one hand and the nitrate ions on the other hand are each present in the bath in a proportion of up to 40 g / l.
  • the bath used in accordance with the invention may also contain hydrofluoric, fluosilicic or fluoboric acids or more of them to regulate the balance between the pickling of the support by the acid solution and the growth of the crystalline layer.
  • the coatings produced by implementing the process according to the invention provide, in the sense of the test according to ASTM B-117, a resistance to salt spray comparable to that obtained according to patent FR-A-2,531,457 while allowing continuous regeneration.
  • the substrates treated by implementing the process according to the invention can be stored or used without further protection, but it is also possible to paint these substrates in order to further increase their resistance to corrosion; they can possibly be deformed cold after a possible operation of applying a lubricant.
  • it contains from 0.02 to 3 g / l of nickel, cobalt or copper.
  • the chemical conversion bath used in accordance with the invention is applied by spraying onto the metal substrate to be treated or by immersion of the substrate in the bath, immersion being preferred.
  • the process is simplified by eliminating the chromic passivation and protection steps, subsequent to the chemical phosphating conversion. and necessary in the processes of the prior art.
  • a conversion bath is constituted according to the prior art containing, in addition to water, the following ions: Zn++: 6 g / l Total PO4: 16.7 g / l NO 3 - : 10 g / l Total Fe: 1 g / l Ni++: 0.2 g / l
  • the plates thus prepared are subjected to 5% salt spray test (according to ASTM B-117).
  • a conversion bath is prepared for implementation in the process according to the invention by adding to the bath according to Example 1 an amount of 30 g / l of citric acid.
  • the free acidity of the new bath is brought to 18/19 points.
  • the cold-rolled steel plates are treated in the same way as in Example 1 and a 10% rusting is obtained locally after 150 hours of exposure.
  • Citric acid content of the bath (g / l) Salt spray test Beginning of rust Rust at 50% 1 0 immediate less than 1 hour 2 10 5 a.m. 8 a.m. 3 30 sailing after 100 h some rust spots after 150 h
  • the purpose of this example is to show the possibility of applying the process to various industrial parts. Parts of HRC 55 case hardened steel (0.55% carbon at heart) and mild steel XC 10 (0.1% carbon) are treated.
  • composition A Composition A
  • the treatment sequence is the same as that described in Example 1, with the exception of step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out in an aqueous solution containing 7.75% v / v d '75% phosphoric acid, for 2 minutes at a temperature of 60 ° C.
  • the bath is heated to 95 ° C. and the free acidity is brought to a value of 20 points with sodium hydroxide.
  • Cold rolled steel sheets of the ZES type are treated in a sequence identical to that described in Example 1 (the conversion step using the above-mentioned bath), with the exception of steps 3 and 4 which are omitted . After treatment, the sheets are tested in a salt spray test (according to ASTM B-117) and, after an exposure of 400 h, no development of rust is observed.

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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)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemically Coating (AREA)
  • Catalysts (AREA)

Abstract

Chemical conversion process characterised in that it comprises the use, at the time of the actual phosphatising stage, of a zinc conversion bath containing phosphate and nitrate ions as well as ferrous or ferric ions and from approximately 21 to approximately 100 g/l of at least one organic chelating agent.

Description

L'invention a pour objet un procédé de conversion chimique de substrats métalliques, notamment à base de fer ou d'acier zingué, en vue d'accroître leur résistance à la corrosion, leur aptitude à la déformation ou simultanément les deux.The subject of the invention is a process for the chemical conversion of metallic substrates, in particular based on iron or zinc-plated steel, with a view to increasing their resistance to corrosion, their ability to deformation or simultaneously both.

Elle vise aussi un bain de conversion chimique propre à être mis en oeuvre dans ce procédé, ainsi qu'un concentré pour la préparation du bain.It also relates to a chemical conversion bath suitable for being used in this process, as well as a concentrate for the preparation of the bath.

Il est connu de réaliser la conversion chimique de substrats métalliques par des traitements classiques de phosphatation cristalline qui conduisent au dépôt, à la surface du métal, d'une couche de phosphates insolubles.It is known to carry out the chemical conversion of metallic substrates by conventional crystalline phosphating treatments which lead to the deposition, on the surface of the metal, of a layer of insoluble phosphates.

