EP0774016B1 - No-rinse phosphatising process - Google Patents

No-rinse phosphatising process Download PDF

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Publication number
EP0774016B1
EP0774016B1 EP95932747A EP95932747A EP0774016B1 EP 0774016 B1 EP0774016 B1 EP 0774016B1 EP 95932747 A EP95932747 A EP 95932747A EP 95932747 A EP95932747 A EP 95932747A EP 0774016 B1 EP0774016 B1 EP 0774016B1
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EP
European Patent Office
Prior art keywords
phosphating solution
phosphating
weight
phosphate
zinc
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EP95932747A
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German (de)
French (fr)
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EP0774016A1 (en
Inventor
Reinhard Seidel
Bernd Mayer
Melanie Joppen
Melita Krause
Jörg Riesop
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
    • C23C22/05—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
    • C23C22/12—Orthophosphates containing zinc 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
    • C23C22/05—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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc 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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/362—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 fluorides or complex fluorides containing also phosphates containing also zinc 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
    • C23C22/05—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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—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 fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel 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
    • C23C22/73—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 characterised by the process
    • C23C22/76—Applying the liquid by spraying

Definitions

  • the invention relates to a method for Phosphating of surfaces made of steel, zinc, aluminum or in each case their alloys. It is particularly suitable for phosphating of electrolytically galvanized or hot dip galvanized Steel.
  • the phosphating solutions are in the sense of a so-called "No-rinse process" after the intended exposure time not rinsed on the surfaces with water but immediately dried up. The method is therefore particularly useful suitable in continuously running belt treatment plants.
  • the phosphating of metals pursues the goal on the metal surface to produce firmly adherent metal phosphate layers already improve the corrosion resistance and in combination with paints and other organic coatings into one Significant increase in paint adhesion and resistance to infiltration contribute to corrosion.
  • Such phosphating processes have been known for a long time.
  • EP-B-141 341 also describes a phosphating process in which is not rinsed with water. This method was used especially for fixed structures such as bridges or the like developed. Treated with a solution the 1 to 5% by weight zinc, 1 to 20% by weight phosphoric acid, 0.01 to 0.5% by weight of cobalt and / or nickel and 0.02 to 1.5% by weight of one Contains accelerator. After applying the phosphating solution, the for example by wiping, brushing, spreading, rolling up or Spraying can take place, the solution is not left for one act for a certain time, whereby the solution reacts or also only partially responded. In both cases, following the Exposure to be rinsed.
  • Phosphating solution described high levels of zinc and phosphate on.
  • Phosphating solutions are in similar concentration ranges also known for depositing phosphate layers on metal parts, that of a cold mechanical shape, for example by pulling or presses to be subjected.
  • the separating ones relatively thick layers of phosphate that you can use to increase their effects can still soak with oil, act as lubricants and reduce the friction between tool and workpiece. They are usually not a pretreatment before painting suitable because the paint adheres to the thick phosphate layers mechanical stress is bad.
  • Such a phosphating solution for the formation of phosphate layers on steel strip or wire as a lubricant before cold drawing or other deformations can be used, for example, in DE-B-25 52 122. Accordingly, solutions are used that contain zinc in in an amount of 5 to 100 g / l and phosphate in an amount of 10 up to 150 g / l and nitrate acting as an accelerator in a quantity from 10 to 80 g / l included.
  • the phosphating solution is with the Surface in contact for a period of 5 to 15 seconds brought and then rinsed with water.
  • EP-A-0 565 346 relates to a phosphating solution for metal surfaces made of steel, zinc, Aluminum or its alloys.
  • the metal surface treated with an aqueous solution containing 0.01 to 1.0 mol / l silicon dioxide, 0.02 to 0.5 mol / l phosphoric acid and 0.001 to 0.5 mol / l of a divalent metal ion contains.
  • divalent metal ions are manganese, cobalt, iron, Nickel, zinc and preferably calcium, zinc or magnesium in question.
  • the metal surface treated in this way is dried and then with a second curable coating, for example a lacquer coating, Mistake.
  • Section 94: 94280a (JP-A-75/139 039) becomes a solution for forming conversion coatings on surfaces of zinc or zinc alloys.
  • the solution contains 3.0 to 20.0 g / l zinc ions, 1.0 up to 5.0 g / l manganese ions, 2.0 to 11.0 g / l nitrate ions, 10 to 100 g / l phosphate ions, 0.2 up to 0.8 vol .-% hydrogen peroxide and preferably 0.02 to 0.25 g / l nickel ions.
  • the object of the invention is phosphating processes to make available for use in continuously running conveyor systems are provided and in which the treated surfaces are rinsed with Water can be dispensed with.
  • Zinc concentrations between 5 and 25 g / l are due to an increased Process security preferable.
  • a phosphating process is required used, in which the phosphating solution 2 to 25 g / l of manganese ions, preferably 5 to 25 g / l, contains.
  • the phosphating solution to optimize the Properties of the phosphate layer for the intended use of the pretreated material contain other components.
  • the phosphating solution can also be one or several divalent metal ions in amounts of 0.1 to 15 each g / l contain, these additional metal ions are selected from nickel, cobalt, calcium and magnesium.
  • the phosphating solution can contain iron in quantities of 0.01 to 5 g / l and / or contain 3 to 200 mg / l copper ions.
  • fluoride in free or complex form, for example as fluorocomplexes of boron, silicon, titanium or Zircon, favorably influence the layer formation. This is particularly so in the phosphating of hot-dip galvanized steel Case.
  • the effective amounts of fluoride are between 0.01 and 5 g / l.
  • pH values above 3 as in the treatment of surfaces of electrolytically galvanized steel can be advantageous, the phosphating solutions tend to instability. You leave by adding 0.1 to 100 g / l of a chelating hydroxycarboxylic acid stabilize with 3 to 6 carbon atoms. Examples of such Hydroxycarboxylic acids are lactic acid and especially citric acid and tartaric acid.
  • the phosphating solution contains free acid in the range of 0 to 100 points.
  • the score will become more free Acidity is determined by adding 10 ml of the phosphating solution to 0.1 N Sodium hydroxide solution titrated to a pH of 3.6. The consumption at Sodium hydroxide solution in ml gives the free acid score. Has the phosphating solution the pH is already at 3.6, the score is on free acid therefore 0. At higher pH values of the phosphating solution is reverse titrated with 0.1N hydrochloric acid until a pH of 3.6 is reached. The free acid score is then negative and will show the consumption with a negative sign Equivalent to hydrochloric acid in ml.
  • the total acid content is determined by 10 ml of the phosphating solution with 0.1 N sodium hydroxide solution titrated to a pH of 8.5. The consumption of 0.1 n sodium hydroxide solution the total acidity is given in ml.
  • Total phosphating solution is in the Range from 40 to 400 points. You set the relationship free acid to total acid preferably so that it is in the range from 1: 4 to 1: 20.
  • Phosphating solutions which have a temperature are preferably used in the range of 15 to 80 ° C, especially in the range of 20 to 40 ° C.
  • the active substance content of the phosphating solutions should Range from about 5.5 to about 35% by weight.
  • the active substance content defined as the sum of the metal ions, phosphoric acid and optionally other components mentioned above.
  • the process is especially designed for the phosphating of running metal strips in strip treatment plants, such as those found in steel mills.
  • a liquid film coating of 2 to 10 ml of phosphating solution per m 2 of metal surface is preferably applied to the surfaces.
  • the optimal value of the liquid film coating depends on the one hand on the active substance content of the phosphating solution and on the other hand on the system-specific exposure time of the phosphating solution.
  • layer weights of the phosphate layers in the range from about 0.3 to about 3 g / m 2 are obtained with liquid film coatings of about 6 ml / m 2 , as is the basis for a subsequent coating are desired.
  • the higher the concentration of the phosphating solution the lower the liquid film coating.
  • the application of the phosphating solution to the surface and the Adjustment of the desired liquid film overlay can vary Procedure. For example, it is possible to spray the phosphating solution onto the surface in such a way that the desired liquid film overlay is set. Greater procedural security is achieved, however, if one looks after the jet the phosphating solution specifically adjusts the liquid film overlay, for example by blowing with compressed air or preferably by Squeeze rollers. Instead of spraying, you can use the phosphating solution also apply to the surface by application rollers, the desired liquid film overlay is set directly leaves.
  • Such application rollers are for the surface treatment of Metal strips known, for example under the name "chemcoater" or "roll coater".
  • the method can be carried out that the surfaces in the phosphating solution immersed. Metal strips can, for example, by the phosphating solution be driven through, leaving after leaving the desired liquid film overlay on the surface of the phosphating solution sets what, for example, by blowing with air or preferably with squeeze rollers.
  • the optimal process parameters depend on the specific material properties of the surfaces to be treated. For example it has been found that in the treatment of surfaces of running belts made of hot-dip galvanized steel Get phosphating results when the phosphating solution Active substance content in the range of 5.5 to 35 wt .-%. Of the preferred pH is in the range 1.0 to 2.2 and the weight ratio the sum of the divalent metal ions to phosphate preferably set in the range 1: 5 to 1: 6.
  • the presence of free or complex-bound fluoride in the phosphating solution has a favorable effect on the layer formation.
  • Fluoride concentrations in the range of 0.5 to 1.5 g / l are particularly effective.
  • Free fluoride is preferably used in the form of hydrofluoric acid, complex fluorides are preferably used as fluoro acids of boron, silicon, titanium and / or zircon.
  • alkali fluoride or acidic alkali fluorides such as KHF 2 to provide free fluoride is also possible.
  • the bath stability can be improved by adding about 1 to 10% by weight of a chelating hydroxycarboxylic acid improve with 3 to 6 carbon atoms, for example by lactic acid and preferably citric acid and / or tartaric acid.
  • accelerators that is to say substances which promote the formation of layers due to their oxidizing or reducing action, is not necessary in particular in the treatment of galvanized steel. However, they can be advantageous if the formation of certain crystal shapes is desired.
  • Suitable accelerators are the compounds known in the relevant prior art, in particular nitrate, nitrite, chlorate, nitrobenzenesulfonic acid or hydrogen peroxide.
  • Hydroxylamine can be used as a rather reducing accelerator. Hydrogen peroxide and hydroxylamine can be used as such, the other accelerators mentioned as free acids or in the form of salts soluble in the phosphating solution.
  • the surfaces are preferably heated to a temperature between 50 and 120 ° C, especially between 60 and 90 ° C.
  • the treated steel strip can be applied by a the appropriate temperature set drying oven become. Drying can also be done by blowing on the surfaces with hot gases, preferably with air and / or by exposure of infrared radiation.
  • the effective exposure time is given by the time between the first contact of the surface with the phosphating solution and the complete drying of the liquid film on the Surface, i.e. the end of the drying measure. Preferably this time period is in the range between approximately 3 and approximately 60 seconds.
  • phosphate layers with a layer weight in the range of 0.3 to 3 g / m 2 are produced on the surfaces.
  • Layer weights in this area are particularly desirable as the basis for subsequent painting, since this means that the two requirements of corrosion protection and paint adhesion are met to a particular extent at the same time.
  • layers are obtained which do not provide any reflections in X-ray diffraction studies, that is to say can be described as X-ray amorphous, or layers in which more or less pronounced reflections from Hopeit can be observed.
  • the sheets pre-phosphated by the process according to the invention can be used in particular in the manufacture of vehicles. It is the rule here that the vehicle bodies according to the assembly again phosphated and then painted become, what is currently a cathodic electrocoating is. In these cases, the method according to the invention Pre-phosphated material in the unpainted state for further processing transported. To improve temporary corrosion protection During storage and transportation the phosphated can Material must also be oiled. This will Simultaneously, subsequent forming operations are made easier. A post-phosphating of the assembled bodies after an alkaline cleaning is easily possible.
  • the phosphating according to the invention can also be carried out directly a tape coating with an organic film or Connect paint.
  • the term "coil coating” is used for this process. common. In this way, coil-coated material becomes currently preferred when building household appliances such as Refrigerators and washing machines as well as for architectural applications used.
  • activation In the prior art, it is customary to have a so-called activation precede the phosphating.
  • the aim of this activation is to allow crystal nuclei to form on the metal surface for the formation of the phosphate layer. This promotes the formation of dense and small crystalline phosphate layers.
  • aqueous solutions or suspensions of titanium phosphates are currently used for this activation.
  • Such activation can also precede the method according to the invention.
  • Commercial titanium-containing activating agents such as Fixodine R 950 from Henkel KGaA are suitable for this. When performing an activation, it is recommended to dry the tape between activation and phosphating.
  • electrolytically galvanized steel sheets (ZE) with a zinc coating of 7.5 .mu.m on each side and hot-dip galvanized steel sheets (Z) with a zinc coating of about 10 .mu.m were used on both sides.
  • the sheets each had the dimensions 10 cm x 20 cm.
  • a commercially available mildly alkaline cleaner Rosinline R 1250 I, Henkel KGaA, Düsseldorf.
  • the no-rinse treatment was simulated by pouring the treatment solution in a paint spinner (model 4302 from Lau GmbH) and at 550 rpm. was thrown out.
  • the layer weight was determined as a parameter for the phosphate layer obtained. Two different methods were used for this: When determining the layer weight by weighing, the sheet was weighed before the coating was carried out, then the phosphating solution was applied and dried and the coated sheet was weighed again. The layer coverage in g / m 2 was calculated from the difference in weight. When determining the layer weight by detaching, the phosphated sheets were weighed, the phosphate layer was removed by detaching with 0.5% by weight chromic acid solution and the sheets were weighed again. The mass of the removed layer g / m 2 was determined from the weight difference.
  • the layer weight determined by detachment is generally higher than that determined by weighing, since part of the metal surface is converted into metal phosphate by the phosphating. This part is not included in the determination of the layer weight by weighing, but is also removed when the layer is detached.
  • Table 1 contains phosphating baths for electrolytically galvanized steel and the layer coatings obtained, Table 2 corresponding examples for the treatment of hot-dip galvanized steel.
  • phosphating solutions are suitable which lead to layer weights in the range from 1 to 3 g / m 2 .
  • Zinc as oxide, manganese and nickel as carbonate were used in the exemplary treatment baths.
  • the baths contained no components other than water.
  • the layer composition was determined by means of EDX (X-ray emission) determined (in% by weight): Zn 7.5, Mn 2.2, P 7.5, Al 0.3, Rest: Can be taken up as oxygen.
  • EDX X-ray emission

