WO2021185449A1 - Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel - Google Patents

Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel Download PDF

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Publication number
WO2021185449A1
WO2021185449A1 PCT/EP2020/057635 EP2020057635W WO2021185449A1 WO 2021185449 A1 WO2021185449 A1 WO 2021185449A1 EP 2020057635 W EP2020057635 W EP 2020057635W WO 2021185449 A1 WO2021185449 A1 WO 2021185449A1
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Prior art keywords
phosphating solution
zinc
contents
salt
carboxylic acid
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PCT/EP2020/057635
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German (de)
English (en)
Inventor
Fabian JUNGE
Gregor Müller
Nicole Weiher
Frank Panter
Oliver Moll
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Thyssenkrupp Steel Europe Ag
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Application filed by Thyssenkrupp Steel Europe Ag filed Critical Thyssenkrupp Steel Europe Ag
Priority to EP20713264.8A priority Critical patent/EP4121580A1/fr
Priority to PCT/EP2020/057635 priority patent/WO2021185449A1/fr
Publication of WO2021185449A1 publication Critical patent/WO2021185449A1/fr

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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
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • the invention relates to a method for producing a phosphating layer on a surface of a flat steel product provided with a metallic protective layer, in which a nickel-free aqueous. Phosphating solution is applied.
  • the invention also relates to an aqueous phosphating solution which is intended in particular for use in the method according to the invention.
  • Flat steel products are understood here to mean rolled products, the length and width of which are each substantially greater than their thickness.
  • a flat steel product or a “sheet metal product” is mentioned below, this refers to rolled products such as steel strips or sheets from which blanks or blanks are cut off for the production of, for example, body components.
  • “Shaped sheet metal parts” or “sheet metal components” are produced from such flat steel or sheet metal products, the terms “shaped sheet metal part” and “sheet metal component” being used synonymously here.
  • the terms “phosphate layer”, “phosphate layer”, “phosphate crystal layer” and “phosphate coating” are to be understood synonymously in the following.
  • the phosphating of metal-coated surfaces of flat steel products is of particular importance for oxyming such flat steel products to form sheet metal parts, such as those required for the manufacture of automobile bodies.
  • the phosphating improves the paint adhesion and the corrosion resistance of the flat steel product.
  • flat steel products with a phosphated metal-coated surface have improved formability, since they leave less abrasion behind in the forming tool and show improved sliding behavior.
  • phosphate crystals form on the surface provided with the metallic protective layer.
  • a trication phosphating solution is used for the phosphating.
  • This type of phosphating is also known in technical terms as “manganese-modified low-zinc phosphating”.
  • the phosphating solution contains not only phosphoric acid but also zinc, nickel and manganese salts.
  • the nickel and manganese cations lead to a significant refinement of the phosphate crystals and increase the degree of coverage on the surface of the flat steel product provided with the respective metallic protective layer.
  • the nickel and manganese cations ensure a higher thermal and alkaline stability of the phosphate crystals and lead to improved paint adhesion.
  • Nickel salts such as nickel nitrate are carcinogenic compounds which, due to their strong oxidative properties, also have a fire-promoting effect and are highly toxic to organisms living in the water.
  • Manganese salts such as manganese nitrate are also oxidizing and also corrosive.
  • EP 0564287 A2 describes a method for phosphating a metallic surface with a nickel-free phosphating solution which, in addition to zinc ions and phosphate ions, also comprises cobalt ions, manganese ions, a phosphating accelerator and fluoride compounds.
  • cobalt compounds such as cobalt nitrate are also carcinogenic and toxic for life forms living in the water.
  • CN 101386980 A describes a nickel-free phosphating solution which, in addition to zinc oxide and phosphoric acid, also includes manganese carbonate, magnesium nitrate, cobalt nitrate, sodium tungstate and sodium carbonate.
  • this approach also requires cobalt nitrate, a carcinogenic and toxic heavy metal salt, in order to be able to do without nickel.
  • a phosphating solution should be specified which enables environmentally friendly phosphating of flat steel products provided with a metallic protective layer and is particularly suitable for use in a method according to the invention.