Les traitements de phosphatation cristalline connus mettent généralement en oeuvre des bains acides qui contiennent au moins les constituants suivants:

  • l'acide orthophosphorique H₃PO₄
  • un ion phosphate primaire H₂PO4-
  • un ou plusieurs métaux choisis parmi le zinc ou le fer, le manganèse, le nickel, le cuivre, le cobalt, le calcium,
  • au moins un accélérateur constitué par un agent oxydant tel que les ions chlorate, nitrate, le nitrite ou le métanitrobenzène sulfonate de sodium.
The known crystalline phosphating treatments generally use acid baths which contain at least the following constituents:
  • orthophosphoric acid H₃PO₄
  • a primary phosphate ion H₂PO 4 -
  • one or more metals chosen from zinc or iron, manganese, nickel, copper, cobalt, calcium,
  • at least one accelerator consisting of an oxidizing agent such as sodium chlorate, nitrate, nitrite or metanitrobenzene sulfonate.

Ces traitements peuvent être effectués sur les substrats à traiter par pulvérisation ou par immersion.These treatments can be carried out on the substrates to be treated by spraying or by immersion.

Ils s'insèrent dans une séquence d'étapes opérationnelles pouvant comprendre:

  • une ou plusieurs étapes de dégraissage,
  • une ou plusieurs étapes de rinçage,
  • éventuellement, une ou plusieurs étapes de décapage, puis de rinçage,
  • éventuellement, une étape de conditionnement de surface,
  • l'étape de phosphatation proprement dite,
  • une ou plusieurs étapes de rinçage,
  • éventuellement une étape de passivation, généralement en milieu chromique et une étape de rinçage,
  • éventuellement, une étape de séchage ou d'étuvage.
They are part of a sequence of operational steps which may include:
  • one or more degreasing steps,
  • one or more rinsing steps,
  • possibly one or more stages of pickling, then rinsing,
  • optionally, a surface conditioning step,
  • the actual phosphating step,
  • one or more rinsing steps,
  • possibly a passivation step, generally in a chromic medium and a rinsing step,
  • optionally, a drying or baking step.

Les substrats ainsi traités peuvent être utilisés tels quels ou bien recevoir une application ultérieure de lubrifiant, d'huile de protection ou de peinture.The substrates thus treated can be used as they are or else receive a subsequent application of lubricant, protective oil or paint.

La nature et la composition de la couche de phosphates insolubles obtenue dépendent essentiellement:

  • de la nature du substrat,
  • de la composition du bain de phosphatation,
  • du mode d'application du produit (aspersion ou immersion),
  • des étapes de prétraitement.
The nature and composition of the insoluble phosphate layer obtained essentially depends on:
  • the nature of the substrate,
  • the composition of the phosphating bath,
  • the method of application of the product (sprinkling or immersion),
  • pretreatment steps.

L'art antérieur décrit divers perfectionnements aux bains de conversion chimique visant à améliorer les performances de ceux-ci.The prior art describes various improvements to chemical conversion baths aimed at improving their performance.

Ainsi, selon le brevet FR-A-1 362 202, on obtient une amélioration de la tenue à la corrosion des couches de phosphatation par ajout d'une faible quantité (jusqu' à 2%) et préférentiellement comprise entre 0,5 et 1,5%) d'agents complexants organiques; des performances de tenue au brouillard salin ASTM B-117 inférieures ou égales à 25 heures sont rapportées dans ce brevet.Thus, according to patent FR-A-1 362 202, an improvement in the corrosion resistance of the phosphating layers is obtained by adding a small amount (up to 2%) and preferably between 0.5 and 1 , 5%) organic complexing agents; ASTM B-117 salt spray performance less than or equal to 25 hours is reported in this patent.

Selon le brevet US-A-3 116 178, il est possible de faire comporter à un bain de phosphatation de 2 à 50 g/l d'acide polyhydroxymonocarboxylique aliphatique, tel que l'acide gluconique.According to US Pat. No. 3,116,178, it is possible for a phosphating bath to contain from 2 to 50 g / l of aliphatic polyhydroxymonocarboxylic acid, such as gluconic acid.

Selon le brevet FR-A-1 585 660, le poids de couche peut être accru par addition d'un polyacide organique dans un bain de phosphatation accéléré au chlorate et à peu près exempt d'ions ferreux.According to patent FR-A-1,585,660, the layer weight can be increased by adding an organic polyacid in an accelerated chlorate phosphating bath and practically free of ferrous ions.