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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)
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Abstract

PCT No. PCT/EP95/03619 Sec. 371 Date Mar. 24, 1997 Sec. 102(e) Date Mar. 24, 1997 PCT Filed Sep. 14, 1995 PCT Pub. No. WO96/09422 PCT Pub. Date Mar. 28, 1996A process for phosphating metal surfaces by treatment with an acidic zinc- and phosphathe-containing solution which does not require rinsing. The metal substrate is contacted with a phosphating solution containing 2 to 25 g/l of zinc ions, 2 to 25 g/l of manganese ions and 50 to 300 g/l of phosphate ions. The solution has a pH value of 1 to 3.6, a free acid content of 0 to 100 points, a total acid content of 40 to 400 points and a ratio of free acid to total acid of 1:4 to 1:20.

Description

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Oberflächen aus Stahl, Zink, Aluminium oder jeweils deren Legierungen. Besonders geeignet ist es für die Phosphatierung von elektrolytisch verzinktem oder schmelztauchverzinktem Stahl. Die Phosphatierlösungen werden dabei im Sinne eines sogenannten "no-rinse-Verfahrens" nach der vorgesehenen Einwirkungsdauer auf die Oberflächen nicht mit Wasser abgespült sondern unmittelbar eingetrocknet. Daher ist das Verfahren insbesondere zur Anwendung in kontinuierlich laufenden Bandbehandlungsanlagen geeignet.The invention relates to a method for Phosphating of surfaces made of steel, zinc, aluminum or in each case their alloys. It is particularly suitable for phosphating of electrolytically galvanized or hot dip galvanized Steel. The phosphating solutions are in the sense of a so-called "No-rinse process" after the intended exposure time not rinsed on the surfaces with water but immediately dried up. The method is therefore particularly useful suitable in continuously running belt treatment plants.

Die Phosphatierung von Metallen verfolgt das Ziel, auf der Metalloberfläche festverwachsene Metallphosphatschichten zu erzeugen, die für sich bereits die Korrosionsbeständigkeit verbessern und in Verbindung mit Lacken und anderen organischen Beschichtungen zu einer wesentlichen Erhöhung der Lackhaftung und der Resistenz gegen Unterwanderung bei Korrosionsbeanspruchung beitragen. Solche Phosphatierverfahren sind seit langem bekannt. Für eine Vorbehandlung vor der Lackierung, insbesondere vor einer elektrolytischen Tauchlackierung, wie sie im Kraftfahrzeugbau üblich ist, wurden in letzter Zeit insbesondere Niedrigzinkphosphatierverfahren bevorzugt, bei denen die Phosphatierlösungen vergleichsweise geringe Gehalte an Zinkionen von z. B. 0,5 bis 2 g/l aufweisen. The phosphating of metals pursues the goal on the metal surface to produce firmly adherent metal phosphate layers already improve the corrosion resistance and in combination with paints and other organic coatings into one Significant increase in paint adhesion and resistance to infiltration contribute to corrosion. Such phosphating processes have been known for a long time. For pretreatment before painting, especially before electrolytic dip painting, as it is common in motor vehicle construction, have been in the latter Time particularly preferred low zinc phosphating process, in which the phosphating solutions have comparatively low levels on zinc ions of e.g. B. 0.5 to 2 g / l.

