EP0134895B1 - Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques - Google Patents

Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques Download PDF

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Publication number
EP0134895B1
EP0134895B1 EP84105731A EP84105731A EP0134895B1 EP 0134895 B1 EP0134895 B1 EP 0134895B1 EP 84105731 A EP84105731 A EP 84105731A EP 84105731 A EP84105731 A EP 84105731A EP 0134895 B1 EP0134895 B1 EP 0134895B1
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Prior art keywords
phosphating
phosphate
layer
compounds
accelerating
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German (de)
English (en)
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EP0134895A1 (fr
Inventor
Heinz Portz
Orthmar Dr. V. Ettingshausen
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Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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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
    • C23C22/12—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
    • 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
    • C23C22/14—Orthophosphates containing zinc cations containing also chlorate anions
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates

Definitions

  • DE-A-30 16576 describes a method for accelerating the formation of phosphate layers based on zinc phosphate, the application solution containing nitrite and chlorate as accelerators.
  • a method based on a solution of zinc phosphate uses a combination of chlorate and a water-soluble aromatic nitro compound, preferably Na-m-nitrobenzenesulfonate (DE-A-32 24 923) as accelerator.
  • a comparable combination is claimed in GB-A-15 42 222.
  • DE-A-30 04 927 also describes a method for forming phosphate layers on metal surfaces with the aid of zinc phosphate solutions which contain nitrite and / or organic nitro compounds and, if appropriate, additionally chlorate.
  • US-A-3 923 554 relates to a method for producing phosphate layers on iron surfaces with the aid of aqueous zinc phosphate solutions which contain nitrite ions.
  • aqueous zinc phosphate solutions which contain nitrite ions.
  • 0.1 to 10 g / l, based on the total solution, of urea or urea nitrate are added to these solutions.
  • the same effect can also be achieved by adding sulfamic acid, alkali metal or ammonium salts of sulfamic acid, ascorbic acid, hydroxylamine or hydroxylamine derivatives to such solutions.
  • the appearance and the corrosion resistance of the layers are not impaired by the additives mentioned, but rather improved.
  • NL-C-102 953 is a phosphating process in which phosphating solutions are used which, in addition to chlorate and / or nitrate or nitrite or halogenate, are also a compound of the general formula RS0 2 NHCI, in which R is an aralkyl radical with at most 5 carbon atoms in the alkyl chain, contained as accelerators.
  • phosphating solutions which, in addition to chlorate and / or nitrate or nitrite or halogenate, are also a compound of the general formula RS0 2 NHCI, in which R is an aralkyl radical with at most 5 carbon atoms in the alkyl chain, contained as accelerators.
  • their salts such as in particular chloramine-T, can also be used.
  • phosphating solutions often contain nitrate. Carrying out the phosphating process at elevated temperature in the presence of nitrates increasingly leads to an autoreduction of the nitrate with the formation of additional nitrite. The formation of these amounts of nitrite is difficult to control and is undesirable since - as mentioned above - there is an increasing passivation of the metal surfaces.
  • a particular disadvantage is that the use of nitrite-containing systems to accelerate phosphating solutions leads to the release of nitrous gases. This disadvantage makes it seem advisable to completely dispense with the use of nitrite and possibly nitrate as a phosphating accelerator or to choose reaction conditions under which nitrite does not form.
  • the adjustment and maintenance of the pH value is of great importance for the formation of a good phosphate layer.
  • the pH can be between 1.8 and 5.8. It is preferably adjusted to the desired value using phosphoric acid.
  • sulfamic acid is also described for this purpose.
  • the subject of DE-A-21 52 446 - or the parallel FR-A-21 10784 and BE-A-767 775 - is, for example, a process for phosphating metal surfaces with the aid of aqueous solutions which contain acidic non-layer-forming phosphates.
  • sulfamic acid is used as the acidic component for adjusting or maintaining the pH in amounts of 0.5 to 10% by weight, preferably 3 to 6% by weight, based on the content of acidic non-layer-forming phosphate in the solution.
  • such solutions contain oxidizing accelerators, such as nitrates, nitrites, chlorates or molybdates.
  • phosphate coatings For corrosion protection and as a lubricant carrier in cold forming, thick and fully developed phosphate coatings with coating weights of 10 to 35 g / m 2 are desirable. Such high contact weights are normally achieved at phosphating bath temperatures of 70 to 100 ° C.