Enfin, selon le brevet FR-A-2 531 457, l'association d'un agent chélatant et d'un polyphosphate soluble permet d'obtenir des couches dont la tenue à la corrosion est sensiblement améliorée, des tenues au brouillard salin pouvant atteindre 310 heures étant mentionnées en rapport avec des pièces uniquement phosphatées.Finally, according to patent FR-A-2 531 457, the combination of a chelating agent and a soluble polyphosphate makes it possible to obtain layers whose resistance to corrosion is appreciably improved, resistance to salt spray being able to reach 310 hours being mentioned in connection with phosphate-only parts.

Le brevet français en question rappelle qu'un excès de polyphosphates peut empêcher la formation de la couche cristalline et propose de faire mûrir les bains revendiqués par évolution du pH avant mise en oeuvre.The French patent in question recalls that an excess of polyphosphates can prevent the formation of the crystalline layer and proposes to cure the baths claimed by evolution of the pH before implementation.

Le mûrissement en question n'étant pas instantané, les opérations de régénération du bain sont obligatoirement discontinues, ce qui constitue un inconvénient, la plupart des bains industriels étant régénérés en continu.Since the ripening in question is not instantaneous, the bath regeneration operations are necessarily discontinuous, which constitutes a drawback, most industrial baths being regenerated continuously.

L'invention a pour but, surtout, de remédier à cet inconvénient et de fournir un bain de conversion chimique qui, tout en procurant des performances équivalentes à celles du procédé décrit dans le brevet FR-A-2 531 457, peut être régénéré en continu.The object of the invention is, above all, to remedy this drawback and to provide a chemical conversion bath which, while providing performance equivalent to that of the process described in patent FR-A-2,531,457, can be regenerated by continued.

En conséquence, le procédé de conversion chimique est caractérisé par le fait qu'il comporte la mise en oeuvre, au moment de l'étape de phosphatation proprement dite, d'un bain de conversion au zinc exempt d'ions chlorate et d'une température de 70 à 99°C, contenant de 0,5 à 25 g/l d'ion zinc, de 5 à 40 g/l d'ions phosphates, de 2 à 40 g/l d'ions nitrate ainsi que de 0,1 à 15 g/l d'ions fer et de 21 à 100 g/l d'au moins un agent chélatant organique constitué par un acide polycarboxylique choisi dans le groupe comprenant les acides oxalique, malique, glutamique, tartrique, aspartique, malonique et l'acide citrique, ou un de ses sels.Consequently, the chemical conversion process is characterized in that it comprises the implementation, at the time of the phosphating step proper, of a zinc conversion bath free of chlorate ions and of a temperature from 70 to 99 ° C, containing from 0.5 to 25 g / l of zinc ion, from 5 to 40 g / l of phosphate ions, from 2 to 40 g / l of nitrate ions as well as from 0 , 1 to 15 g / l of iron ions and 21 to 100 g / l of at least one organic chelating agent consisting of a polycarboxylic acid chosen from the group comprising oxalic, malic, glutamic, tartaric, aspartic, malonic acids and citric acid, or a salt thereof.

Les sels des susdits acides polycarboxyliques sont choisis parmi ceux des métaux alcalins, alcalino-terreux, d'ammonium, de fer, de zinc, de manganèse, de molybdène, de cobalt et de nickel.The salts of the above polycarboxylic acids are chosen from those of alkali metals, alkaline earth metals, ammonium, iron, zinc, manganese, molybdenum, cobalt and nickel.

L'ion zinc, présent à raison d'une proportion de 0,5 à 25 g/l, peut être introduit de toute manière appropriée, et notamment sous la forme de ses sels avec les acides nitrique, phosphorique, carbonique, gluconique, citrique, ou sous la forme de son oxyde. Il peut être associé à tous les métaux couramment utilisés dans un bain de phosphatation comme, par exemple, le manganèse, le nickel, le cobalt, le calcium, le magnésium.The zinc ion, present in an amount of 0.5 to 25 g / l, can be introduced in any suitable way, and in particular in the form of its salts with nitric, phosphoric, carbonic, gluconic, citric acids. , or in the form of its oxide. It can be combined with all the metals commonly used in a phosphating bath such as, for example, manganese, nickel, cobalt, calcium, magnesium.