  • the invention has achieved this object in that at least the work steps specified in claim 1 are carried out during the phosphating of a flat steel product provided with a metallic protective layer. It goes without saying that those not mentioned here are customary for the person skilled in the art in the phosphating of flat steel products of the type in question here Completed procedural steps can also be carried out in the method according to the invention if there is a need for this.
  • a phosphating solution that achieves the above-mentioned object is composed according to the invention in the manner specified in claim 15.
  • a nickel-free aqueous phosphating solution is applied to a surface of a flat steel product provided with a metallic protective layer to produce a phosphating layer
  • a nickel-free aqueous phosphating solution according to the invention consists of phosphoric acid in contents of 0.1-10 g / l, a zinc salt in contents of 0.5-15 g / l, and an alkaline earth metal salt in contents of 1 - 100 g / l and a mono- or polyvalent organic carboxylic acid containing 1 - 8 carbon atoms or a salt of this carboxylic acid in contents of 0.5 - 25 g / l and optionally at least one additive from the group of "surfactants and iron salts" in Contents of up to 10 g / l in each case, the remainder of the phosphating solution being taken up by water and technically unavoidable impurities which, however, do not affect the effect of the phosphating solution according to the invention.
  • a phosphate layer on a flat steel product provided with a metallic protective coating which is characterized by fine phosphate crystals and has an optimized degree of coverage on the surface of the flat steel product provided with a metallic protective layer.
  • the flat steel products coated according to the invention are suitable for a large number of areas of application.
  • the flat steel products phosphated by the process according to the invention are particularly suitable for processing flat steel products in automobile bodies.
  • the nickel-free phosphating solution according to the invention is particularly suitable for forming a phosphate crystal layer with a finely crystalline structure on a surface of a flat steel product provided with a metallic protective layer.
  • a "nickel-free" phosphating solution is mentioned in the present text, this means a phosphating solution that does not contain any nickel in the technical sense, i.e. in which nickel is at most present as a technically ineffective impurity, which is unavoidable in the phosphating solution according to the invention in the course of the manufacturing process reaches, but is present there in such low levels that it neither has an impact on the properties and behavior of the phosphating solution itself or the phosphate layer produced from it, nor does it have any impact on the environment.
  • a phosphating solution according to the invention is to be regarded as “nickel-free” in particular if it contains less than 100 ppm, in particular if it contains less than 10 ppm nickel or nickel compounds.
  • a phosphating layer produced according to the invention is nickel-free. Nevertheless, despite the fact that a phosphating solution according to the invention is free of Ni in the technical sense explained above, it can happen that Ni is also present in the phosphate layer produced by means of a phosphating solution according to the invention. These Ni contents are typically due to a Ni content of the metallic protective layer to which the phosphating solution according to the invention has been applied, and as a result of diffusion processes pass from the metallic protective layer into the phosphate layer produced by the nickel-free phosphating solution according to the invention.
  • the invention is based on the knowledge that the size and coating density of the phosphate crystals are in a complex interaction with the alkaline earth metal salt and the mono- or polybasic organic carboxylic acid or a salt of this carboxylic acid having 1-8 carbon atoms. According to the findings of the invention, the optimum ratio of the size of the is only achieved through the use of these two components Phosphate crystals to the degree of coverage of the crystals on the surface of the metal-coated flat steel product.
  • the zinc phosphate crystals formed in the phosphating layer produced according to the invention have a size that is typical for surfaces of electrolytically zinc-coated flat steel products strip-phosphated by means of conventional trication-phosphating solutions.
  • the phosphate coating after nickel-free phosphating according to the invention is also comparable to that after conventional trication-phosphating.
  • the method according to the invention achieves a phosphate coating weight of 1.0-1.7 g / m 2.
  • the coating weight for tape phosphating is in the range of 1.0-1.4 g / m 2 , while it is also in the range of 1.3-1.7 g / m 2 for phosphatizing.
  • the phosphate crystals of the phosphate layer applied according to the method according to the invention and formed from a phosphating solution according to the invention have an average crystal diameter of at most 20 ⁇ m, in particular of at most 10 ⁇ m or at most 5 ⁇ m.
  • the crystal diameters are typically at least 0.5 ⁇ m, in particular at least 0.7 ⁇ m. Such small diameters are achieved in particular with strip phosphating.
  • crystals with a size of at least 2 ⁇ m are typically formed.
