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EP1963545B1 - Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches - Google Patents

Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches Download PDF

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Publication number
EP1963545B1
EP1963545B1 EP06847093A EP06847093A EP1963545B1 EP 1963545 B1 EP1963545 B1 EP 1963545B1 EP 06847093 A EP06847093 A EP 06847093A EP 06847093 A EP06847093 A EP 06847093A EP 1963545 B1 EP1963545 B1 EP 1963545B1
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EP
European Patent Office
Prior art keywords
mixture
acids
bath
eutectic
carboxylation
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English (en)
French (fr)
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EP1963545A1 (de
Inventor
Hervé Derule
Lydia Rachiele
Sophie Jacques
Nicole Genet
Jean Steinmetz
Emmanuel Rocca
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ArcelorMittal France SA
TotalEnergies Marketing Services SA
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ArcelorMittal France SA
Total Raffinage Marketing SA
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Priority to PL06847093T priority Critical patent/PL1963545T3/pl
Priority to EP06847093A priority patent/EP1963545B1/de
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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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon

Definitions

  • the invention relates to a method for the formation of conversion layers on a metal surface selected from zinc, iron, aluminum, copper, lead and their alloys, as well as galvanized, electrozinced, aluminized, coppered steels. , making it possible to produce at high speed conversion layers formed of very small crystals, from 1 to 20 ⁇ m.
  • the conversion baths essentially contain anions and cations capable of forming insoluble compounds with the dissolved metal of the surface.
  • the main conversion treatments applied to the steels are thus chromating treatments on galvanized steel (by dip galvanizing or electrogalvanizing) or aluminized, phosphating on unalloyed bare steels or coated steels, or even oxalation on alloy steels such as as stainless steels, for example.
  • the treated surface After being brought into contact with a conversion bath, the treated surface is generally rinsed to remove unreacted surface and / or treatment solution components, and this surface is dried, particularly to harden the coating layer. conversion and / or to improve its properties.
  • the conversion treatment may itself be preceded by a pretreatment, generally consisting of a preliminary degreasing and rinsing of the surface followed by a so-called refining operation using a pretreatment solution adapted to create and / or promote germination sites on the surface to be treated.
  • a pretreatment generally consisting of a preliminary degreasing and rinsing of the surface followed by a so-called refining operation using a pretreatment solution adapted to create and / or promote germination sites on the surface to be treated.
  • sols or colloidal suspensions of titanium salts which allow the subsequent production of a conversion layer having smaller crystals in a denser layer.
  • a post-treatment can be carried out on a conversion layer obtained by phosphatation.
  • conversion layers are formed by bringing the surface into contact with an aqueous, organic or hydro-organic bath comprising one or more carboxylic acids in solution or in emulsion at a concentration of at least 0.1 mol / liter, and this in oxidizing conditions vis-à-vis the metal surface.
  • This or these acids are saturated or unsaturated aliphatic monocarboxylic or dicarboxylic acids.
  • the object of the invention is to propose treatments by carboxylation of metal surfaces, in particular zinc and zinc alloy layers coating the galvanized and electrogalvanized steel sheets, solving better than the existing treatments the problems that we have just described. to quote.
  • the respective proportions of the acids are x ⁇ 3% - y ⁇ 3%.
  • Said oxidizing conditions can be created by the presence in the bath of an oxidizing compound for the metal surface.
  • Said oxidizing compound may be hydrogen peroxide.
  • Said oxidizing compound may be sodium perborate.
  • Said oxidizing conditions can be created by the bath application of an electric current.
  • the bath may be a hydro-organic bath and contain a co-solvent.
  • This co-solvent may be chosen from 3-methoxy-3-methylbutan-1-ol, ethanol, n-propanol, dimethylsulfoxide, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl.