Les ions fer, présents à raison d'une proportion de 0,1 à 15 g/l, peuvent être introduits soit par dissolution de fer à l'état solide, comme par exemple de la paille de fer, des pièces massives ou des rebuts de pièces en acier, soit grâce à des sels de fer avec les acides sulfurique, chlorhydrique, fluorhydrique, phosphorique ou nitrique; il peut s'agir de l'ion ferreux, de l'ion ferrique ou d'un mélange des deux.The iron ions, present in a proportion of 0.1 to 15 g / l, can be introduced either by dissolving iron in the solid state, such as for example iron wool, massive pieces or scrap steel parts, either thanks to iron salts with sulfuric, hydrochloric, hydrofluoric, phosphoric or nitric acids; it can be the ferrous ion, the ferric ion or a mixture of the two.

Les ions phosphates d'une part et nitrate d'autre part sont présents chacun dans le bain en une proportion pouvant atteindre 40 g/l.The phosphate ions on the one hand and the nitrate ions on the other hand are each present in the bath in a proportion of up to 40 g / l.

Le bain utilisé conformément à l'invention peut également contenir les acides fluorhydrique, fluosilicique ou fluoborique ou plusieurs d'entre eux pour régler l'équilibre entre le décapage du support par la solution acide et la croissance de la couche cristalline.The bath used in accordance with the invention may also contain hydrofluoric, fluosilicic or fluoboric acids or more of them to regulate the balance between the pickling of the support by the acid solution and the growth of the crystalline layer.

Le bain utilisé conformément à l'invention est préparé par dilution à partir d'un concentré caractérisé par le fait qu'il contient

  • jusqu'à 500 g/l d'acide polycarbonylique, notamment d'ion citrate
  • jusqu'à 200 g/l d'ions phosphate
  • jusqu'à 125 g/l d'ions zinc
  • jusqu'à 200 g/l d'ion nitrate.
The bath used according to the invention is prepared by dilution from a concentrate characterized in that it contains
  • up to 500 g / l polycarbonylic acid, especially citrate ion
  • up to 200 g / l of phosphate ions
  • up to 125 g / l zinc ions
  • up to 200 g / l of nitrate ion.

Les revêtements produits par mise en oeuvre du procédé conforme à l'invention procurent, au sens du test selon la norme ASTM B-117, une résistance au brouillard salin comparable à celle obtenue selon le brevet FR-A-2.531.457 tout en autorisant une régénération continue.The coatings produced by implementing the process according to the invention provide, in the sense of the test according to ASTM B-117, a resistance to salt spray comparable to that obtained according to patent FR-A-2,531,457 while allowing continuous regeneration.

Les substrats traités par mise en oeuvre du procédé conforme à l'invention peuvent être stockés ou utilisés sans protection ultérieure mais il est possible également de peindre ces substrats afin d'augmenter encore leur tenue à la corrosion; ils peuvent éventuellement être déformés à froid après une opération éventuelle d'application d'un lubrifiant.The substrates treated by implementing the process according to the invention can be stored or used without further protection, but it is also possible to paint these substrates in order to further increase their resistance to corrosion; they can possibly be deformed cold after a possible operation of applying a lubricant.

Suivant un mode de réalisation avantageux du procédé conforme à l'invention, le bain mis en oeuvre contient :

  • de 5 à 20 g/l d'ions phosphates
  • de 21 à 60 g/l d'ion citrique
  • de 2 à 40 g/l d'ion nitrate
  • de 2 à 10 g/l d'ion zinc
  • de 0,1 à 15 g/l de fer.
According to an advantageous embodiment of the process according to the invention, the bath used contains:
  • from 5 to 20 g / l of phosphate ions
  • from 21 to 60 g / l of citric ion
  • from 2 to 40 g / l of nitrate ion
  • from 2 to 10 g / l of zinc ion
  • 0.1 to 15 g / l of iron.

Suivant une variante, il contient de 0,02 à 3 g/l de nickel, de cobalt ou de cuivre.According to a variant, it contains from 0.02 to 3 g / l of nickel, cobalt or copper.

Le bain de conversion chimique mis en oeuvre conformément à l'invention est appliqué par pulvérisation sur le substrat métallique à traiter ou par immersion du substrat dans le bain, l'immersion étant préférée.The chemical conversion bath used in accordance with the invention is applied by spraying onto the metal substrate to be treated or by immersion of the substrate in the bath, immersion being preferred.