  • the samples coated according to the invention each showed better friction behavior than those samples which had been provided with a conventional trication phosphate due to the fineness of the crystals of their phosphating layer.
  • the examined samples were also oiled with the oil "Anti corit PL3802-39S” from the supplier FUCHS SCHMIERSTOFFE GMBH, which was applied at a level of 1.2 g / m2.
  • the “mean crystal diameter” mentioned here can be determined using scanning electron microscopy (SEM) by measuring the length of the longest edge of the respective crystal in an SEM image and then determining the crystal diameter from the measured edge length with the aid of a comparative scale.
  • SEM scanning electron microscopy
  • the phosphate coating is determined by means of glow discharge spectroscopy (GDOS / GDOES).
  • the measurement was carried out with a glow discharge spectrometer "Spectruma GDA750" (vacuum simultaneous spectrometer with a focal length of 750 mm and a discharge source constructed according to the Grimm type) and the measurement option in DC mode.
  • the measurement was carried out in RF mode.
  • the following working conditions were observed: The basic operation of the glow discharge spectrometer was carried out in accordance with the manufacturer's operating instructions (Spectruma).
  • the device was operated with a 4 mm anode and argon 5.0 (99.999%) gas.
  • Typical parameters of the respective device for operation with a 4 mm anode were a voltage of 800 V, a current of 20 mA, an output of 16 W and a lamp pressure of 3 - 10 hPa Quantified sputter profiles measured and integrated to a depth of 2 ⁇ m to calculate the overlay.
  • the phosphate coating weight can also be carried out gravimetrically or using the methods known under the names “X-ray fluorescence analysis (XRF)” or “wet chemical detachment in combination with ICP-OES (optical emission spectrometry with inductively coupled plasma)” Differential weighing before and after selective chemical detachment can be determined on a defined area.
  • XRF X-ray fluorescence analysis
  • ICP-OES optical emission spectrometry with inductively coupled plasma
  • the steel of which the steel substrate of flat steel products coated according to the invention is made are basically all steels which can be coated with a metallic protective layer by using processes belonging to the prior art.
  • Flat steel products that can be provided with a Zn-based coating are particularly suitable for this purpose.
  • Examples include soft unalloyed steels, such as the steels CR3, CR4, CR5 so designated according to the VDA guideline VDA 239-100, higher-strength IF steels, such as the HC180Y steel according to DIN EN 10346, Bakehardening steels, such as For example, the steels CR180B, CR210B so designated according to the VDA guideline VDA 239-100, higher-strength steels, such as the steels known under the designation HC340LA (material number 1.0548) and HC420 (material number 1.0556), or dual-phase or multi-phase steels, such as the Steels known under the names "DP500” and "DP800” (see brochure "Product Information DP-W and DP-K", published by thyssenkrupp Steel Europe AG, Duisburg, Germany, as of February 2018, version 0).
  • the method according to the invention can in principle be used for phosphating flat steel products provided with all metallic protective layers customary on the market.
  • the metallic protective layer of a flat steel product coated according to the invention can be based on aluminum, such as an AISi coating, or on the basis of zinc with alloyed higher contents of magnesium, such as a so-called "ZM coating" be formed.
  • Al- or Mg-containing coatings can easily be oxidized due to their low standard electrode potential and, during phosphating according to the invention, form poorly soluble phosphate crystals on the surface of the protective layer.
  • Flat steel products whose metallic protective layer is conventionally designed as a zinc coating are particularly suitable for the phosphating according to the invention.
  • These coatings include all coatings that are formed on the basis of zinc, i.e. in particular coatings formed exclusively from Zn or zinc alloy coatings, such as ZnAI, ZnMg or ZnAIMg coatings, which are applied to the steel substrate in a conventional manner, in particular by hot-dip coating or an electrolytic coating.
  • the phosphating according to the invention is particularly suitable for coating electrolytically Zn-coated flat steel products, since these generally have a very low Ni content.
  • a phosphating solution according to the invention When a phosphating solution according to the invention is applied to a Zn-based metallic corrosion layer, the zinc is converted in a redox reaction with the formation of hydrogen gas to zinc phosphate, which forms directly on the surface of the coating of the flat steel product and is thus particularly stable.