Im Automobil- und insbesondere im Haushaltsgerätebau, aber auch für Architekturanwendungen, zeigt sich eine Tendenz zum Einsatz von im Stahlwerk vorphosphatierten verzinkten Stahlbändern, um die günstigeren Umformeigenschaften der mit einer Phosphatschicht versehenen Bleche zu nutzen und um chemische Behandlungsschritte vor der Lackierung einzusparen. Daher gewinnen Phosphatierverfahren an Bedeutung, die unter den Bedingungen der kurzen Phosphatierzeiten der Bandanlage von wenigen Sekunden zu qualitativ hochwertigen Phosphatschichten führen. Die Behandlung erfolgt üblicherweise im Spritzen, im Tauchen oder in kombinierten Verfahren, wobei die Phosphatierlösung nach der erwünschten Einwirkungszeit von der Metalloberfläche mit Wasser abgespült wird. Ein solches Verfahren ist beispielsweise in der DE-A-42 41 134 beschrieben, wonach Phosphatierlösungen zum Einsatz kommen, die 1,0 bis 6,0 g/l Zink und 8 bis 25 g/l Phosphat enthalten. Weitere fakultative Bestandteile sind Nickel, Kobalt, Mangan, Magnesium und Calcium in Mengen von jeweils 0,5 bis 5,0 g/l, Eisen(II) in Mengen bis 2 g/l und Kupfer in Mengen von 3 bis 50 mg/l.In automotive and especially in household appliance construction, but also for Architectural applications, there is a tendency to use im Steel plant pre-phosphated galvanized steel strips to make the cheaper Forming properties of those with a phosphate layer Use sheet metal and to perform chemical treatment steps before Saving paintwork. Therefore, phosphating processes are becoming increasingly important which under the conditions of the short phosphating times of Conveyor line of a few seconds to high quality phosphate layers to lead. Treatment is usually in the Syringes, in diving or in combined processes, the Phosphating solution after the desired exposure time from the metal surface is rinsed with water. Such a procedure is described for example in DE-A-42 41 134, according to which phosphating solutions the 1.0 to 6.0 g / l zinc and 8 to Contain 25 g / l phosphate. Other optional components are Nickel, cobalt, manganese, magnesium and calcium in amounts of each 0.5 to 5.0 g / l, iron (II) in quantities up to 2 g / l and copper in quantities from 3 to 50 mg / l.

Das bisher erforderliche Abspülen der Phosphatierlösung mit Wasser führt einerseits zu einem hohen Frischwasserverbrauch in der Phosphatieranlage und hat andererseits den Anfall von mit Schwermetallen verunreinigtem Abwasser zur Folge, das zur Wiederverwendung oder zum Ablassen in den Kanal aufbereitet werden muß. Das Konzept einer Phosphatierung ohne Nachspülung wurde bereits in der Literatur diskutiert (G.Carreras-Candi: "Caracteristiques de la Phosphatation sans Rincage"..., Surfaces 106 (1976), Heft 15, S. 25-28), ohne daß konkrete Angaben über die Durchführung des Verfahrens und dafür geeignete Behandlungsbäder gemacht wurden.The previously required rinsing of the phosphating solution with water on the one hand leads to high fresh water consumption in the phosphating plant and on the other hand has the attack of heavy metals contaminated wastewater resulting in reuse or prepared for draining into the sewer. The concept Phosphating without rinsing has already been reported in the literature discussed (G.Carreras-Candi: "Caracteristiques de la Phosphatation sans Rincage "..., Surfaces 106 (1976), No. 15, pp. 25-28), without concrete information about the implementation of the procedure and suitable treatment baths have been made for this.

Die DE-A-2 739 006, entsprechend FR-A-2 365 642, beschreibt ein Phosphatierverfahren, bei dem auf die unter Umwelt- und Kostenaspekten unerwünschte Wasserspülung verzichtet werden kann. Bei diesem Verfahren werden die Oberflächen während einer Dauer von 1 bis 5 Sekunden mit einer Phosphatierungslösung einer Temperatur von 50 bis 75 °C in Berührung gebracht, die 0,1 bis 5 g/l Zink, 1 bis 10 Gew.-Teile Nickel und/oder Kobalt pro Gew.-Teil Zink, 5 bis 50 g/l Phosphat und als Beschleuniger 0,5 bis 5 g/l Wasserstoffperoxid enthält. Danach wird ohne Zwischenspülung unmittelbar getrocknet. Dabei wird von einer Verwendung von Phosphatierlösungen mit einem Zinkgehalt über 5 g/l abgeraten, da sonst die Lackfilmhaftung verschlechtert wird.DE-A-2 739 006, corresponding to FR-A-2 365 642, describes a phosphating process in which the undesirable water rinsing from an environmental and cost perspective can be dispensed with. In this process, the surfaces for 1 to 5 seconds with a phosphating solution brought into contact with a temperature of 50 to 75 ° C, the 0.1 to 5 g / l zinc, 1 to 10 parts by weight nickel and / or cobalt per Part by weight zinc, 5 to 50 g / l phosphate and as an accelerator 0.5 to Contains 5 g / l hydrogen peroxide. After that, without intermediate rinsing immediately dried. This involves the use of phosphating solutions with a zinc content of over 5 g / l is discouraged, otherwise the paint film adhesion is deteriorated.

Die EP-B-141 341 beschreibt ebenfalls ein Phosphatierverfahren, bei dem auf eine Nachspülung mit Wasser verzichtet wird. Dieses Verfahren wurde insbesondere für ortsfeste Konstruktionen wie Brücken oder ähnliches entwickelt. Behandelt wird demnach mit einer Lösung, die 1 bis 5 Gew.-% Zink, 1 bis 20 Gew.-% Phosphorsäure, 0,01 bis 0,5 Gew.-% Kobalt und/oder Nickel und 0,02 bis 1,5 Gew.-% eines Beschleunigers enthält. Nach dem Auftrag der Phosphatierlösung, der beispielsweise durch Wischen, Bürsten, Aufstreichen, Aufrollen oder Aufspritzen erfolgen kann, läßt man die Lösung für eine nicht näher bestimmte Zeit einwirken, wobei die Lösung ausreagiert oder auch nur teilweise reagiert. In beiden Fällen kann im Anschluß an die Einwirkung gespült werden.EP-B-141 341 also describes a phosphating process in which is not rinsed with water. This method was used especially for fixed structures such as bridges or the like developed. Treated with a solution the 1 to 5% by weight zinc, 1 to 20% by weight phosphoric acid, 0.01 to 0.5% by weight of cobalt and / or nickel and 0.02 to 1.5% by weight of one Contains accelerator. After applying the phosphating solution, the for example by wiping, brushing, spreading, rolling up or Spraying can take place, the solution is not left for one act for a certain time, whereby the solution reacts or also only partially responded. In both cases, following the Exposure to be rinsed.

Im Vergleich zu üblichen Phosphatierverfahren, die als Vorbehandlung vor einer Lackierung eingesetzt werden, weist die vorstehend beschriebene Phosphatierlösung hohe Gehalte an Zink und Phosphat auf. Phosphatierlösungen in ähnlichen Konzentrationsbereichen sind auch bekannt zum Abscheiden von Phosphatschichten auf Metallteilen, die einer kalten mechanischen Formgebung, beispielsweise durch Ziehen oder Pressen, unterworfen werden sollen. Die sich hierbei abscheidenden relativ dicken Phosphatschichten, die man zur Erhöhung ihrer Wirkung noch mit Öl tränken kann, wirken dabei als Schmiermittel und verringern die Reibung zwischen Werkzeug und Werkstück. Als Vorbehandlung vor einer Lackierung sind sie üblicherweise nicht geeignet, da auf den dicken Phosphatschichten die Lackhaftung bei mechanischer Beanspruchung nur schlecht ist. Eine solche Phosphatierlösung, die zur Ausbildung von Phosphatschichten auf Stahlband oder -draht als Gleitmittel vor dem Kaltziehen oder anderen Verformungen eingesetzt werden kann, ist beispielsweise in der DE-B-25 52 122 beschrieben. Demnach werden Lösungen eingesetzt, die Zink in einer Menge von 5 bis 100 g/l und Phosphat in einer Menge von 10 bis 150 g/l sowie als Beschleuniger wirkendes Nitrat in einer Menge von 10 bis 80 g/l enthalten. Die Phosphatierlösung wird mit der Oberfläche für eine Zeitspanne von 5 bis 15 Sekunden in Kontakt gebracht und anschließend mit Wasser abgespült. Compared to conventional phosphating processes that are used as pretreatment be used before painting, the above Phosphating solution described high levels of zinc and phosphate on. Phosphating solutions are in similar concentration ranges also known for depositing phosphate layers on metal parts, that of a cold mechanical shape, for example by pulling or presses to be subjected. The separating ones relatively thick layers of phosphate that you can use to increase their effects can still soak with oil, act as lubricants and reduce the friction between tool and workpiece. They are usually not a pretreatment before painting suitable because the paint adheres to the thick phosphate layers mechanical stress is bad. Such a phosphating solution, for the formation of phosphate layers on steel strip or wire as a lubricant before cold drawing or other deformations can be used, for example, in DE-B-25 52 122. Accordingly, solutions are used that contain zinc in in an amount of 5 to 100 g / l and phosphate in an amount of 10 up to 150 g / l and nitrate acting as an accelerator in a quantity from 10 to 80 g / l included. The phosphating solution is with the Surface in contact for a period of 5 to 15 seconds brought and then rinsed with water.