Le procédé de conversion chimique conforme à l'invention comprend un ensemble d'étapes de traitement, à savoir:

  • une ou plusieurs étapes de dégraissage,
  • une ou plusieurs étapes de rinçage,
  • éventuellement, une ou plusieurs étapes d'activation ou de décapage,
  • une étape de rinçage,
  • l'étape de conversion chimique proprement dite par mise en oeuvre du bain conforme à l'invention,
  • une étape de rinçage,
  • une étape de séchage.
The chemical conversion process according to the invention comprises a set of treatment steps, namely:
  • one or more degreasing steps,
  • one or more rinsing steps,
  • possibly one or more stages of activation or pickling,
  • a rinsing step,
  • the chemical conversion stage proper by implementing the bath according to the invention,
  • a rinsing step,
  • a drying step.

De par la tenue exceptionnelle à la corrosion sèche des couches de phosphatation obtenues avec le bain mis en oeuvre conformément à l'invention, le procédé se trouve simplifié par la suppression des étapes de passivation chromique et de protection, postérieures à la conversion chimique de phosphatation et nécessaires dans les procédés de l'art antérieur.Due to the exceptional resistance to dry corrosion of the phosphating layers obtained with the bath used in accordance with the invention, the process is simplified by eliminating the chromic passivation and protection steps, subsequent to the chemical phosphating conversion. and necessary in the processes of the prior art.

L'invention sera bien comprise grâce aux exemples non limitatifs qui suivent et dans lesquels sont indiqués des modes de réalisation avantageux du bain mis en oeuvre conformément à l'invention.The invention will be better understood thanks to the nonlimiting examples which follow and in which are indicated advantageous embodiments of the bath used in accordance with the invention.

EXEMPLE 1 (comparatif)EXAMPLE 1 (comparative)

On constitue un bain de conversion selon l'art antérieur contenant, outre l'eau, les ions suivants: Zn⁺⁺ : 6 g/l PO₄ total : 16,7 g/l NO3- : 10 g/l Fe total : 1 g/l Ni⁺⁺ : 0,2 g/l A conversion bath is constituted according to the prior art containing, in addition to water, the following ions: Zn⁺⁺: 6 g / l Total PO₄: 16.7 g / l NO 3 - : 10 g / l Total Fe: 1 g / l Ni⁺⁺: 0.2 g / l

On porte sa température à 95°C; l'acidité libre est amenée dans la zone de fonctionnement à 8,0 points avec de la soude concentrée (l'acidité libre est déterminée en titrant 10 ml de solution froide avec une solution de soude N/10 jusqu'à pH = 3,6).Its temperature is brought to 95 ° C; the free acidity is brought into the operating zone at 8.0 points with concentrated soda (the free acidity is determined by titrating 10 ml of cold solution with an N / 10 soda solution until pH = 3, 6).

Des plaquettes d'acier laminé à froid à 0,02% de carbone de qualité ZES couramment utilisée dans l'industrie automobile, de dimensions 150 mm x 140 mm, sont soumises à la gamme de traitement suivante:

Etape 1:
Dégraissage alcalin en solution aqueuse à base des dégraissants commercialisés par la Société Demanderesse sous les marques RIDOLINE 1550 CF/2 (à 1,5% v/v) et RIDOSOL 550 CF (1,5% v/v).
Température: 60°C.
Temps de traitement: 3 minutes.
Etape 2:
Rinçage froid à l'eau courante pendant 2 minutes.
Etape 3:
Décapage nitrique
Décapant: acide nitrique à 60% en solution aqueuse (10% v/v).
Température: 20°C.
Temps de traitement: 10 secondes.
Etape 4:
Rinçage froid à l'eau courante pendant 1 minute.
Etape 5:
Conversion proprement dite à 95°C pendant 30 minutes.
Etape 6:
Rinçage à l'eau froide courante pendant 10 secondes.
Etape 7:
Séchage à l'étuve à une température d'environ 95°C pendant 10 minutes.
Cold rolled steel plates with 0.02% carbon of ZES quality commonly used in the automotive industry, dimensions 150 mm x 140 mm, are subjected to the following treatment range:
Step 1 :
Alkaline degreasing in aqueous solution based on degreasers sold by the Applicant Company under the brands RIDOLINE 1550 CF / 2 (at 1.5% v / v) and RIDOSOL 550 CF (1.5% v / v).
Temperature: 60 ° C.
Processing time: 3 minutes.
Step 2 :
Cold rinse with running water for 2 minutes.
Step 3 :
Nitric pickling
Stripper: 60% nitric acid in aqueous solution (10% v / v).
Temperature: 20 ° C.
Processing time: 10 seconds.
Step 4 :
Cold rinse with running water for 1 minute.
Step 5:
Conversion proper at 95 ° C for 30 minutes.
Step 6 :
Rinse with running cold water for 10 seconds.
Step 7 :
Dry in an oven at a temperature of around 95 ° C for 10 minutes.