  • -2-pentanone diacetone alcohol.
  • Said bath may be an aqueous bath and include a surfactant and / or a dispersant.
  • Said surfactant may be chosen from alkylpolyglycosides, ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylated oils, ethoxylated nonylphenols and ethoxylated sorbitan esters.
  • Said dispersant may be chosen from high molecular weight polyols, carboxylic acid salts such as (meth) acrylic copolymers, polyamide derivatives such as polyamide waxes.
  • Said saturated carboxylic acids may each have an even number of carbon atoms.
  • Said saturated carboxylic acids may be lauric acid and palmitic acid.
  • Said metal surface may be a galvanized steel sheet, and the bath may contain an Al 3+ complexing agent .
  • said mixture is an eutectic mixture.
  • the invention also relates to a method of temporary protection against corrosion of a metal surface, according to which a conversion by carboxylation of said surface is carried out, characterized in that said conversion is carried out by the above method.
  • Said metal surface may be selected from zinc, iron, aluminum, copper, lead and their alloys, galvanized, aluminized, copper-plated steels.
  • the subject of the invention is also a process for manufacturing a shaped sheet having a metal surface chosen from zinc, iron, aluminum, copper, lead, and their alloys, as well as galvanized, aluminized steels. , copper-coated, in which a carboxylation treatment of said sheet is carried out and shaped, characterized in that said carboxylation treatment is carried out by the above method.
  • Said sheet may be steel coated with zinc or a zinc alloy and is shaped by stamping.
  • the invention is based on the use, for composing the solution or the carboxylation emulsion, of a binary or ternary eutectic of linear fatty acids saturated with C 10 -C 18 , or of a mixture having the composition of such a eutectic.
  • the acids used are all even-numbered acids of carbon atoms.
  • the binary eutectic of C 12 - C 16 acids is particularly preferred.
  • the concentration of the eutectic or mixture in the carboxylate bath is greater than or equal to 20 g / l.
  • eutectic refers to either a simple mixture with the eutectic composition or a eutectic containing two or three C 10 -C 18 saturated linear fatty acids, is a true eutectic having this composition, obtained by melting the mixture of fatty acids.
  • the treatment bath may contain only the eutectic or the mixture of acids in the composition of the eutectic, a surfactant and water, if the necessary oxidizing conditions are obtained by electrochemical means.
  • electrochemical means namely by adding an oxidizing compound, such as hydrogen peroxide.
  • oxidizing compound such as hydrogen peroxide.
  • the minimum concentration of 20 g / l of the eutectic is chosen because, below this limit, the rate of formation of the carboxylated layer is no longer sufficient to obtain an effective conversion layer with a duration of treatment compatible with industrial requirements.
  • the ability of saturated linear aliphatic monocarboxylates to inhibit the aqueous corrosion of metals (Cu, Fe, Pb, Zn and Mg) in neutral and aerated solution has been widely demonstrated.
  • the protection provided is due to the presence of a thin film consisting of crystals of metal soap and hydroxide of the treated metal.
  • the protective layer is formed under oxidizing conditions and has a corrosion resistance closely dependent on the length of the carbon chain and the concentration of the carboxylate.
  • a carboxylation bath contains a linear C n saturated carboxylic acid of the general formula (CH 3 (CH 2 ) n-2 COOH), with n ⁇ 7, denoted HC n , dissolved in water or in a mixture generally equivolumic water-non-aqueous solvent (ethanol, ).
  • An oxidant such as hydrogen peroxide or sodium perborate, is added to the bath to produce a sufficient amount of Zn ++ cations at the zinc / solution interface.
  • the pH of the bath is close to 5.
  • the oxidizing conditions producing the Zn ++ cations are obtained by circulating an electric current between the surface to be protected and a counter electrode immersed in the bath.
  • the essential formation reaction of the carboxylated layer on the zinc surface is: Zn 2+ + 2 C n - ⁇ Zn (C n ) 2 ⁇
  • the compounds that can be used in the context of the invention may be derived from products of the green chain, that is to say from agricultural production for non-food use (sunflower oils, flax, colza ). They advantageously replace the polluting mineral oils used for the lubrication of metal surfaces and the phosphating and chromating solutions used for the protection of these same surfaces against corrosion.