EP-A-0 565 346 betrifft eine Phosphatierlösung für Metalloberflächen aus Stahl, Zink, Aluminium oder deren Legierungen. In einer ersten Verfahrensstufe wird die Metalloberfläche mit einer wäßrigen Lösung behandelt, die 0,01 bis 1,0 mol/l Siliciumdioxid, 0,02 bis 0,5 mol/l Phosphorsäure und 0,001 bis 0,5 mol/l eines zweiwertigen Metallions enthält. Als zweiwertige Metallionen kommen beispielsweise Mangan, Kobalt, Eisen, Nickel, Zink und vorzugsweise Calcium, Zink oder Magnesium in Frage. Ohne Zwischenspülung wird die so behandeltes Metalloberfläche getrocknet und anschließend mit einem zweiten härtbaren Überzug, beispielsweise einem Lacküberzug, versehen.EP-A-0 565 346 relates to a phosphating solution for metal surfaces made of steel, zinc, Aluminum or its alloys. In a first process step, the metal surface treated with an aqueous solution containing 0.01 to 1.0 mol / l silicon dioxide, 0.02 to 0.5 mol / l phosphoric acid and 0.001 to 0.5 mol / l of a divalent metal ion contains. Examples of divalent metal ions are manganese, cobalt, iron, Nickel, zinc and preferably calcium, zinc or magnesium in question. Without Intermediate rinsing, the metal surface treated in this way is dried and then with a second curable coating, for example a lacquer coating, Mistake.

In Chemical Abstracts, Vol. 84 (1976), Seite 283, Referat 94:94280a (JP-A-75/139 039) wird eine Lösung zur Bildung von Konversionsüberzügen auf Oberflächen von Zink oder Zinklegierungen beschrieben. Die Lösung enthält 3,0 bis 20,0 g/l Zinkionen, 1,0 bis 5,0 g/l Manganionen, 2,0 bis 11,0 g/l Nitrationen, 10 bis 100 g/l Phosphationen, 0,2 bis 0,8 Vol.-% Wasserstoffperoxid und vorzugsweise 0,02 bis 0,25 g/l Nickelionen.In Chemical Abstracts, Vol. 84 (1976), page 283, Section 94: 94280a (JP-A-75/139 039) becomes a solution for forming conversion coatings on surfaces of zinc or zinc alloys. The solution contains 3.0 to 20.0 g / l zinc ions, 1.0 up to 5.0 g / l manganese ions, 2.0 to 11.0 g / l nitrate ions, 10 to 100 g / l phosphate ions, 0.2 up to 0.8 vol .-% hydrogen peroxide and preferably 0.02 to 0.25 g / l nickel ions.

Die Erfindung stellt sich die Aufgabe, Phosphatierverfahren zur Verfügung zu stellen, die zum Einsatz in kontinuierlich laufenden Bandanlagen vorgesehen sind und bei denen auf ein Abspülen der behandelten Oberflächen mit Wasser verzichtet werden kann.The object of the invention is phosphating processes to make available for use in continuously running conveyor systems are provided and in which the treated surfaces are rinsed with Water can be dispensed with.

Die Erfindung betrifft ein Verfahren zur Phosphatierung von Oberflächen aus Stahl, Zink, Aluminium oder jeweils deren Legierungen durch Behandlung mit sauren, zink- und phosphathaltigen Lösungen und Eintrocknen der Lösungen ohne Zwischenspülung, dadurch gekennzeichnet, daß die Oberflächen mit einer Phosphatierlösung in Kontakt gebracht werden, die

  • 2 bis 25 g/l Zinkionen,
  • 2 bis 25 g/l Manganionen und
  • 50 bis 300 g/l Phosphationen enthält und einen pH-Wert im Bereich von 1 bis 3,6,
  • einen Gehalt an Freier Säure im Bereich von 0 bis 100 Punkten und
  • einen Gehalt an Gesamtsäure im Bereich von 40 bis 400 Punkten aufweist.
    • The invention relates to a method for phosphating surfaces made of steel, zinc, aluminum or their alloys in each case by treatment with acidic, zinc- and phosphate-containing solutions and drying the solutions without intermediate rinsing, characterized in that the surfaces are brought into contact with a phosphating solution. the
  • 2 to 25 g / l zinc ions,
  • 2 to 25 g / l manganese ions and
  • Contains 50 to 300 g / l phosphate ions and a pH in the range from 1 to 3.6,
  • a free acid content in the range from 0 to 100 points and
  • has a total acid content in the range of 40 to 400 points.

    • Zinkkonzentrationen zwischen 5 und 25 g/l sind wegen einer erhöhten Verfahrenssicherheit vorzuziehen. Für einen verbesserten Korrosionsschutz, wie er beispielsweise für die Anwendung im Fahrzeugbau erforderlich ist, wird ein Phosphatierverfahren eingesetzt, bei dem die Phosphatierlösung 2 bis 25 g/l Manganionen, vorzugsweise 5 bis 25 g/l, enthält. Zusätzlich kann die Phosphatierlösung zur Optimierung der Eigenschaften der Phosphatschicht für den beabsichtigten Verwendungszweck des vorbehandelten Materials weitere Komponenten enthalten. Beispielsweise kann die Phosphatierlösung weiterhin eines oder mehrere zweiwertige Metallionen in Mengen von jeweils 0,1 bis 15 g/l enthalten, wobei diese zusätzlichen Metallionen ausgewählt sind aus Nickel, Kobalt, Calcium und Magnesium. Weiterhin kann die Phosphatierlösung Eisen in Mengen von 0,01 bis 5 g/l und/oder 3 bis 200 mg/l Kupferionen enthalten. Je nach Substrat können Zusätze von Fluorid in freier oder komplex gebundener Form, beispielsweise als Fluorokomplexe von Bor, Silicium, Titan oder Zirkon, die Schichtausbildung günstig beeinflussen. Dies ist insbesondere bei der Phosphatierung von schmelztauchverzinktem Stahl der Fall. Die wirksamen Fluoridmengen liegen zwischen 0,01 und 5 g/l. Bei pH-Werten oberhalb von 3, wie sie bei der Behandlung von Oberflächen von elektrolytisch verzinktem Stahl vorteilhaft sein können, neigen die Phosphatierlösungen zur Instabilität. Sie lassen sich durch Zusatz von 0,1 bis 100 g/l einer chelatisierenden Hydroxycarbonsäure mit 3 bis 6 C-Atomen stabilisieren. Beispiele solcher Hydroxycarbonsäuren sind Milchsäure und insbesondere Citronensäure und Weinsäure. Zinc concentrations between 5 and 25 g / l are due to an increased Process security preferable. For an improved Corrosion protection, such as for use in vehicle construction a phosphating process is required used, in which the phosphating solution 2 to 25 g / l of manganese ions, preferably 5 to 25 g / l, contains. In addition can the phosphating solution to optimize the Properties of the phosphate layer for the intended use of the pretreated material contain other components. For example, the phosphating solution can also be one or several divalent metal ions in amounts of 0.1 to 15 each g / l contain, these additional metal ions are selected from nickel, cobalt, calcium and magnesium. Farther the phosphating solution can contain iron in quantities of 0.01 to 5 g / l and / or contain 3 to 200 mg / l copper ions. Depending on the substrate can add fluoride in free or complex form, for example as fluorocomplexes of boron, silicon, titanium or Zircon, favorably influence the layer formation. This is particularly so in the phosphating of hot-dip galvanized steel Case. The effective amounts of fluoride are between 0.01 and 5 g / l. At pH values above 3, as in the treatment of surfaces of electrolytically galvanized steel can be advantageous, the phosphating solutions tend to instability. You leave by adding 0.1 to 100 g / l of a chelating hydroxycarboxylic acid stabilize with 3 to 6 carbon atoms. Examples of such Hydroxycarboxylic acids are lactic acid and especially citric acid and tartaric acid.