  • DE-A-22 41 798 describes such a nitrate-accelerated immersion process in which the weight ratio of P 2 0 5 : Zn: N0 3 is 1: (0.7 to 2.0): (0.3 to 0.7) must be set.
  • DE-C-15 21f927 also claims a nitrate-accelerated process in which the weight ratio P 2 O 5 : Zn: N0 3 should be 1: (1.4 to 2.6): (2.0 to 4.3) .
  • soaps in combination with phosphate layers are used as lubricants.
  • the zinc phosphate layers on the workpiece can partially do so with alkali soaps be implemented so that the particularly effective zinc soap is formed.
  • the tertiary zinc phosphate of the layer reacts with sodium soap to form zinc soap and tertiary sodium phosphate.
  • the phosphated workpieces are immersed in a soaping bath at 70 to 80 ° C. for 2 to 10 minutes. The greatest possible conversion and thus the best forming results are obtained with special reactive soap lubricants, the immersion baths used with 2 to 10% by weight of which have a pH between 8 and 1-0.
  • the formation of the phosphate layers can be influenced by special pre-rinses. With such pre-rinses, it is often possible to exaggerate the effects of previous treatments, e.g. B. an alkaline degreasing or pickling. Such pre-rinses are therefore widely used in practice.
  • Zinc phosphating processes based on the so-called low zinc technology are also used. This is a process variant that differs from normal zinc technology in some essential points. These variants concern in particular the concentrations in which the determining bath components zinc and phosphate are present in the treatment solution and the weight and molar ratios of these two components to one another. While the weight ratio of zinc to phosphate is about 1: (1 to 12) in the normal zinc phosphating baths, with which metal surfaces are treated for subsequent painting, it is 1: (14 to 30) in the low zinc phosphating baths.
  • the monitoring of the phosphating baths is relatively complex, especially since the ratio of chemical consumption to mechanical discharge, which in turn u. a. depends on the shape of the metal piece being treated, on the draining options and on the type of phosphating system, is not a constant.
  • the object of the present invention is to provide a method for accelerated and layer-improving application of phosphate coatings on metal surfaces which does not have the aforementioned disadvantages.
  • a process should be made available that does not require nitrite as an accelerator component and also leads to the same results in terms of paint adhesion and corrosion protection in normal zinc technology that can be achieved with low zinc technology.
  • simplifying the monitoring of the contents of the individual accelerator components was intended to simplify bath management and reduce the amount of sludge in the phosphating baths.
  • the new process should also be based on the use of environmentally friendly and toxicologically safe compounds.
  • N-substitution products of amidosulfonic acid also called sulfamic acid
  • salts generally formula 1
  • sulfonamides generally formula I
  • benzenesulfanilides generally formula
  • Benzoeklaresulfimide generally formula
  • 1,2.3-oxathiazin-4 (3H) -one salts and their 6-alkyl derivatives (general formula 111) used individually or in combination with one another in addition to other components commonly used in phosphating solutions.
  • the invention accordingly relates to the use of one or more compounds of the general formulas (I), (II) and (111) defined above as accelerating and layer-refining components, in an amount of 0.1 to 6 g / l, in phosphating solutions on the Basis of zinc phosphate and / or iron phosphate and / or zinc iron phosphate, which are used to apply phosphate coatings on metal surfaces, in addition to other components that are commonly used in such phosphating solutions.
  • the compounds of the general formulas (I), (11) and (III) according to the invention are used in combination with m-nitrobenzenesulfonic acid as a co-accelerator. This leads to an effective acceleration of the phosphating process.
  • nitrate and - in the presence of compounds of the general formulas (III) - nitrite can also be used as co-accelerators.
  • one or more compounds from the group N-cyclohexanesulfamic acid and its salts, benzenesulfanilide, benzoic acid sulfimide, 1,2.3-oxathiazin-4 (3H) -one potassium and its 6-methyl derivative are used as accelerating and layer-refining components used.
  • Other sulfonamides are also suitable, in particular those whose aromatic radical carries further polar radicals which improve the water solubility of the compounds, such as, for. B. hydroxy or amino residues or amido residues of dicarboxylic acids.