  • saturated fatty acids those containing an even number of carbon atoms are preferred.
  • the study of their binary mixtures makes it possible to highlight the existence of two particular proportions for which appear respectively an inflection and a minimum in the curve of the melting point.
  • the figure 1 schematizes the equilibrium diagram of fatty acid mixtures A and B as a function of temperature.
  • the minimum e indicates the formation of a eutectic and the change of slope at point u is due, in general, to the existence of a defined molecular compound c of formula A m B n (m and n denote the molar fractions of A and B respectively).
  • the figures 2b and 2d represent the HC 12 / HC 16 and HC 12 / HC 18 binary diagrams. It can be seen that the eutexte point e, as well as the point of inflection u corresponding to the complex, do not appear respectively at 25 and 50%, as is the case with acid mixtures whose chain lengths differ by only two carbon atoms ( fig.2a for HC 10 / HC 12 and 2C for HC 16 / HC 18 ). Eutectic is shifted to higher molar concentrations of the shortest fatty acid.
  • the shape of the binary diagram and the positions of the points u and e are a function of the more or less limited stability of the complex.
  • Table 1 shows the compositions of the eutectics e of various binary mixtures and their melting points T f (e) .
  • Table 1 The eutectic compositions given in Table 1 are approximate. According to the publications, they can vary from a few percent. These differences are due to the purity of the fatty acids used. Table 1 - Properties of the studied fatty acid mixtures HC blends n Composition e (% mol ) T f (e) (° C) HC 10 / HC 12 65/35 18 HC 12 / HC 14 69/31 34.2 HC 12 / HC 16 81/19 32.7 HC 12 / HC 18 81.5 / 18.5 37.0 HC 14 / HC 16 58/42 42.6 HC 14 / HC 18 61/39 44.1 HC 16 / HC 18 72.5 / 27.5 51.1
  • the sheets were degreased in an alkaline degreasing bath, similar to those used in industrial alkaline phosphating. They were then rinsed. Then the carboxylation treatment took place chemically (presence of an oxidant in the bath, such as hydrogen peroxide or a sodium perborate tetrahydrate) or electrochemical.
  • an oxidant in the bath such as hydrogen peroxide or a sodium perborate tetrahydrate
  • the oxidizing conditions allow a rapid reaction between Zn 2+ and C n - , providing fine crystals of Zn carboxylate.
  • the concentration of H 2 O 2 in the solution is, for example, from 2 to 15 g / l. Below 2 g / l the medium is generally not enough oxidizing to form enough Zn 2+ in solution. The duration of the reaction may not be compatible with industrial requirements. Above 15 g / l, the medium is generally too oxidizing and the crystals are poorly formed. The optimum concentration is about 8 to 12 g / l H 2 O 2 in the solution.
  • sodium perborate Compared to hydrogen peroxide, sodium perborate has the disadvantage of less solubility in water. The use of hydrogen peroxide thus provides greater flexibility in the choice of oxidant concentrations.
  • the preferred co-solvent is 3-methoxy-3-methylbutan-1-ol (MMB). It is a green and biodegradable solvent. In addition, its flash point, which is the temperature from which it becomes flammable, is 71 ° C, compared for example with that of ethanol which is 12 ° C. MMB therefore provides better safety conditions than ethanol. It is also possible to use, in particular, ethanol, n-propanol, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone or diacetone alcohol.
  • a first advantage is the lowering of the melting temperature compared to the use of a single fatty acid, as is apparent from the figure 2 . This makes it possible to keep the carboxylate bath at a relatively low temperature of about 45 ° C. in many cases, particularly if a hydro-organic medium is used.
  • Eutectic is prepared by melting for several hours the mixture of fatty acids component. The mixture is then slowly cooled to room temperature.
  • electrogalvanized steel sheets (thickness of the Zn layer: 7.5 ⁇ m) were treated to obtain a weight of carboxylated layer of between 1 and 2 g / m 2 , of which experience shows that it provides a maximum coverage rate of the sheet.
  • the weight of the carboxylate layer is evaluated by measuring the difference in mass between the carboxylate substrate and the substrate etched with dichloroethane under ultrasound, which treatment causes the dissolution of the carboxylate layer.