  • the zinc phosphate layer formed in this way provides good protection against corrosion and provides the basis for good paint adhesion.
  • Phosphating according to the invention on flat steel products coated with a Zn or Zn alloy layer results in phosphate layers whose special properties are particularly complex for flat steel products phosphated in this way make formed sheet metal components, such as components for automobile bodies, suitable.
  • a phosphating solution used according to the invention contains 0.1-10 g / l of phosphate acid. Contents of at least 0.1 g / l phosphate acid are required so that the oxidation processes used by the invention to form the fine phosphate crystals occur on the surface wetted with the phosphating solution during phosphating.
  • phosphoric acid contents of at least 2 g / l, in particular at least 3 g / l, in the aqueous Phosphating solution turned out to be particularly advantageous.
  • the content of phosphoric acid in the aqueous phosphating solution can be increased either by adding the stated amount of phosphoric acid per volume of the aqueous solution or by the formation of phosphoric acid in situ in the solution result.
  • the phosphoric acid content can result from the combination of a dihydrogen phosphate, a hydrogen phosphate, a phosphate such as zinc phosphate and / or a suitable phosphorus oxide such as diphosphorus pentoxide (P 2 O 5 ) with a proton donor.
  • the inventively provided contents of 0.5-15 g / l of a zinc salt in the aqueous phosphating solution also contribute to a high level of coverage of the flat steel product with a phosphating layer applied according to the invention.
  • the zinc salt used as the source of zinc is provided with contents of at least 1 g / l, in particular at least 4 g / l or at least 6 g / l.
  • zinc salts from the group “zinc nitrate, zinc nitrite, zinc sulfate, zinc chloride, zinc hydroxide, zinc oxide, metallic zinc” are particularly suitable as zinc salts in the aqueous phosphating solution. If metallic zinc is used, it dissolves in the acidic phosphating solution with the formation of hydrogen and is consequently in the Phosphating solution in the form of Zn 2+ ions, that is, as a dissolved zinc salt.
  • salts are mentioned here or elsewhere, the term always also includes possible solvates of the salts, in particular hydrates.
  • the term “zinc nitrate” also includes “zinc nitrate hexahydrate”,
  • the interaction of the alkaline earth metal salt and the mono- or polybasic organic carboxylic acid or a salt of this carboxylic acid having 1-8 carbon atoms is of particular importance for the inventive formation of a particularly finely crystalline and homogeneous phosphate layer on the metallic protective layer of the flat steel product coated according to the invention.
  • alkaline earth metal salt contents of at least 1 g / l in the aqueous phosphating solution are required for this.
  • phosphate crystals with a particularly small average crystal size, ie a small average crystal diameter or crystal thickness are formed in the course of the phosphating carried out according to the invention in a resource-saving manner.
  • Alkaline earth metal salt contents of at least 3 g / l, in particular at least 5 g / l, have proven to be particularly favorable with regard to a reliable use of this effect.
  • alkaline earth metal salt content is more than 100 g / l, there is no further reduction in the average crystal diameter or in the crystal thickness of the phosphate crystals formed.
  • the positive influence of the presence of alkaline earth metal salts in the invention can be used particularly effectively phosphating used with alkaline earth metal salt contents of up to 20 g / l, in particular of up to 10 g / l.
  • alkaline earth metal salts are those with sufficient solubility in the phosphating solution.
  • the alkaline earth metal salts of magnesium or calcium have proven particularly useful for forming a phosphate layer that is as dense and finely divided as possible on the surface of the flat steel product provided with a metallic protective layer.
  • the investigations carried out by the inventors indicate that the magnesium ions, due to their ionic radius, which is similar to the zinc ions, form particularly suitable crystallization nuclei, which lead to an accelerated formation of phosphate crystals with a small average crystal diameter or small crystal thickness.
  • Alkaline earth metal salts selected from the group consisting of magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium hydroxide, magnesium oxide, metallic magnesium, magnesium fluoride, magnesium carbonate, magnesium sulfide, calcium nitrate, calcium sulfate, calcium chloride, calcium hydroxide, calcium oxide, metallic calcium, calcium fluoride, calcium carbonate and calcium carbonate are particularly suitable for the purposes according to the invention ".