Les plaquettes ainsi préparées sont soumises à l'épreuve du brouillard salin à 5% (selon la norme ASTM B-117).The plates thus prepared are subjected to 5% salt spray test (according to ASTM B-117).

Après 1 heure d'exposition, on a un enrouillement de 50% très homogène.After 1 hour of exposure, there is a very homogeneous 50% rustling.

EXEMPLE 2 (comparatif)EXAMPLE 2 (comparative)

On prépare un bain de conversion selon l'art antérieur en ajoutant au bain selon l'exemple 1 une quantité de 10 g/l d'acide citrique. L'acidité libre du bain est amenée à 15,0 points. On réalise le même traitement que précédemment sur les mêmes plaques d'acier laminé à froid. On obtient, au bout de 8 heures d'exposition, un enrouillement homogène de 50%.Preparing a conversion bath according to the prior art by adding to the bath according to Example 1 an amount of 10 g / l of citric acid. The free acidity of the bath is brought to 15.0 points. The same treatment is carried out as above on the same cold-rolled steel plates. Obtained, after 8 hours of exposure, a homogeneous scalding of 50%.

EXEMPLE 3EXAMPLE 3

On prépare un bain de conversion pour mise en oeuvre dans le procédé conforme à l'invention en ajoutant au bain selon l'exemple 1 une quantité de 30 g/l d'acide citrique. L'acidité libre du nouveau bain est amenée à 18/19 points. On traite de la même manière que dans l'exemple 1 des plaques d'acier laminé à froid analogues et l'on obtient localement, au bout de 150 heures d'exposition, un enrouillement de 10%. TABLEAU I Exemple No. Teneur du bain en acide citrique (g/l) Test au brouillard salin Début de rouille Rouille à 50% 1 0 immédiat moins de 1 h 2 10 5 h 8 h 3 30 voile après 100 h quelques points de rouille après 150 h A conversion bath is prepared for implementation in the process according to the invention by adding to the bath according to Example 1 an amount of 30 g / l of citric acid. The free acidity of the new bath is brought to 18/19 points. The cold-rolled steel plates are treated in the same way as in Example 1 and a 10% rusting is obtained locally after 150 hours of exposure. TABLE I Example No. Citric acid content of the bath (g / l) Salt spray test Beginning of rust Rust at 50% 1 0 immediate less than 1 hour 2 10 5 a.m. 8 a.m. 3 30 sailing after 100 h some rust spots after 150 h

EXEMPLE 4EXAMPLE 4

Cet exemple a pour but de montrer la possibilité d'appliquer le procédé à des pièces industrielles variées. On réalise le traitement de pièces en acier cémenté HRC 55 (à 0,55% de carbone à coeur) et en acier doux XC 10 (à 0,1% de carbone).The purpose of this example is to show the possibility of applying the process to various industrial parts. Parts of HRC 55 case hardened steel (0.55% carbon at heart) and mild steel XC 10 (0.1% carbon) are treated.

On prépare les trois compositions suivantes:The following three compositions are prepared:

Composition AComposition A

On mélange 56,7 g d'eau, 20 g d'acide citrique et 22,3 g d'acide phosphorique à 75%. On dissout dans ce mélange 1 g de fer métallique.56.7 g of water, 20 g of citric acid and 22.3 g of 75% phosphoric acid are mixed. 1 g of metallic iron is dissolved in this mixture.

Composition BComposition B

On mélange 46,7 g d'eau, 30 g d'acide citrique et 22,3 g d'acide phosphorique à 75%. On dissout dans ce mélange 1 g de fer métallique.46.7 g of water, 30 g of citric acid and 22.3 g of 75% phosphoric acid are mixed. 1 g of metallic iron is dissolved in this mixture.

Composition CComposition C

On dissout dans un mélange contenant 74,8 g d'eau et 16,7 g d'acide nitrique à 60%, 7,5 g d'oxyde de zinc et 1 g de nitrate de nickel à 20% de nickel.Dissolve in a mixture containing 74.8 g of water and 16.7 g of 60% nitric acid, 7.5 g of zinc oxide and 1 g of nickel nitrate of 20% nickel.