    Der Gehalt der Phosphatierlösung an freier Säure liegt im Bereich von 0 bis 100 Punkten. Dabei wird die Punktzahl an freier Säure bestimmt, indem man 10 ml der Phosphatierlösung mit 0,1 n Natronlauge bis zu einem pH-Wert von 3,6 titriert. Der Verbrauch an Natronlauge in ml gibt die Punktzahl freier Säure an. Hat die Phosphatierlösung bereits einen pH-Wert von 3,6, ist die Punktzahl an freier Säure demnach 0. Bei höheren pH-Werten der Phosphatierlösung wird umgekehrt mit 0,1 n Salzsäure titriert, bis ein pH-Wert von 3,6 erreicht ist. Die Punktzahl an freier Säure ist dann negativ und wird dem mit einem negativen Vorzeichen versehenen Verbrauch an Salzsäure in ml gleichgesetzt. Der Gehalt an Gesamtsäure wird bestimmt, indem man 10 ml der Phosphatierlösung mit 0,1 n Natronlauge bis zu einem pH-Wert von 8,5 titriert. Der Verbrauch an 0,1 n Natronlauge in ml gibt die Punktzahl Gesamtsäure an. Für die erfindungsgemäße Phosphatierlösung liegt die Gesamtsäure im Bereich von 40 bis 400 Punkten. Dabei stellt man das Verhältnis freie Säure zu Gesamtsäure vorzugsweise so ein, daß es im Bereich von 1 : 4 bis 1 : 20 liegt.The phosphating solution contains free acid in the range of 0 to 100 points. The score will become more free Acidity is determined by adding 10 ml of the phosphating solution to 0.1 N Sodium hydroxide solution titrated to a pH of 3.6. The consumption at Sodium hydroxide solution in ml gives the free acid score. Has the phosphating solution the pH is already at 3.6, the score is on free acid therefore 0. At higher pH values of the phosphating solution is reverse titrated with 0.1N hydrochloric acid until a pH of 3.6 is reached. The free acid score is then negative and will show the consumption with a negative sign Equivalent to hydrochloric acid in ml. The total acid content is determined by 10 ml of the phosphating solution with 0.1 N sodium hydroxide solution titrated to a pH of 8.5. The consumption of 0.1 n sodium hydroxide solution the total acidity is given in ml. For the invention Total phosphating solution is in the Range from 40 to 400 points. You set the relationship free acid to total acid preferably so that it is in the range from 1: 4 to 1: 20.

    Vorzugsweise verwendet man Phosphatierlösungen, die eine Temperatur im Bereich 15 bis 80 °C, insbesondere im Bereich 20 bis 40 °C aufweisen. Der Aktivsubstanzgehalt der Phosphatierlösungen soll im Bereich von etwa 5,5 bis etwa 35 Gew.-% liegen. Dabei wird der Aktivsubstanzgehalt definiert als Summe der Metallionen, Phosphorsäure und gegebenenfalls weiterer vorstehend genannter Komponenten.Phosphating solutions which have a temperature are preferably used in the range of 15 to 80 ° C, especially in the range of 20 to 40 ° C. The active substance content of the phosphating solutions should Range from about 5.5 to about 35% by weight. The active substance content defined as the sum of the metal ions, phosphoric acid and optionally other components mentioned above.

    Das Verfahren ist insbesondere konzipiert zur Phosphatierung laufender Metallbänder in Bandbehandlungsanlagen, wie sie beispielsweise in Stahlwerken angetroffen werden. Hierbei bringt man auf die Oberflächen vorzugsweise eine Flüssigfilmauflage von 2 bis 10 ml Phosphatierlösung pro m2 Metalloberfläche auf. Der optimale Wert der Flüssigfilmauflage hängt einerseits vom Aktivsubstanzgehalt der Phosphatierlösung und andererseits von der anlagenspezifischen Einwirkungszeit der Phosphatierlösung ab. Bei den derzeit üblichen Bandgeschwindigkeiten der Größenordnung 10 bis 300 m/Minute werden mit Flüssigfilmauflagen von etwa 6 ml/m2 Schichtgewichte der Phosphatschichten im Bereich von etwa 0,3 bis etwa 3 g/m2 erhalten, wie sie als Grundlage für eine nachfolgende Lackierung erwünscht sind. Allgemein sind die Konzentrationen der Phosphatierlösung umso höher zu wählen, je geringer die Flüssigfilmauflage ist.The process is especially designed for the phosphating of running metal strips in strip treatment plants, such as those found in steel mills. Here, a liquid film coating of 2 to 10 ml of phosphating solution per m 2 of metal surface is preferably applied to the surfaces. The optimal value of the liquid film coating depends on the one hand on the active substance content of the phosphating solution and on the other hand on the system-specific exposure time of the phosphating solution. At the currently usual belt speeds of the order of 10 to 300 m / minute, layer weights of the phosphate layers in the range from about 0.3 to about 3 g / m 2 are obtained with liquid film coatings of about 6 ml / m 2 , as is the basis for a subsequent coating are desired. In general, the higher the concentration of the phosphating solution, the lower the liquid film coating.

    Die Applikation der Phosphatierlösung auf die Oberfläche und die Einstellung der erwünschten Flüssigfilmauflage kann dabei nach unterschiedlichen Verfahren erfolgen. Beispielsweise ist es möglich, die Phosphatierlösung auf die Oberfläche derart aufzudüsen, daß sich die erwünschte Flüssigfilmauflage einstellt. Eine höhere Verfahrenssicherheit wird jedoch erreicht, wenn man nach dem Aufdüsen der Phosphatierlösung die Flüssigfilmauflage gezielt einstellt, beispielsweise durch Abblasen mit Preßluft oder vorzugsweise durch Abquetschwalzen. Anstelle des Aufdüsens kann man die Phosphatierlösung auch durch Auftragswalzen auf die Oberfläche aufbringen, wobei sich die erwünschte Flüssigfilmauflage direkt einstellen läßt. Solche Auftragswalzen sind für die Oberflächenbehandlung von Metallbändern bekannt, beispielsweise unter der Bezeichnung "chemcoater" oder "roll-coater". Weiterhin kann das Verfahren derart ausgeführt werden, daß man die Oberflächen in die Phosphatierlösung eintaucht. Metallbänder können beispielsweise durch die Phosphatierlösung hindurch gefahren werden, wobei man nach dem Verlassen der Phosphatierlösung auf der Oberfläche die erwünschte Flüssigfilmauflage einstellt, was beispielsweise durch Abblasen mit Luft oder vorzugsweise mit Abquetschwalzen erfolgen kann.The application of the phosphating solution to the surface and the Adjustment of the desired liquid film overlay can vary Procedure. For example, it is possible to spray the phosphating solution onto the surface in such a way that the desired liquid film overlay is set. Greater procedural security is achieved, however, if one looks after the jet the phosphating solution specifically adjusts the liquid film overlay, for example by blowing with compressed air or preferably by Squeeze rollers. Instead of spraying, you can use the phosphating solution also apply to the surface by application rollers, the desired liquid film overlay is set directly leaves. Such application rollers are for the surface treatment of Metal strips known, for example under the name "chemcoater" or "roll coater". Furthermore, the method can be carried out that the surfaces in the phosphating solution immersed. Metal strips can, for example, by the phosphating solution be driven through, leaving after leaving the desired liquid film overlay on the surface of the phosphating solution sets what, for example, by blowing with air or preferably with squeeze rollers.

    Die optimalen Verfahrensparameter hängen von den spezifischen Materialeigenschaften der zu behandelnden Oberflächen ab. Beispielsweise wurde gefunden, daß man bei der Behandlung von Oberflächen von laufenden Bändern aus schmelztauchverzinktem Stahl dann optimale Phosphatierergebnisse erhält, wenn die Phosphatierlösung einen Aktivsubstanzgehalt im Bereich von 5,5 bis 35 Gew.-% aufweist. Der bevorzugte pH-Wert liegt im Bereich 1,0 bis 2,2 und das Gewichtsverhältnis der Summe der zweiwertigen Metallionen zu Phosphat wird vorzugsweise im Bereich 1 : 5 bis 1 : 6 eingestellt.The optimal process parameters depend on the specific material properties of the surfaces to be treated. For example it has been found that in the treatment of surfaces of running belts made of hot-dip galvanized steel Get phosphating results when the phosphating solution Active substance content in the range of 5.5 to 35 wt .-%. Of the preferred pH is in the range 1.0 to 2.2 and the weight ratio the sum of the divalent metal ions to phosphate preferably set in the range 1: 5 to 1: 6.

    Bei der Behandlung von schmelztauchverzinktem Stahl wirkt sich die Anwesenheit von freiem oder komplexgebundenem Fluorid in der Phosphatierlösung günstig auf die Schichtausbildung aus. Dabei sind Fluoridkonzentrationen im Bereich von 0,5 bis 1,5 g/l besonders wirkungsvoll. Freies Fluorid wird vorzugsweise in Form von Flußsäure, komplexe Fluoride werden vorzugsweise als Fluorosäuren von Bor, Silicium, Titan und/oder Zirkon eingesetzt. Die Verwendung von Alkalifluorid oder sauren Alkalifluoriden wie KHF2 zur Bereitstellung von freiem Fluorid ist ebenfalls möglich.When treating hot-dip galvanized steel, the presence of free or complex-bound fluoride in the phosphating solution has a favorable effect on the layer formation. Fluoride concentrations in the range of 0.5 to 1.5 g / l are particularly effective. Free fluoride is preferably used in the form of hydrofluoric acid, complex fluorides are preferably used as fluoro acids of boron, silicon, titanium and / or zircon. The use of alkali fluoride or acidic alkali fluorides such as KHF 2 to provide free fluoride is also possible.