  • the aqueous corrosion resistance of the test samples was tested in a conventional three-electrode electrochemical cell, by monitoring the corrosion potential and measuring the polarization resistance.
  • the electrolyte used is water according to ASTM D1384-87 (148 mg / l of Na 2 SO 4 , 138 mg / l of NaHCO 3 , 165 mg / l of NaCl, pH 7.8). This corrosive solution is usually used to evaluate the effectiveness of corrosion inhibitors in the laboratory.
  • the resistance to atmospheric corrosion of 50 cm 2 samples was studied according to DIN 50017 using a climatic chamber where the samples were placed vertically and subjected to cycles of 24 h, each with successive exposure. from 8 h to 100% humidity (twice water at 40 ° C) and then to ambient air for 16 h.
  • the degradation of the coating was estimated by visual observation and X-ray diffraction.
  • Dusting of the samples was evaluated by measuring the mass difference of the substrate before and after successive passes between two squeezing rollers.
  • the loss of mass thus measured can be related to the dusting tendency of the coating.
  • Tribological tests were carried out to evaluate the lubricating properties of the coating during stamping. They were carried out on a plane / plane tribometer with tightening force control, by scrolling the sample of pressed sheet at a speed of 1 to 100 mm / s, and by measuring the evolution of the distance between the tools. plans ensuring the tightening of the sample. It is thus possible to determine the coefficient of friction as a function of the clamping pressure.
  • compositions of the baths were as follows: medium 50% by volume of water and 50% by volume of 3-methoxy-3-methylbutan-1-ol (MMB); concentration of H 2 O 2 5 g / l; temperature 45 ° C .; compositions and concentrations of eutectics and duration of carboxylation according to Table 2: Table 2: compositions and concentrations of eutectics tested and duration of carboxylation Mixed % mol eutectic Concentration (g / l) Duration of the carboxylation (s) HC 10 / HC 12 65/35 85 4 HC 12 / HC 16 ; 81/19 55 4 HC 12 / HC 18 81.5 / 18.5 45 2
  • the residence times of the sheet samples in the bath were determined to obtain a carboxylate layer weight of between 1 and 1.5 g / m 2 .
  • the figure 3 shows the evolution over time of the polarization resistance R p of the coatings, and the figure 4 shows this same development for the corrosion potential E corr in the corrosive water, for the three coatings tested previously defined and, by reference, for a galvanized coating EG not carboxylated.
  • the coatings according to the invention have much better performances than coatings resulting from simple electrogalging.
  • the polarization resistance is of the order of 2 k ⁇ .cm 2
  • the carboxylation coatings usually made with water-solvent solutions based on a single fatty acid provide only one relatively weak improvement of this value (up to 15 k ⁇ .cm 2 ).
  • the coatings according to the invention provide values of the order of 5 to 15 times higher than those observed for coatings electrozinced alone. Coatings obtained with HC 12 / HC 16 in the first place, and with HC 12 / HC 18 second, provide the best results in absolute value and stability over time.
  • those of the coatings according to the invention are 80 to 140 mV higher than the values obtained for the electrogalvanized coating.
  • the HC 12 / HC 16 again gives the best result.
  • Coatings obtained using a single fatty acid in a water-solvent medium usually provide corrosion potentials of the order of -1020 to -1080 mV, and therefore less favorable than those of the coatings according to the invention.
  • the resistance to atmospheric corrosion was also estimated by observing the percentage of the surface of the corroded sample after 20 cycles of exposure, as defined above.
  • Tribology tests were carried out on the coating formed with HC 12 / HC 16 as compared to electrogalvanized coating. The result is reported on the figure 5 which shows the coefficient of friction of the coating as a function of the contact pressure for the two coatings.
  • the tribological behavior of uncoated electrogalvanized steel degrades substantially with the increase of the contact pressure, which is not the case with the coating according to the invention which constantly has a low coefficient of friction, of the same order of magnitude. larger than coatings formed with single fatty acids.
  • This coating is well suited to be used as a lubricant during stamping of a steel sheet coated with zinc or zinc alloy.