La séquence de traitement est la même que celle décrite dans l'exemple 1, à l'exception de l'étape 3, le décapage nitrique étant remplacé par un décapage phosphorique aqueux réalisé dans une solution aqueuse contenant 7,75% v/v d'acide phosphorique à 75%, pendant 2 minutes à une température de 60°C.The treatment sequence is the same as that described in Example 1, with the exception of step 3, the nitric pickling being replaced by an aqueous phosphoric pickling carried out in an aqueous solution containing 7.75% v / v d '75% phosphoric acid, for 2 minutes at a temperature of 60 ° C.

Les bains mis en oeuvre au moment de l'étape de conversion proprement dite sont constitués comme suit:

. Bain 1 :
- 800 ml d'eau
- 100 ml de composition A
- 100 ml de composition C
. Bain 2 :
- 800 ml d'eau
- 100 ml de composition B
- 100 ml de composition C.
The baths used at the time of the conversion step proper are constituted as follows:
. Bath 1:
- 800 ml of water
- 100 ml of composition A
- 100 ml of composition C
. Bath 2:
- 800 ml of water
- 100 ml of composition B
- 100 ml of composition C.

Deux séries de pièces en acier, respectivement de qualité XC 10 et HRC 55, ayant été soumises à la séquence de traitement selon l'exemple 1 avec mise en oeuvre du bain 1 pour les pièces en acier XC 10 et du bain 2 pour les pièces en acier HRC 55, sont soumises au test du brouillard salin selon norme ASTM B-117 et on note le temps au bout duquel apparaît la rouille rouge.Two series of steel parts, of quality XC 10 and HRC 55 respectively, having been subjected to the treatment sequence according to Example 1 with the use of bath 1 for steel parts XC 10 and bath 2 for parts made of HRC 55 steel, are subjected to the salt spray test according to standard ASTM B-117 and the time after which the red rust appears.

Les résultats sont consignés dans le tableau II. TABLEAU II Pièces en acier de type Traitement selon l'exemple 1 avec le bain 1 (20 g/l d'acide citrique) le bain 2 (30 g/l d'acide citrique) XC 10 début de rouille après 400 h pas de rouille après 700 h HRC 55 début de rouille après 10 h début de rouille après 40 h The results are reported in Table II. TABLE II Type steel parts Treatment according to Example 1 with bath 1 (20 g / l citric acid) bath 2 (30 g / l citric acid) XC 10 start of rust after 400 h no rust after 700 h HRC 55 rust starts after 10 a.m. rust begins after 40 h

On constate que le fait d'utiliser dans le bain de conversion une concentration supérieure à 20 g/l d'ion citrate apporte un gain significatif sur le plan de la résistance à la corrosion, même sur un acier difficile à traiter comme un acier cémenté HRC 55.It is found that the fact of using in the conversion bath a concentration greater than 20 g / l of citrate ion brings a significant gain in terms of corrosion resistance, even on a steel which is difficult to treat like a case hardened steel. HRC 55.

EXEMPLE 5EXAMPLE 5

On prépare un bain aqueux contenant (en poids/ volume):

  • 25 g/l d'acide citrique
  • 10 g/l d'ion NO₃
  • 16,7 g/l d'ion PO₄
  • 1 g/l d'ion Fe⁺⁺
  • 6 g/l d'ion Zn⁺⁺
  • 1 g/l d'ion Mn⁺⁺.
An aqueous bath is prepared containing (by weight / volume):
  • 25 g / l citric acid
  • 10 g / l NO₃ ion
  • 16.7 g / l PO₄ ion
  • 1 g / l of Fe⁺⁺ ion
  • 6 g / l of Zn⁺⁺ ion
  • 1 g / l of Mn⁺⁺ ion.

On chauffe le bain à 95°C et on amène l'acidité libre à une valeur de 20 points avec de la soude.The bath is heated to 95 ° C. and the free acidity is brought to a value of 20 points with sodium hydroxide.