    Bei der Behandlung von Oberflächen von laufenden Bändern aus elektrolytisch verzinktem Stahl erhält man dagegen die besten Ergebnisse, wenn man folgende Bedingungen einstellt: Aktivsubstanzgehalt der Phosphatierlösung im Bereich 5,5 bis 20 Gew.-%, pH-Wert im Bereich 1,5 bis 3,5, Gewichtsverhältnis der Summe der zweiwertigen Metallionen zu Phosphat im Bereich 1 : 5 bis 1 : 6. Phosphatierlösungen mit diesen Badparametern neigen zur Instabilität, insbesondere, wenn der pH-Wert in der oberen Hälfte des genannten Bereichs eingestellt wird. Die Badstabilität läßt sich durch Zugabe von etwa 1 bis 5 Gew.-% einer chelatisierenden Hydroxycarbonsäure mit 3 bis 6 C-Atomen verbessern. Hierfür kommen beispielsweise Milchsäure, und vorzugsweise Citronensäure und/oder Weinsäure in Betracht.When treating surfaces of moving belts from electrolytic galvanized steel gives you the best results, if you set the following conditions: Active substance content the phosphating solution in the range 5.5 to 20 wt .-%, pH in Range 1.5 to 3.5, weight ratio of the sum of the divalent Metal ions to phosphate in the range 1: 5 to 1: 6. Phosphating solutions with these bath parameters tend to instability, in particular, if the pH is in the upper half of the range is set. The bath stability can be increased by adding about 1 to 5 wt .-% of a chelating hydroxycarboxylic acid with 3 to Improve 6 carbon atoms. Lactic acid, for example, and preferably citric acid and / or tartaric acid.

    Bei der Behandlung von Oberflächen von laufenden Bändern aus kaltgewalztem, ungalvanisiertem Stahl wählt man vorzugsweise folgende Bedingungen: Aktivsubstanzgehalt der Phosphatierlösung im Bereich von 5,5 bis 25 Gew.-%, pH-Wert im Bereich 2,0 bis 3,6, Gewichtsverhältnis der Summe der zweiwertigen Metallionen zu Phosphat im Bereich 1 : 5 bis 1 : 6. Auch hierbei läBt sich die Badstabilität durch Zugabe von etwa 1 bis 10 Gew.-% einer chelatisierenden Hydroxycarbonsäure mit 3 bis 6 C-Atomen verbessern, beispielsweise durch Milchsäure und vorzugsweise Citronensäure und/oder Weinsäure.When treating surfaces of running strips made of cold-rolled, ungalvanized steel is preferably chosen from the following Conditions: Active substance content of the phosphating solution in the range from 5.5 to 25% by weight, pH in the range from 2.0 to 3.6, weight ratio the sum of the divalent metal ions to phosphate in the range 1: 5 to 1: 6. Here too the bath stability can be improved by adding about 1 to 10% by weight of a chelating hydroxycarboxylic acid improve with 3 to 6 carbon atoms, for example by lactic acid and preferably citric acid and / or tartaric acid.

    Die Verwendung von sogenannten Beschleunigern, also von Substanzen, die aufgrund ihrer oxidierenden oder reduzierenden Wirkung die Schichtausbildung fördern, ist insbesondere bei der Behandlung von verzinktem Stahl nicht erforderlich. Sie können jedoch Vorteile bringen, wenn die Ausbildung bestimmter Kristallformen erwünscht ist. Als Beschleuniger kommen die im einschlägigen Stand der Technik bekannten Verbindungen in Frage, insbesondere Nitrat, Nitrit, Chlorat, Nitrobenzolsulfonsäure oder Wasserstoffperoxid. Als eher reduzierend wirkender Beschleuniger läßt sich Hydroxylamin einsetzen. Dabei können Wasserstoffperoxid und Hydroxylamin als solche eingesetzt werden, die anderen genannten Beschleuniger als freie Säuren oder in Form von in der Phosphatierlösung löslichen Salzen. Da nach dem Eintrocknen der Phosphatierlösung auf der Oberfläche möglichst wenig und vorzugsweise keine wasserlöslichen Salze zurückbleiben sollen, ist es jedoch empfehlenswert, Alkalimetall- und Ammoniumsalze sowie Sulfate zu vermeiden. Besonders bevorzugt sind Beschleuniger, die keine salzartigen Rückstände auf den behandelten Oberflächen hinterlassen. Daher sind Hydroxylamin und insbesondere Wasserstoffperoxid besonders geeignet. Im Falle der Verwendung von Beschleunigern liegen deren bevorzugte Konzentrationen für Hydroxylamin, Nitrobenzolsulfonsäure und Chlorat im Bereich 2 bis 5 g/l, für Nitrit im Bereich 0,2 bis 1 g/l und für H2O2 im Bereich 20 bis 100 ppm. The use of so-called accelerators, that is to say substances which promote the formation of layers due to their oxidizing or reducing action, is not necessary in particular in the treatment of galvanized steel. However, they can be advantageous if the formation of certain crystal shapes is desired. Suitable accelerators are the compounds known in the relevant prior art, in particular nitrate, nitrite, chlorate, nitrobenzenesulfonic acid or hydrogen peroxide. Hydroxylamine can be used as a rather reducing accelerator. Hydrogen peroxide and hydroxylamine can be used as such, the other accelerators mentioned as free acids or in the form of salts soluble in the phosphating solution. Since as little and preferably no water-soluble salts as possible should remain on the surface after the phosphating solution has dried on, it is advisable to avoid alkali metal and ammonium salts and sulfates. Accelerators which do not leave any salt-like residues on the treated surfaces are particularly preferred. Hydroxylamine and in particular hydrogen peroxide are therefore particularly suitable. If accelerators are used, their preferred concentrations for hydroxylamine, nitrobenzenesulfonic acid and chlorate are in the range from 2 to 5 g / l, for nitrite in the range from 0.2 to 1 g / l and for H 2 O 2 in the range from 20 to 100 ppm.

    Der nach der Applikation der Phosphatierlösung auf der Oberfläche verbleibende Flüssigfilm wird erfindungsgemäß nicht abgespült, sondern eingetrocknet. Hierzu erwärmt man die Oberflächen vorzugsweise auf eine Temperatur zwischen 50 und 120 °C, insbesondere zwischen 60 und 90 °C. Hierfür stehen verschiedene Möglichkeiten zur Verfügung. Beispielsweise kann das behandelte Stahlband durch einen auf die entsprechende Temperatur eingestellten Trockenofen gefahren werden. Die Trocknung kann aber auch durch Anblasen der Oberflächen mit heißen Gasen, vorzugsweise mit Luft und/oder durch Einwirkung von Infrarotstrahlung erfolgen. Da die saure Phosphatierungslösung so lange mit der Metalloberfläche chemisch reagieren kann, wie sie noch flüssig ist, ist die effektive Einwirkungszeit gegeben durch die Zeit zwischen dem ersten Kontakt der Oberfläche mit der Phosphatierlösung und dem völligen Eintrocknen des Flüssigfilms auf der Oberfläche, also dem Ende der Trocknungsmaßnahme. Vorzugsweise liegt diese Zeitspanne im Bereich zwischen etwa 3 und etwa 60 Sekunden.The one after the application of the phosphating solution on the surface The remaining liquid film is not rinsed off according to the invention, but instead dried up. For this purpose, the surfaces are preferably heated to a temperature between 50 and 120 ° C, especially between 60 and 90 ° C. Various options are available for this. For example, the treated steel strip can be applied by a the appropriate temperature set drying oven become. Drying can also be done by blowing on the surfaces with hot gases, preferably with air and / or by exposure of infrared radiation. Because the acidic phosphating solution can react with the metal surface as long as it can is still liquid, the effective exposure time is given by the time between the first contact of the surface with the phosphating solution and the complete drying of the liquid film on the Surface, i.e. the end of the drying measure. Preferably this time period is in the range between approximately 3 and approximately 60 seconds.

    Unter den genannten Verfahrensbedingungen werden auf den Oberflächen Phosphatschichten mit einem Schichtgewicht im Bereich von 0,3 bis 3 g/m2 erzeugt. Als Grundlage für eine nachfolgende Lackierung sind Schichtgewichte in diesem Bereich besonders erwünscht, da hierdurch die beiden Anforderungen Korrosionsschutz und Lackhaftung in besonderem Maße gleichzeitig erfüllt werden. Je nach Verfahrensführung werden Schichten erhalten, die bei Röntgenbeugungsuntersuchungen keine Reflexe liefern, also als röntgenamorph zu bezeichnen sind, oder solche, bei denen mehr oder weniger ausgeprägte Reflexe von Hopeit beobachtbar sind.Under the stated process conditions, phosphate layers with a layer weight in the range of 0.3 to 3 g / m 2 are produced on the surfaces. Layer weights in this area are particularly desirable as the basis for subsequent painting, since this means that the two requirements of corrosion protection and paint adhesion are met to a particular extent at the same time. Depending on the procedure, layers are obtained which do not provide any reflections in X-ray diffraction studies, that is to say can be described as X-ray amorphous, or layers in which more or less pronounced reflections from Hopeit can be observed.