  • the carboxylation coatings obtained with the aid of binary mixtures of fatty acids with the composition of the eutectic have performance at least equal, and often superior to all points of view, to those coatings obtained with the aid of single fatty acids in water-solvent medium.
  • the HC 12 / HC 16 mixture is the most satisfactory of those tested.
  • composition difference (in mol%) with respect to the eutectic x% - y% should not exceed x ⁇ 5% - y ⁇ 5% and preferably x ⁇ 3% - y ⁇ 3%, for binary eutectics or x ⁇ 3%, y ⁇ 3% - z ⁇ 3% for ternary eutectics.
  • dispersants it is possible to use especially high molecular weight polyols, carboxylic acid salts such as (meth) acrylic copolymers, polyamide derivatives such as polyamide waxes.
  • the optimum for the oxygenated water concentration is between 2 and 8 g / l.
  • carboxylation emulsions containing water, the surfactant APG 215 mentioned above and the eutectic HC 12 / HC 16 at 81/19% were prepared.
  • emulsion A with a low concentration of APG 215 makes it possible to release the fatty acids more rapidly.
  • a coat weight of 1.2 g / m 2 is reached in 5 s, while 10 s are needed to achieve a layer weight comparable with other emulsions.
  • contents of APG 215 of 1 to 3% no marked effect of surfactant concentration is observed.
  • the oxidant concentration also has no very appreciable effect in the explored range.
  • the size of the crystals does not seem to be related to the composition of the emulsion. Again, the product of the carboxylation is not well crystallized, and its composition is close to ZnC 12 C 16 .
  • An HC 12 / HC 16 mixture was also prepared in respective molar proportions of 77 and 23% (thus deviating a little from the 81-19% eutectic but remaining in accordance with the invention) in a water / solvent medium ( MMB).
  • Solubilization took place at 45 ° C.
  • This reference sample has a coefficient of friction of the order of 0.13 to 0.17 ⁇ according to the contact pressure.
  • the carboxylated sheets according to the invention have friction coefficients of up to 0.05 ⁇ , and still very significantly lower, at equal contact pressure, than those of the reference sheets. It is also seen that the replacement of the phosphate mixture of Al + oxalic acid (solution 1) with Al oxalate (solution 2) has no appreciable influence on the tribological properties. The fact that the composition of the mixture deviates slightly from that given as being that of the eutectic (in the range of ⁇ 5% for each constituent), does not compromise, either, the good quality of the result.
  • all solutions 1 to 4 provided a covering and homogeneous deposit.
  • the weight of the layer formed reaches 1.2 g / m 2 after 3 to 7 s in all cases.
  • the performance of carboxylation coatings formed from eutectics or mixtures with the composition of the eutectic in a water / organic solvent medium are generally greater than those of similar coatings formed by emulsions in water / surfactant medium.
  • the performance of the coatings formed without organic solvent are considered sufficient, for example because the coated products are not intended to remain long in a corrosive atmosphere, it is advantageous to use them because the toxicological risks are less for the manipulators and for the environment.
  • their implementation does not require or little control and post-treatment effluents.
  • the oxidizing conditions have been obtained using hydrogen peroxide. But, as is known, they could have been obtained with other oxidants, or by the application to the carboxylation bath of an electrical current of the order of intensity, for example, from 10 to 25 mA / cm. 2 .
  • the invention is not limited to the examples that have been described.
  • the eutectics of the other couples of saturated C 10 -C 18 linear fatty acids would be usable, whether these acids each have an even or odd number of carbon atoms.
  • Eutectics of ternary mixtures of such fatty acids can also be used.
  • even-numbered fatty acids which is the preferred embodiment of the invention. These even fatty acids are of plant origin and are generally derived from the green products sector, from renewable sources. Odd fatty acids do not exist in nature and must be synthesized. In addition, odd fatty acid eutectics require chemical treatments for their preparation.
  • the conversion treatments according to the invention are applicable to other metal surfaces than galvanized steels. They may concern any metal surface capable of undergoing carboxylation, namely zinc, iron, aluminum, copper, lead and their alloys, aluminized or copper-coated steels.