  • the water solubility of the compounds according to the invention should be so good. that at least Dissolve 2 g of the compounds of the general formulas (I), (11) and / or (111) in one liter of phosphating solution.
  • water-soluble salts preferably alkali metal salts of the N-substituted derivatives of amidosulfonic acid, and / or further compounds are selected which carry polar groups which improve water solubility as substituents.
  • the active constituents of the phosphating solution can be introduced into water in the form of water-soluble or acid-soluble salts or compounds or as acids in a manner known per se.
  • the presence of chlorate is not absolutely necessary for the formation of phosphate layers. Rather, phosphate layers with high coating weights are formed by the process accelerated according to the invention in the presence and in the absence of chlorate. In the absence of chlorate, small additions of molybdate can also be used.
  • Optimal phosphate layer formation for subsequent coating with paints and other organic coatings with regard to paint adhesion and corrosion is obtained if chlorate is used as a further accelerator component in accordance with a preferred embodiment of the present invention and the ratio of the compounds of the general formulas (I), ( 11) and / or (111) for C10 3 to a value in the range from (0.1 to 10): 1.
  • a further preferred embodiment of the invention leads to optimal phosphate layer formation if the ratio of the compounds of the general formulas (I), (11) and / or (111) according to the invention to Mo0 4 is set to a value in the range of (10 to 100): 1.
  • the process accelerated according to the invention is particularly suitable for producing phosphate coatings on steel, galvanized steel, aluminum or on surfaces which contain several of these metals. It is advantageously used to produce phosphate layers which are suitable both as a corrosion protection layer and layer for improving paint adhesion and as a sliding layer for cold forming.
  • the phosphating solutions used to produce phosphate layers on metal surfaces can have further constituents. It is advantageous to use solutions for the phosphating of aluminum surfaces which additionally contain 0.1 to 5.0 g / l of fluoride, which can be present in the phosphating solution as free or complex-bound fluoride ion. Suitable complex fluorides are e.g. B. fluoroborates and / or fluorosilicates.
  • Phosphating solutions which additionally contain Ni, Co and / or Fe ions can advantageously be used for the layer formation on galvanized steel. However, these ions should not be present in a total amount above 3.0 g / l. Salts of these metals are advantageously used in a concentration of 0.1 to 4.5 g / l as salts of the aforementioned simple or complex fluorides. Phosphating solutions containing nickel, cobalt and / or iron and fluoride are particularly well suited for the formation of layers on surfaces consisting of several metals. However, the total amount of nickel, cobalt and / or iron ions must not be greater than the amount of zinc ions.
  • phosphating solutions which additionally contain a total of 0.3 to 5.0 g / l of a mixture of nonionic surfactants.
  • sulfamic acid derivatives are impaired in phosphating solutions that contain calcium ions.
  • Accelerators which do not form poorly soluble calcium salts for example benzoic acid sulfimide or benzene sulfanilides, are therefore used in such phosphating solutions according to the invention.
  • the pH of the phosphating solution with which the metal surfaces intended for subsequent painting are brought into contact should be between 1.8 and 5.8, preferably between 2.0 and 3.5.
  • the process accelerated according to the invention has the advantage of delivering well-formed phosphate coatings of up to 30 g / m 2 on metal surfaces with a total acidity of less than 40 points and with a free acidity of 20 points, which are then subjected to cold forming.
  • the metal surfaces can be treated in any manner to form homogeneous phosphate layers. Diving and spraying systems and combined diving / spraying systems are particularly suitable.
  • the treatment times for spraying are between 20 and 300, preferably between 30 and 180 seconds.
  • well-formed phosphate layers of up to 22 g / m 2 were formed after only 300 seconds.
  • the treatment times depend on the process conditions (temperature of the phosphating solution, pH value, spray pressure), the nature of the metal surfaces to be phosphated and the upstream treatment of the metals to be phosphated.
  • the temperatures at which the metal surfaces can be brought into contact with phosphating solutions using the accelerators according to the invention in the phosphating agents are from 25 to 70 ° C., for the formation of phosphate layers with high coating weights, preferably between 45 to 60 ° C. and thus significantly below the commonly used Treatment temperatures. Treatment temperatures of 25 ° C are possible in special process combinations and specially adjusted phosphating solutions.
  • the process accelerated according to the invention has the further advantage that the sludge formation is largely suppressed.