    Die nach dem erfindungsgemäßen Verfahren vorphosphatierten Bleche lassen sich insbesondere bei der Herstellung von Fahrzeugen einsetzen. Hierbei ist es die Regel, daß die Fahrzeugkarosserien nach dem Zusammenbau nochmals phosphatiert und anschließend lackiert werden, wofür derzeit eine kathodische Elektrotauchlackierung üblich ist. In diesen Fällen wird das nach dem erfindungsgemäßen Verfahren vorphosphatierte Material im unlackierten Zustand zum Weiterverarbeiter transportiert. Zur Verbesserung des temporären Korrosionsschutzes während Lagerung und Transport kann das phosphatierte Material zusätzlich eingeölt werden. Hierdurch werden gleichzeitig spätere Umformvorgänge erleichtert. Eine Nachphosphatierung der montierten Karosserien nach einer alkalischen Reinigung ist problemlos möglich.The sheets pre-phosphated by the process according to the invention can be used in particular in the manufacture of vehicles. It is the rule here that the vehicle bodies according to the assembly again phosphated and then painted become, what is currently a cathodic electrocoating is. In these cases, the method according to the invention Pre-phosphated material in the unpainted state for further processing transported. To improve temporary corrosion protection During storage and transportation the phosphated can Material must also be oiled. This will Simultaneously, subsequent forming operations are made easier. A post-phosphating of the assembled bodies after an alkaline cleaning is easily possible.

    Der erfindungsgemäßen Phosphatierung kann sich jedoch auch unmittelbar eine Bandbeschichtung mit einem organischen Film oder einem Lack anschließen. Für diesen Prozeß ist die Bezeichnung "coil-coating" geläufig. Auf diese Weise bandbeschichtetes Material wird derzeit bevorzugt beim Bau von Haushaltsgeräten wie beispielsweise Kühlschränken und Waschmaschinen sowie für Architekturanwendungen eingesetzt.However, the phosphating according to the invention can also be carried out directly a tape coating with an organic film or Connect paint. The term "coil coating" is used for this process. common. In this way, coil-coated material becomes currently preferred when building household appliances such as Refrigerators and washing machines as well as for architectural applications used.

    Im Stand der Technik ist es üblich, der Phosphatierung eine sogenannte Aktivierung vorausgehen zu lassen. Diese Aktivierung hat das Ziel, auf der Metalloberfläche Kristallkeime für die Ausbildung der Phosphatschicht entstehen zu lassen. Hierdurch wird die Ausbildung von dichten und kleinkristallinen Phosphatschichten gefördert. In der Praxis werden derzeit für diese Aktivierung ausschließlich wäßrige Lösungen bzw. Suspensionen von Titanphosphaten eingesetzt. Eine solche Aktivierung kann auch dem erfindungsgemäßen Verfahren vorgeschaltet werden. Geeignet hierfür sind handelsgängige titanphosphathaltige Aktiviermittel wie beispielsweise FixodineR 950 der Henkel KGaA. Bei Durchführung einer Aktivierung ist es empfehlenswert, das Band zwischen Aktivierung und Phosphatierung zu trocknen. In the prior art, it is customary to have a so-called activation precede the phosphating. The aim of this activation is to allow crystal nuclei to form on the metal surface for the formation of the phosphate layer. This promotes the formation of dense and small crystalline phosphate layers. In practice, only aqueous solutions or suspensions of titanium phosphates are currently used for this activation. Such activation can also precede the method according to the invention. Commercial titanium-containing activating agents such as Fixodine R 950 from Henkel KGaA are suitable for this. When performing an activation, it is recommended to dry the tape between activation and phosphating.

    AusführungsbeispieleEmbodiments

    Für die labormäßige Abprüfung des erfindungsgemäßen Phosphatierverfahrens wurden beidseitig elektrolytisch verzinkte Stahlbleche (ZE) mit einer Zinkauflage von jeweils 7,5 µ und beidseitig schmelztauchverzinkte Stahlbleche (Z) mit einer Zinkauflage von etwa 10 µ verwendet. Die Bleche hatten jeweils die Abmessungen 10 cm x 20 cm. Vor der Phosphatierung wurden diese mit einem handelsüblichen mildalkalischen Reiniger (RidolineR 1250 I, Henkel KGaA, Düsseldorf) entfettet. Die no-rinse-Behandlung wurde dadurch simuliert, daß die Behandlungslösung in einer Lackschleuder (Modell 4302 der Firma Lau GmbH) aufgegossen und bei 550 U/Min. abgeschleudert wurde. Hierdurch ließ sich ein Naßfilm mit einer Auflage von etwa 6 ml/m2 erzeugen. Nach dem etwa 5 Sekunden dauernden Aufschleudern der Behandlungslösung wurden die Bleche unmittelbar in einem auf 75 °C aufgeheizten Umluft-Trockenschrank für die Dauer von etwa 120 Sekunden getrocknet.For the laboratory testing of the phosphating process according to the invention, electrolytically galvanized steel sheets (ZE) with a zinc coating of 7.5 .mu.m on each side and hot-dip galvanized steel sheets (Z) with a zinc coating of about 10 .mu.m were used on both sides. The sheets each had the dimensions 10 cm x 20 cm. Before phosphating, these were degreased with a commercially available mildly alkaline cleaner (Ridoline R 1250 I, Henkel KGaA, Düsseldorf). The no-rinse treatment was simulated by pouring the treatment solution in a paint spinner (model 4302 from Lau GmbH) and at 550 rpm. was thrown out. This made it possible to produce a wet film with a circulation of about 6 ml / m 2 . After the treatment solution had been spun on for about 5 seconds, the sheets were immediately dried in a circulating air drying oven heated to 75 ° C. for about 120 seconds.

    Als Parameter für die erhaltene Phosphatschicht wurde das Schichtgewicht bestimmt. Hierfür wurden 2 unterschiedliche Methoden herangezogen: Bei der Bestimmung des Schichtgewichtes durch Auswiegen wurde das Blech vor der Durchführung der Beschichtung gewogen, danach wurde die Phosphatierlösung aufgebracht und eingetrocknet und das beschichtete Blech wieder gewogen. Aus der Gewichtsdifferenz wurde die Schichtauflage in g/m2 errechnet. Bei der Bestimmung des Schichtgewichts durch Ablösen wurden die phosphatierten Bleche gewogen, die Phosphatschicht durch Ablösen mit 0,5 gew.-%iger Chromsäurelösung entfernt und die Bleche wieder gewogen. Aus der Gewichtsdifferenz wurde die Masse der entfernten Schicht g/m2 ermittelt. Das durch Ablösen ermittelte Schichtgewicht ist in der Regel höher als das durch Auswiegen bestimmte, da durch die Phosphatierung ein Teil der Metalloberfläche in Metallphosphat umgewandelt wird. Dieser Teil wird bei der Schichtgewichtsbestimmung durch Auswiegen nicht mit erfaßt, beim Ablösen der Schicht jedoch mit entfernt.The layer weight was determined as a parameter for the phosphate layer obtained. Two different methods were used for this: When determining the layer weight by weighing, the sheet was weighed before the coating was carried out, then the phosphating solution was applied and dried and the coated sheet was weighed again. The layer coverage in g / m 2 was calculated from the difference in weight. When determining the layer weight by detaching, the phosphated sheets were weighed, the phosphate layer was removed by detaching with 0.5% by weight chromic acid solution and the sheets were weighed again. The mass of the removed layer g / m 2 was determined from the weight difference. The layer weight determined by detachment is generally higher than that determined by weighing, since part of the metal surface is converted into metal phosphate by the phosphating. This part is not included in the determination of the layer weight by weighing, but is also removed when the layer is detached.

    Die Tabelle 1 enthält Phosphatierbäder für elektrolytisch verzinkten Stahl und die erhaltenen Schichtauflagen, Tabelle 2 entsprechende Beispiele für die Behandlung von schmelztauchverzinktem Stahl. Für die Behandlung dieser Substrate sind jeweils solche Phosphatierlösungen geeignet, die zu Schichtgewichten im Bereich von 1 bis 3 g/m2 führen. In die beispielhaften Behandlungsbäder wurden Zink als Oxid, Mangan und Nickel als Carbonat eingesetzt. Die Bäder enthielten außer Wasser keine weiteren Komponenten.Table 1 contains phosphating baths for electrolytically galvanized steel and the layer coatings obtained, Table 2 corresponding examples for the treatment of hot-dip galvanized steel. For the treatment of these substrates such phosphating solutions are suitable which lead to layer weights in the range from 1 to 3 g / m 2 . Zinc as oxide, manganese and nickel as carbonate were used in the exemplary treatment baths. The baths contained no components other than water.

    Für Beispiel 7 wurde die Schichtzusammensetzung mittels EDX (Röntgenemission) bestimmt (in Gew.-%): Zn 7,5, Mn 2,2, P 7,5, Al 0,3, Rest: Kann als Sauerstoff aufgenommen werden.For example 7, the layer composition was determined by means of EDX (X-ray emission) determined (in% by weight): Zn 7.5, Mn 2.2, P 7.5, Al 0.3, Rest: Can be taken up as oxygen.