  • Metallic magnesium and metallic calcium both react directly in water to form Mg 2+ or Ca 2+ ions, which are both present as dissolved salts in the phosphating solution.
  • a phosphating solution used according to the invention contains 0.5-25 g / l of a mono- or polybasic organic carboxylic acid having 1-8 carbon atoms or a salt of this carboxylic acid. At least 0.5 g / l are required here in order not only to reduce the phosphate crystal size, but also one sufficient coating density, ie to ensure a high degree of coverage, of the phosphate layer on the metallic protective layer of the flat steel product.
  • a complete covering of the metallic protective layer with a dense phosphate crystal layer can be achieved reliably in that the content of the mono- or polyvalent organic carboxylic acid or its salt containing 1-8 carbon atoms is at least 3 g / l in the phosphating solution. At the same time, with these contents, optimal small average crystal diameters or crystal thicknesses of the phosphate crystals contained in a phosphate layer produced according to the invention result.
  • the phosphating solution according to the invention contains more than 25 g / l of a mono- or polybasic organic carboxylic acid or a salt of this carboxylic acid containing 1-8 carbon atoms, there are no increases in the effects explained above, these effects being achieved at contents of at most 10 g / l can be used particularly effectively.
  • polybasic carboxylic acids or carboxylic acid salts with at least 4 carbon atoms makes it possible to further reduce the environmentally harmful effect of the process according to the invention.
  • polybasic carboxylic acids or carboxylic acid salts with a maximum of 8, in particular a maximum of 6 carbon atoms have proven particularly useful.
  • tartaric acid or citric acid or tartrates (tartaric acid salts) or citrates (Citric acid salts) are harmless to health and environmentally friendly and can be handled easily and safely.
  • Caprylic acid or caprylate has also proven to be environmentally friendly and particularly suitable carboxylic acid or carboxylic acid salt for the process according to the invention.
  • a nickel-free phosphating solution composed according to the invention therefore consists, in a particularly practical embodiment, only of water, phosphoric acid, zinc nitrate, magnesium nitrate and tartaric acid in the amounts described here according to the invention.
  • a phosphating produced according to the invention is comparable here to a trication phosphating, since the phosphate layers produced by both methods are completely closed.
  • an additive from the group consisting of “surfactants and iron salts” to the nickel-free aqueous phosphating solution.
  • the wettability of the flat steel product with the phosphating solution provided according to the invention can be optimized and, as a result, a further improvement in quality can be achieved with the phosphate layer produced according to the invention.
  • Surface-active additives such as surfactants are particularly suitable for this purpose.
  • a phosphating solution according to the invention can optionally contain 0.1-7 g / l of at least one surfactant to improve the wettability.
  • the hue of the phosphate layer produced according to the invention can also be shifted into the darker area. This proves to be beneficial when the flat steel products coated according to the invention are to be welded or soldered by means of a laser beam.
  • the dark color improves the coupling of the laser radiation and thus increases the effectiveness of the welding or soldering process.
  • Suitable additives for this are, for example, nitrates, such as iron nitrate, in contents of 0.1-10 g / l, in particular 1-5 g / l.
  • the phosphating solution can additionally contain manganese and / or iron salts.
  • Manganese and / or iron salts from the group consisting of "manganese nitrate, manganese carbonate, manganese chloride, manganese phosphate, manganese sulfate, manganese oxide, manganese bis (dihydrogen phosphate), iron nitrate, iron carbonate, iron chloride, iron phosphate, iron sulfate and iron oxide" are particularly suitable for the formation of finely crystalline phosphate crystals.
  • the alkali and thermal stability of the phosphate layer can be further increased.
  • both the manganese and the iron salts ensure that the color of the phosphate layer is shifted to a darker area with the advantages described above for further processing of the flat steel product.
  • the use of manganese and / or iron salts, but in particular manganese salts, has the disadvantage, however, that heavy metals cannot be completely dispensed with in the course of the process according to the invention. However, if heavy metals are completely dispensed with, the process can be designed to be particularly environmentally friendly.