  • the incrustation of the heating register is almost completely avoided.
  • the sludge formation in the bath is considerably smaller than in the known phosphating baths which work with continuous or repeated additions of sodium nitrite as accelerators.
  • the baths according to the invention need e.g. B. in diving operation and normal throughput only to be desludged every 12 to 15 months.
  • the method accelerated according to the invention also has the advantage of still delivering excellent values with regard to paint adhesion and corrosion protection when the normal zinc phosphating technology is used.
  • the process engineering advantages of normal zinc phosphating technology can be combined with the application engineering advantages of low zinc phosphating technology.
  • the accelerated according to the invention provides the new and surprising effect that the zinc phosphate baths can be operated immediately with very high bath loads and low temperatures without incorporation. Furthermore, a particularly economical production of the desired phosphate coatings is possible. This is due to the low consumption of chemicals required to produce a certain layer weight.
  • coating weights of 0.2 to 30 g / m 2 for steel and of 0.5 to 3.0 g / m 2 for galvanized steel can be achieved.
  • the respective value results from the type of treatment, the treatment time, the accelerator concentration and the temperature of the phosphating bath solutions used.
  • the process accelerated according to the invention is carried out within a process sequence known to the person skilled in the art, which consists of cleaning the metal surfaces, water rinsing, optionally preactivation with a solution containing titanium salt, phosphating with formation of the phosphate layer, water rinsing, post-treatment (passivation) and rinsing with demineralized water.
  • a characteristic feature of the process accelerated according to the invention is furthermore that the preactivation with a solution containing titanium salt can be dispensed with.
  • the process sequence consists of a cleaning step with a strongly alkaline cleaner, subsequent rinsing, phosphating with the formation of the phosphate layer, post-treatment (passivation) and rinsing with deionized water.
  • the process for the preparation of phosphate coatings on steel and iron using an acidic zinc phosphate solution accelerated according to the invention at temperatures of 45 to 60 ° C in the immersion process is characterized in that bath solutions can be used which are prepared with aqueous acidic concentrates in which the weight ratio is widely variable from zinc to phosphate without the advantages according to the invention, such as reduced sludge accumulation, extremely fine crystalline layer formation, possibly also eliminating the need for preactivation with solutions containing titanium salts, fully formed phosphate layers, being lost at low treatment temperatures.
  • a weight ratio of zinc to phosphate of 1: 1 to 12 has proven to be particularly advantageous.
  • the fine-grained phosphate coatings offer excellent corrosion protection, as a review based on the test methods mentioned in the examples showed. It also shows that the fine-grained phosphate layers in particular represent an excellent anchorage for subsequent applied lacquer coatings.
  • the process accelerated according to the invention is particularly advantageous as a pretreatment before electrocoating, in particular cathodic electrocoating.
  • the metal surfaces covered with the phosphate layers can not only be painted, but can also be coated with different types of materials.
  • Another important advantage is that the process according to the process accelerated according to the invention is characterized by reduced sludge and crust formation in the phosphating plants, which leads to economical process management and an extended service life of the phosphating solution.
  • the phosphating solution used in carrying out the process accelerated according to the invention is normally prepared as an acid concentrate and diluted accordingly before use.
  • the Concentrate can have a sufficiently high free acid content to avoid solid separation during storage, when the temperature drops or during transport.
  • the concentrate is diluted to the desired concentration and adjusted to the required pH or the free acid content.
  • the continuously used phosphating solution can be supplemented with the aid of a supplementary solution which contains all active constituents or with the use of several supplementary solutions which contain all active constituents in their entirety.
  • Concentrate A was first prepared by mixing the following components in a container made of plastic or stainless steel:
  • Cold-rolled steel sheets were subjected to the following process: First, the sheets were spray-treated with an alkaline cleaner (based on sodium hydroxide, pentasodium tripolyphosphate and surfactant) at 55 ° C. for 25 seconds. This was followed by a second cleaning by spraying with an alkaline cleaner (based on disodium hydrogenphosphate, activating titanium salt and surfactant) at 45 ° C. for 25 seconds. Then it was rinsed with cold water for 25 seconds.
  • an alkaline cleaner based on sodium hydroxide, pentasodium tripolyphosphate and surfactant
  • the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 60 seconds.