On traite des tôles en acier laminé à froid du type ZES selon une séquence identique à celle décrite dans l'exemple 1 (l'étape de conversion mettant en oeuvre le susdit bain), à l'exception des étapes 3 et 4 qui sont supprimées. Après traitement, les tôles sont testées à l'épreuve du brouillard salin (selon ASTM B-117) et, après une exposition de 400 h, on n'observe aucun développement de rouille.Cold rolled steel sheets of the ZES type are treated in a sequence identical to that described in Example 1 (the conversion step using the above-mentioned bath), with the exception of steps 3 and 4 which are omitted . After treatment, the sheets are tested in a salt spray test (according to ASTM B-117) and, after an exposure of 400 h, no development of rust is observed.

Claims (2)

  1. Process for the chemical conversion characterized by the fact that it comprises the use, at the moment of the phosphatization step proper, of a zinc conversion bath free of chlorate ions and having a temperature from 70 to 99°c, the said bath containing from 0.5 to 25 g/l of zinc ion, from 5 to 40 g/l of phosphate ions, from 2 to 40 g/l of nitrate ions as well as from 0.1 to 15 g/l of iron ions and from 21 to 100 g/l of at least one organic chelating agent consisting of a polycarboxylic acid selected from the group comprising oxalic acid, malic acid, glutamic acid, tartaric acid, aspartic acid, malonic acid and citric acid, or one of its salts.
  2. Process according to claim 1, characterized by the fact that the bath used comprises:
    - from 5 to 20 g/l of phosphate ions
    - from 21 to 60 g/l of citric ions
    - from 2 to 40 g/l of nitrate ions
    - from 2 to 10 g/l of zinc ions
    - from 0,1 to 15 g/l of iron ions.
EP90403233A 1989-11-16 1990-11-15 Chemical metal substrate conversion process, bath used therefor and concentrate for preparing the bath Expired - Lifetime EP0433118B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8915042 1989-11-16
FR8915042A FR2654440B1 (en) 1989-11-16 1989-11-16 PROCESS FOR THE CHEMICAL CONVERSION OF METAL SUBSTRATES, BATH USED IN THIS PROCESS AND CONCENTRATE FOR THE PREPARATION OF THE BATH.

Publications (2)

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JP2968127B2 (en) * 1992-04-24 1999-10-25 日本パーカライジング株式会社 Acid displacement plating solution for zinc or galvanized steel sheet
JP2968147B2 (en) * 1993-04-07 1999-10-25 日本パーカライジング株式会社 Acid displacement plating solution composition for zinc-containing metal plated steel sheet
DE19733972A1 (en) * 1997-08-06 1999-02-11 Henkel Kgaa Alkaline band passivation
EP1875003B1 (en) * 2005-04-06 2013-03-06 REM Technologies, Inc. Superfinishing of high density carbide steel components
JP4845050B2 (en) * 2007-10-04 2011-12-28 ユケン工業株式会社 Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability
JP5225466B2 (en) * 2009-12-07 2013-07-03 新日鐵住金株式会社 Chromate-free precoated steel plate with excellent red rust corrosion resistance
WO2014039541A1 (en) * 2012-09-05 2014-03-13 North American Salt Company Methods and compositions to prevent caking of sodium chloride and prevent transition metal stains

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FR1243081A (en) * 1958-11-28 1960-10-07 Parker Ste Continentale Process for the phosphating of metals, in particular ferrous metals

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DE975008C (en) * 1952-08-06 1961-08-03 American Chem Paint Co Process for the production of phosphate coatings on zinc and its alloys
US3116178A (en) * 1961-05-29 1963-12-31 Lubrizol Corp Phosphating solutions
BE635970A (en) * 1962-11-13
FR1585660A (en) * 1967-10-18 1970-01-30
US3767476A (en) * 1971-08-31 1973-10-23 Us Army Method and composition for phosphatizing steel under pressure
SU1090761A1 (en) * 1982-07-19 1984-05-07 Московский Ордена Трудового Красного Знамени Вечерний Металлургический Институт Solution for catodic application of protective films to titanium alloys
DE3927613A1 (en) * 1989-08-22 1991-02-28 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES

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Publication number Priority date Publication date Assignee Title
FR1243081A (en) * 1958-11-28 1960-10-07 Parker Ste Continentale Process for the phosphating of metals, in particular ferrous metals

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ES2084680T3 (en) 1996-05-16
EP0433118A1 (en) 1991-06-19
CA2030126A1 (en) 1991-05-17
FR2654440B1 (en) 1993-07-30
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JPH03173778A (en) 1991-07-29
FR2654440A1 (en) 1991-05-17

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