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  • Coating With Molten Metal (AREA)

Claims (19)

  1. Verfahren zur Umwandlung einer Metallfläche durch Carboxylierung, welche Metallfläche ausgewählt ist aus Zink, Eisen, Aluminium, Kupfer, Blei und deren Legierungen, aus galvanisierten, elektroverzinkten, aluminierten oder verkupferten Stählen, und zwar unter gegenüber dem Metall oxidierenden Bedingungen, indem sie mit einem wässrigen oder wässrig-organischen Bad, das ein Gemisch von organischen Säuren enthält, in Kontakt gebracht wird, dadurch gekennzeichnet, dass:
    - die organischen Säuren gesättigte geradkettige Carboxylsäuren mit 10 bis 18 Kohlenstoffatomen sind;
    - das Gemisch ein binäres oder ternäres Gemisch solcher Säuren ist;
    - die jeweiligen Anteile dieser Säuren derart sind, dass
    • für ein binäres Gemisch x ± 5% - y ± 5%, wobei x und y in Mol-% die jeweiligen Anteile der zwei Säuren in einem Gemisch mit der Zusammensetzung des Eutektikums sind;
    • für ein ternäres Gemisch x ± 3% - y ± 3% - z ± 3%, wobei x, y und z in Mol-% die jeweiligen Anteile der drei Säuren in einem Gemisch mit der Zusammensetzung des Eutektikums sind;
    - die Konzentration des Gemischs im Bad höher als oder gleich 20 g/l ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Gemisch binär ist, und dass die jeweiligen Anteile der Säuren x ± 3% - y ± 3% betragen.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die oxidierenden Bedingungen dadurch geschaffen werden, dass eine für die Metallfläche oxidierende Verbindung in dem Bad vorhanden ist.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die oxidierende Verbindung Wasserstoffperoxid ist.
  5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die oxidierende Verbindung Natriumperborat ist.
  6. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die oxidierenden Bedingungen dadurch geschaffen werden, dass das Bad einem elektrischen Strom ausgesetzt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Bad ein wässrig-organisches Bad ist und ein Co-Lösungsmittel enthält.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Co-Lösungsmittel ausgewählt ist aus 3-Methoxy-3-methylbutan-1-ol, Ethanol, n-Propanol, Dimethylsulfoxid, N-methyl-2-pyrrolidon, 4-Hydroxy-4-methyl-2-pentanon, Diazetonalkohol.
  9. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Bad ein wässriges Bad ist und einen grenzflächenaktives und/oder dispergierendes Mittel enthält.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das grenzflächenaktive Mittel ausgewählt ist aus Alkylpolyglycosiden, ethoxylierten Fettalkoholen, ethoxylierten Fettsäuren, ethoxylierten Ölen, ethoxylierten Nonylphenolen, ethoxylierten Sorbitanestern.
  11. Verfahren nach einem der Ansprüche 9 oder 10, dadurch gekennzeichnet, dass das dispergierende Mittel ausgewählt ist aus Polyolen mit hohem Molekulargewicht, Carboxylsäuresalzen wie etwa (Methacryl)copolymeren, Polyamidderivaten wie etwa Polyamidwachsen.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die gesättigten Carboxylsäuren jeweils eine gerade Zahl an Kohlenstoffatomen haben.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die gesättigten Carboxylsäuren Laurinsäure und Palmitinsäure sind.
  14. Verfahren nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, das die Metallfläche ein galvanisiertes Stahlblech ist, und dass das Bad einen Al3+-Komplexbildner enthält.
  15. Verfahren nach einem der Ansprüche 1 bis, 14, dadurch gekennzeichnet, dass das Gemisch ein eutektisches Gemisch ist.
  16. Verfahren zum temporären Korrosionsschutz einer Metallfläche, gemäß dem eine Umwandlung durch Carboxylierung der Fläche erfolgt, dadurch gekennzeichnet, dass die Umwandlung durch das Verfahren nach einem der Ansprüche 1 bis 15 geschieht.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, dass die Metallfläche aus Zink, Eisen, Aluminium, Kupfer, Blei und deren Legierungen, galvanisierten, aluminierten, verkupferten Stählen ausgewählt ist.
  18. Verfahren zur Herstellung eines Formblechs, das eine Metallfläche aufweist, die aus Zink, Eisen, Aluminium, Kupfer, Blei und deren Legierungen, sowie galvanisierten, aluminierten, verkupferten Stählen ausgewählt ist, wobei eine Carboxylierungsbehandlung des Blechs durchgeführt wird, und es geformt wird, dadurch gekennzeichnet, dass die Carboxylierungsbehandlung nach einem der Ansprüche 1 bis 15 geschieht.
  19. Verfahren nach Anspruch 18, dadurch gekennzeichnet, dass das Blech aus mit Zink oder einer Zinklegierung beschichtetem Stahl besteht, und dass es durch Pressen geformt wird.
EP06847093A 2005-12-22 2006-12-20 Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches Not-in-force EP1963545B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL06847093T PL1963545T3 (pl) 2005-12-22 2006-12-20 Sposób obróbki przez karboksylowanie powierzchni metalowych, zastosowanie tego sposobu celem zapewnienia czasowej ochrony przed korozją oraz sposób wytwarzania blachy kształtowej tak karboksylowanej
EP06847093A EP1963545B1 (de) 2005-12-22 2006-12-20 Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05292773A EP1801262B1 (de) 2005-12-22 2005-12-22 Behandlungsverfahren der metallischen Oberflächen durch Carboxilierung, Benutzung dieses Verfahrens für den zeitweiligen Korrosionsschutz und Verfahren zur Herstellung eines geformten carboxylierten Bleches
PCT/FR2006/002814 WO2007077336A1 (fr) 2005-12-22 2006-12-20 Procede de traitement par carboxylatation de surfaces metalliques, utilisation de ce procede pour la protection temporaire contre la corrosion, et procede de fabrication d'une tole mise en forme ainsi carboxylatee
EP06847093A EP1963545B1 (de) 2005-12-22 2006-12-20 Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches

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EP1963545A1 EP1963545A1 (de) 2008-09-03
EP1963545B1 true EP1963545B1 (de) 2010-11-17

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EP05292773A Not-in-force EP1801262B1 (de) 2005-12-22 2005-12-22 Behandlungsverfahren der metallischen Oberflächen durch Carboxilierung, Benutzung dieses Verfahrens für den zeitweiligen Korrosionsschutz und Verfahren zur Herstellung eines geformten carboxylierten Bleches
EP06847093A Not-in-force EP1963545B1 (de) 2005-12-22 2006-12-20 Behandlungsverfahren der metallischen oberflächen durch carboxilierung, benutzung dieses verfahrens für den zeitweiligen korrosionsschutz und verfahren zur herstellung eines geformten carboxylierten bleches

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KR (1) KR101033913B1 (de)
CN (1) CN101448974B (de)
AR (1) AR058727A1 (de)
AT (2) ATE415504T1 (de)
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MA (1) MA30081B1 (de)
MX (1) MX2008007702A (de)
PL (2) PL1801262T3 (de)
RU (1) RU2384653C1 (de)
TW (1) TWI376428B (de)
UA (1) UA86726C2 (de)
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CN103422085A (zh) * 2012-05-22 2013-12-04 广州市泓硕环保科技有限公司 一种改善铁或铝基材料对涂料附着力的处理方法及组合物
FR3000103B1 (fr) 2012-12-21 2015-04-03 Total Raffinage Marketing Composition lubrifiante a base d'ether de polyglycerol
CA2982739C (en) 2015-04-15 2023-06-27 Henkel Ag & Co. Kgaa Thin corrosion protective coatings incorporating polyamidoamine polymers
CN113106434B (zh) * 2021-04-12 2022-01-04 南昌大学 一种环保型铝合金化学氧化液及化学氧化方法
CN119374995B (zh) * 2024-12-30 2025-03-18 河北燕山钢铁集团有限公司 一种冷轧金属材料金相试样制备方法

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JP3267853B2 (ja) * 1996-01-12 2002-03-25 ユシロ化学工業株式会社 水溶性潤滑剤組成物及び金属腐食防止方法
FR2767079B1 (fr) * 1997-08-11 1999-10-29 Lorraine Laminage Procede de traitement de surfaces de toles metalliques pour ameliorer leur aptitude au collage, a l'emboutissage et au degraissage
TW574353B (en) * 2000-01-17 2004-02-01 Nihon Parkerizing Agents, liquid compositions and process for hydrophilization
FR2822852B1 (fr) * 2001-03-27 2003-12-12 Usinor Procede de traitement par carboxylatation de surfaces metalliques
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US7223299B2 (en) * 2003-09-02 2007-05-29 Atotech Deutschland Gmbh Composition and process for improving the adhesion of a siccative organic coating compositions to metal substrates

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DE602006018357D1 (de) 2010-12-30
TW200728499A (en) 2007-08-01
JP2009520879A (ja) 2009-05-28
DE602005011317D1 (de) 2009-01-08
ES2355438T3 (es) 2011-03-25
CA2632928C (fr) 2011-08-09
BRPI0621113A2 (pt) 2011-11-29
PL1801262T3 (pl) 2009-05-29
MX2008007702A (es) 2008-09-12
CA2632928A1 (fr) 2007-07-12
ATE488618T1 (de) 2010-12-15
CN101448974A (zh) 2009-06-03
JP4981062B2 (ja) 2012-07-18
EP1801262B1 (de) 2008-11-26
ZA200805274B (en) 2009-06-24
EP1801262A1 (de) 2007-06-27
ES2318436T3 (es) 2009-05-01
PL1963545T3 (pl) 2011-07-29
WO2007077336A1 (fr) 2007-07-12
US8273189B2 (en) 2012-09-25
CN101448974B (zh) 2011-09-14
RU2384653C1 (ru) 2010-03-20
KR20080088596A (ko) 2008-10-02
UA86726C2 (ru) 2009-05-12
MA30081B1 (fr) 2008-12-01
EP1963545A1 (de) 2008-09-03
US20090242079A1 (en) 2009-10-01
AR058727A1 (es) 2008-02-20
TWI376428B (en) 2012-11-11
RU2008130099A (ru) 2010-01-27
ATE415504T1 (de) 2008-12-15
KR101033913B1 (ko) 2011-05-11

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