  • the phosphated sheets were rinsed cold for 25 seconds and then with a solution containing Cr (VI) / Cr (III) ions at a pH from 4.0 treated at 30 ° C for 30 sec. in spraying. This was followed by rinsing with fully demineralized water for 10 seconds. Finally, the sheets were dried in an oven at 110 ° C. for 4 minutes.
  • the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
  • the tests to determine resistance to corrosion and various other physical properties gave excellent results.
  • the sheets were immersed in an alkaline cleaner (based on sodium hydroxide, water glass, sodium orthophosphate and surfactant) at 70 ° C for 10 minutes. treated. Then 3 min. rinsed with water. It was then treated with a hydrochloric acid-containing pickling agent at 25 ° C. for 25 min. stained. This was followed by treatment with the phosphating solution described above by immersion at 50 ° C. for 10 minutes. The phosphated sheets were rinsed with water for 3 minutes and then with a solution containing Cr (VI) / Cr (III) ions at a pH of 4.0 at 40 ° C. for 3 min. treated in diving and finally with demineralized water for 2 min. rinsed.
  • an alkaline cleaner based on sodium hydroxide, water glass, sodium orthophosphate and surfactant
  • the sheets treated in this way were dip-coated cathodically with an electro-dip coating from Wiederhold / ICI.
  • the phosphated and painted sheets were then subjected to tests to determine corrosion resistance and other physical properties. The properties observed in each case were excellent.
  • the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 60 seconds.
  • the phosphated sheets were rinsed cold for 25 seconds and then with a solution containing Cr (VI) / Cr (III) ions at a pH from 4.0 treated at 30 ° C for 30 sec. in spraying. This was followed by rinsing with demineralized water for 10 seconds. Finally, the sheets were dried in an oven at 110 ° C. for 4 minutes.
  • the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
  • the tests to determine resistance to corrosion and various other physical properties gave excellent results.
  • Cold-rolled steel sheets were subjected to the following process steps: First, the sheets were treated with an alkaline cleaner (based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant) at 55 ° C. for 60 s by spraying. Then it was rinsed with cold water for 30 seconds.
  • an alkaline cleaner based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant
  • the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 90 s.
  • the phosphated sheets were rinsed cold and then with a Cr (VI) / Cr (III) - Solution containing ions treated at pH 4.0 at room temperature for 30 s by spraying.
  • the sheets treated in this way were dip-coated cathodically with an electrodeposition paint from BASF.
  • the tests to determine resistance to corrosion and various other physical properties gave excellent results.
  • Cold-rolled steel sheets were subjected to the following process steps: First, the sheets were treated with an alkaline cleaner (based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant) at 55 ° C. for 60 s by spraying. Then it was rinsed with cold water for 30 seconds.
  • an alkaline cleaner based on sodium orthophosphate, sodium pyrophosphate, activating titanium salt and surfactant
  • the treatment with the phosphating solution described above was then carried out by spraying at 55 ° C. for 90 s.
  • the phosphated sheets were rinsed cold for 30 s and then sprayed with a solution containing Cr (VI) / Cr (III) ions at a pH of 4.0 at room temperature for 30 s.
  • a concentrate was prepared by mixing the following ingredients in a stainless steel container.
  • the phosphated blanks were rinsed with water for 3 minutes and then soaped with a soap-containing aqueous solution (6% sodium stearate, 1% sodium myristate) at 80 ° C. for 5 minutes.
  • a soap-containing aqueous solution 6% sodium stearate, 1% sodium myristate
  • the phosphated blanks were rinsed with water for 3 minutes and then soaped with a soap-containing aqueous solution (6% sodium stearate, 1% sodium myristate) at 80 ° C. for 5 minutes.