  • Suitable accelerators for the formation of the phosphate layer are in particular compounds selected from the group consisting of “nitric acid, nitrous acid, sodium nitrite, sodium nitrate, ammonium nitrite, ammonium nitrate, hydrogen peroxide, sodium chlorate, ammonium chlorate, zinc nitrate, magnesium nitrate, hydroxylamine and nitroguanidine”. Used as a peroxide If accelerators are used, only very small amounts of 30-60 mg / l are required to accelerate the formation of a phosphate layer.
  • the aqueous phosphating solution can be heated to 40-75 ° C. for application to the flat steel product.
  • the phosphating solution can be heated to the flat steel product at an application temperature in this range, the finely crystalline phosphate crystals form particularly quickly in the phosphate layer produced according to the invention.
  • Targeted adjustment of the pH of the phosphating solution according to the invention can cause the redox reaction on the reactive metallic Protective layer can be designed particularly efficiently.
  • the pH of the aqueous phosphating solution provided according to the invention can be 1–3.5, in particular 2.5–3, before application.
  • the flat steel product to be phosphated according to the invention can be exposed to the aqueous phosphating solution for an application time of 3 - 125 s. If the duration is shorter, the coating may be incomplete, while a longer application duration has no further advantages.
  • the phosphating solution can be applied in any manner known from the prior art.
  • spray, spray / immersion or immersion systems are suitable for the application, the person skilled in the art selecting the respective system depending on the specific application.
  • thicker phosphate layers can be produced in a particularly cost-effective manner.
  • the preferred application time is 80-120 s, since a complete application time is required Phosphate layer in immersion systems requires a longer duration than in spray systems.
  • the flat steel product provided with the phosphating layer produced according to the invention can also optionally and in a conventional manner be used in order to protect it from environmental influences.
  • Fig. 1 is an FE-SEM image (field emission
  • Fig. 2 is an FE-SEM image (field emission
  • an aqueous phosphating solution according to the invention was prepared in which to
  • the steel sheet samples were alkaline-cleaned in a conventional manner, degreased and, after a rinsing process, by immersion for a period of 60 s in an activating solution containing 2.1 g / l of an activating agent commercially available under the brand Fixodine ® 50 CF, containing titanium phosphate, prepared for phosphating.
  • an activating solution containing 2.1 g / l of an activating agent commercially available under the brand Fixodine ® 50 CF, containing titanium phosphate, prepared for phosphating.
  • One of the surface-activated samples prepared in this way was then immersed in the phosphating solution heated to 60 ° C. for an application time of 5 s.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne un procédé de génération d'un revêtement de conversion de phosphate sur une surface d'un produit plat en acier pourvu d'un revêtement protecteur métallique dont l'effet polluant est réduit au minimum. À cet effet, selon l'invention, une solution aqueuse de phosphatation exempte de nickel est appliquée sur le revêtement protecteur métallique, ladite solution contenant 0,1-10 g/l d'acide phosphorique, 0,5-15 g/l d'un sel de zinc, 1-100 g/l d'un sel de métal alcalino-terreux et 0,5-25 g/l d'un acide carboxylique organique monovalent ou polyvalent comprenant 1-8 atomes de carbone ou un sel dudit acide carboxylique et éventuellement au moins un additif choisi dans le groupe des tensioactifs et des sels de fer, en des teneurs allant jusqu'à 10 g/l chacun.
PCT/EP2020/057635 2020-03-19 2020-03-19 Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel WO2021185449A1 (fr)

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EP20713264.8A EP4121580A1 (fr) 2020-03-19 2020-03-19 Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel
PCT/EP2020/057635 WO2021185449A1 (fr) 2020-03-19 2020-03-19 Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel

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PCT/EP2020/057635 WO2021185449A1 (fr) 2020-03-19 2020-03-19 Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115838927A (zh) * 2022-12-01 2023-03-24 湖南金裕环保科技有限公司 除油、除锈、钝化、磷化四合一处理液及其制备方法

Citations (7)

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DE3800835A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren zur phosphatierung von metalloberflaechen
EP0385251A1 (fr) * 1989-03-03 1990-09-05 Henkel Kommanditgesellschaft auf Aktien Phosphatation au zinc-barium de surfaces métalliques
EP0564287A2 (fr) 1992-04-03 1993-10-06 Nippon Paint Co., Ltd. Procédé de zinc-phosphatation d'une surface métallique par traitement de revêtement par électro-déposition cationique
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