    Eine Auswahl erfindungsgemäß behandelter Z-Bleche wurde, wie beim praktischen Einsatz vorgesehen, einer im Karosseriebau üblichen Nachphosphatierung mit einem handelsgängigen Trikation-Phosphatierverfahren (GranodineR 1994, Henkel KGaA, Düsseldorf) unterzogen und mit einem kathodischen Elektrotauchlack (AqualuxR K, Firma IDAC) lackiert. Nach einem Korrosionstest (10 Zyklen Wechselklima gemäß VDA 621 415) wurde die Lackunterwanderung an einem Einschnitt gemäß DIN 53167 gemessen. Ergebnisse:

  • Beisp. 6 1,9 mm
  • Beisp. 7 2,2 mm
  • Beisp. 8 2,4 mm.
    • No-rinse Phosphatierung von elektrolytisch verzinktem Stahl Bsp. Nr. Badzusammensetzung [g/l] Aktivsubstanz [Gew.-%] pH Freie Säure [Punkte] Gesamtsäure [Punkte] Schichtgew. [g/m2] 1 210 H3PO4-85%ig 15 Zn 21,4 1,5 65 303 1,57 (W) 20 Mn 2 210 H3PO4-85%ig 15 Zn 21,4 2,4 31 281 1,75 (W) 10 Mn 3 175 H3PO4-85%ig 12,5 Zn 17,8 2,5 29 228 1,34 (W) 16,6 Mn 1,96 (A) 4 110 H3PO4-85%ig 7,5 Zn 11,4 2,5 27 190 1,24 (A) 10,0 Mn 2,5 Ni No-rinse Phosphatierung von schmelztauchverzinktem Stahl Bsp. Nr. Badzusammensetzung [g/l] Aktivsubstanz [Gew.-%] pH Freie Säure [Punkte] Gesamtsäure [Punkte] Schichtgew.1) [g/m2] 5 280 H3PO4-85%ig 20 Zn 20 Mn 27,8 1,3 81 365 0,73 (W) 6 210 H3PO4-85%ig 15,3 Zn 20,9 1,4 73 294 1,50 (W) 15,0 Mn 7 210 H3PO4-85%ig 15 Zn 22,0 1,5 65 303 1,8 (W) 20 Mn 8 221 H3PO4-85%ig 15 Zn 22,3 1,5 67 321 1,55 (W) 15 Mn 5 Ni A selection of Z-sheets treated according to the invention was subjected, as intended for practical use, to a postphosphating process customary in body construction with a commercial trication-phosphating process (Granodine R 1994, Henkel KGaA, Düsseldorf) and with a cathodic electrocoat material (Aqualux R K, company IDAC). painted. After a corrosion test (10 cycles alternating climate according to VDA 621 415), the infiltration of paint was measured on an incision according to DIN 53167. Results:
  • Ex. 6 1.9 mm
  • Ex. 7 2.2 mm
  • Ex. 8 2.4 mm.
    • No-rinse phosphating of electrolytically galvanized steel Example No. Bath composition [g / l] Active substance [% by weight] pH Free acidity [points] Total acidity [points] Layer weight [g / m 2 ] 1 210 H 3 PO 4 -85% 15 rooms 21.4 1.5 65 303 1.57 (W) 20 mn 2nd 210 H 3 PO 4 -85% 15 rooms 21.4 2.4 31 281 1.75 (W) 10 mn 3rd 175 H 3 PO 4 -85% 12.5 Zn 17.8 2.5 29 228 1.34 (W) 16.6 Mn 1.96 (A) 4th 110 H 3 PO 4 -85% 7.5 Zn 11.4 2.5 27 190 1.24 (A) 10.0 Mn 2.5 Ni No-rinse phosphating of hot-dip galvanized steel Example No. Bath composition [g / l] Active substance [% by weight] pH Free acidity [points] Total acidity [points] Layer weight 1) [g / m 2 ] 5 280 H 3 PO 4 -85% 20 Zn 20 Mn 27.8 1.3 81 365 0.73 (W) 6 210 H 3 PO 4 -85% 15.3 Zn 20.9 1.4 73 294 1.50 (W) 15.0 Mn 7 210 H 3 PO 4 -85% 15 rooms 22.0 1.5 65 303 1.8 (W) 20 mn 8th 221 H 3 PO 4 -85% 15 rooms 22.3 1.5 67 321 1.55 (W) 15 mn 5 Ni

    Claims (13)

    1. A process for phosphating surfaces of steel, zinc, aluminium or their alloys by treatment with acidic, zinc- and phosphate-containing solutions and drying the solutions without rinsing, characterized in that the surfaces are contacted with a phosphating solution which contains 2 to 25 g/l of zinc ions, 2 to 25 g/l of manganese ions and 50 to 300 g/l of phosphate ions and which has a pH value of 1 to 3.6, a free acid content of 0 to 100 points and a total acid content of 40 to 400 points.
    2. A process as claimed in claim 1, characterized in that the phosphating solution additionally contains one or more of the following components:
      one or more additional divalent metal ions selected from
      Ni, Co, Ca, Mg in quantities of 0.1 to 15 g/l,
      copper in quantities of 3 to 200 mg/l,
      iron in quantities of 0.01 to 5 g/l,
      0.01 to 5 g/l of fluoride in free or complexed form,
      0.1 to 100 g/l of chelating hydroxycarboxylic acids containing 3 to 6 carbon atoms.
    3. A process as claimed in one or more of claims 1 and 2, characterized in that the phosphating solution has a temperature of 15 to 80°C.
    4. A process as claimed in one or more of claims 1 to 3, characterized in that the phosphating solution has an active substance content, defined as the sum of the metal ions and phosphoric acid, of 5.5 to 35% by weight.
    5. A process as claimed in one or more of claims 1 to 4 for the treatment of surfaces of travelling metal strips.
    6. A process as claimed in one or more of claims 1 to 5, characterized in that the phosphating solution is sprayed onto the surface and is adjusted to a liquid film add-on of 2 to 10 ml/m2.
    7. A process as claimed in one or more of claims 1 to 5, characterized in that the phosphating solution is applied to the surface by applicator rolls as a liquid film add-on of 2 to 10 ml/m2.
    8. A process as claimed in one or more of claims 1 to 5, characterized in that the surfaces are immersed in the phosphating solution and in that, after leaving the phosphating solution, a liquid film add-on of 2 to 10 ml/m2 is adjusted on the surface.
    9. A process as claimed in one or more of claims 1 to 8 for treating the surfaces of liquid strips of hot-dip-galvanized steel, characterized in that the phosphating solution has
      an active substance content of 5.5 to 35% by weight,
      a pH value of 1.0 to 2.2 and/or
      a ratio by weight of (sum of divalent metal ions) to phosphate of 1:5 to 1:6.
    10. A process as claimed in one or more of claims 1 to 8 for treating the surfaces of travelling strips of electrolytically galvanized steel, characterized in that the phosphating solution has
      an active substance content of 5.5 to 20% by weight,
      a pH value of 1.5 to 3.5 and/or
      a ratio by weight of (sum of divalent metal ions) to phosphate of 1:5 to 1:6.
    11. A process as claimed in one or more of claims 1 to 8 for treating surfaces of cold-rolled ungalvanized steel, characterized in that the phosphating solution has
      an active substance content of 5.5 to 25% by weight,
      a pH value of 2.0 to 3.6 and/or
      a ratio by weight of (sum of divalent metal ions) to phosphate of 1:5 to 1:6.
    12. A process as claimed in one or more of claims 1 to 11, characterized in that drying is carried out at a temperature of 50 to 120°C, the time elapsing between the first contact of the surface with the phosphating solution and the end of the drying step being 3 to 60 seconds.
    13. A process as claimed in one or more of claims 1 to 12 for pretreating surfaces of steel, zinc, aluminium or their alloys to produce crystalline or X-ray-amorphous, zinc-containing phosphate coatings with a coating weight of 0.3 to 3 g/m2.
    EP95932747A 1994-09-23 1995-09-14 No-rinse phosphatising process Expired - Lifetime EP0774016B1 (en)

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    DE4433946 1994-09-23
    DE4433946A DE4433946A1 (en) 1994-09-23 1994-09-23 Phosphating process without rinsing
    PCT/EP1995/003619 WO1996009422A1 (en) 1994-09-23 1995-09-14 No-rinse phosphatising process

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    EP0774016B1 true EP0774016B1 (en) 1999-07-28

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    DE19639597C2 (en) * 1996-09-26 2000-01-20 Henkel Kgaa Process for the phosphating of running strips made of cold or hot rolled steel in high-speed conveyor systems
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    KR100347405B1 (en) 2002-12-05
    KR970706420A (en) 1997-11-03
    ES2135090T3 (en) 1999-10-16
    CA2200893A1 (en) 1996-03-28
    US5976272A (en) 1999-11-02
    EP0774016A1 (en) 1997-05-21
    JPH10505881A (en) 1998-06-09
    DE59506484D1 (en) 1999-09-02
    DE4433946A1 (en) 1996-03-28
    WO1996009422A1 (en) 1996-03-28
    ATE182632T1 (en) 1999-08-15

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