  • a soap-containing aqueous solution 6% sodium stearate, 1% sodium myristate

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  • Mechanical Engineering (AREA)
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  • Chemical Treatment Of Metals (AREA)
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Claims (7)

1. Utilisation d'un ou plusieurs composés de formules générales (I), (II) ou (III) :
Figure imgb0026
dans laquelle
R1 représente un atome d'hydrogène, un radical alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, un radical carboxylique ou hétérocyclique saturé à 5 ou 6 chaînons, ou un radical aryle ou aralkyle à six chaînons au moins, et
R2 représente un groupe hydroxyle, un groupe ayant la composition ―O-M- dans lequel M-représente un ion alcalin ou un ion ammonium, ou un noyau aromatique à six chaînons au moins, éventuellement substitué par un groupe hydroxyle ou amino, avec la condition que lorsque R1 représente un atome d'hydrogène, R2 ne doit pas représenter un groupe
OH ou O―M- :
Figure imgb0027
dans laquelle R3 représente un atome d'hydrogène, un groupe hydroxyl ou amino, et/ou les sels alcalins et d'ammonium de composés correspondant à cette formule :
Figure imgb0028
dans laquelle R4 représente un atome d'hydrogène ou un radical alkyle linéaire ou ramifié ayant de 1 à 4 atomes de carbone, et M+ a la signification donnée plus haut ;
en tant que composant accélérateur et affinant le grain des couches, en une quantité de 0,1 à 6 g/I, dans des solutions de phosphatation à base de phosphate de zinc et/ou phosphate de fer et/ou phosphate de fer et zinc, qui servent à l'application de revêtements de phosphate sur des surfaces métalliques, en plus d'autres composants utilisés habituellement dans de telles solutions de phosphatation.
2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise, en tant que composant accélérateur et affinant le grain des couches, un ou plusieurs composés choisis parmi l'acide N-cyclohexanesulfamique et ses sels, le benzènesulfanilide, le benzosulfimide, la 1,2,3-oxathiazine-4(3H)-one potassique et son dérivé 6-méthyle.
3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'on utilise, en tant que composant accélérateur et affinant le grain des couches, des composés de formules générales (I), (II) et/ou (III), conjointement avec un chlorate, le rapport des composés cités au chlorate allant de 0,1 1 à 10,0 :1.
4. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'on utilise, en tant que composant accélérateur et affinant le grain des couches, des composés de formules générales (I), (II) et/ou (III), conjointement avec un molybdate, le rapport des composés cités au molybdate allant de 10 1 à 100 1.
5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que l'on utilise les composants accélérateurs et affinant le grain des couches, dans des solutions de phosphatation qui contiennent en outre des ions Ni, Co et/ou Fe, la quantité totale de ces ions ne devant pas excéder 3,0 g/litre.
6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'on utilise les composants accélérateurs et affinant le grain des couches, dans des solutions de phosphatation qui présentent un pH dans l'intervalle de 1,8 à 5,8, de préférence dans l'intervalle de 2,0 à 3,5.
7. Utilisation selon l'une quelconque des revendications 1 à 7, caractérisée en ce que l'on utilise les composants accélérateurs et affinant le grain des couches, dans des solutions de phosphatation qui sont à des températures dans la plage de 25 à 70 °C, de préférence dans la plage de 45 à 60 °C.
EP84105731A 1983-07-19 1984-05-19 Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques Expired EP0134895B1 (fr)

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AT84105731T ATE39003T1 (de) 1983-07-19 1984-05-19 Verfahren und mittel zum beschleunigten und schichtverfeinernden aufbringen von phosphatueberzuegen auf metalloberflaechen.

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DE3325974 1983-07-19
DE19833325974 DE3325974A1 (de) 1983-07-19 1983-07-19 Verfahren und universell anwendbare mittel zum beschleunigten aufbringen von phosphatueberzuegen auf metalloberflaechen

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006024614A1 (de) * 2006-05-26 2007-11-29 Schaeffler Kg Verfahren zum Behandeln einer Wälzlagerkomponente und Wälzlagerkomponente

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3631667A1 (de) * 1986-09-18 1988-03-24 Collardin Gmbh Gerhard Schichtbildende passivierung bei multimetall-verfahren
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
DE4417965A1 (de) * 1994-05-21 1995-11-23 Henkel Kgaa Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
WO2003054250A1 (fr) * 2001-12-13 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal
WO2005071139A1 (fr) * 2004-01-13 2005-08-04 Mccully Timothy R Composition et procede de formation de surfaces contenant du phosphate sur des composes dans des zones de combustion d'hydrocarbures
EP2064365A1 (fr) * 2006-09-18 2009-06-03 Henkel AG & Co. KGaA Revêtement hybride organique-inorganique mince sans chrome sur des métaux zincifères
EP2971245B1 (fr) * 2013-03-14 2017-04-19 Buckman Laboratories International, Inc Procédé pour éliminer la corrosion d'une surface métallique à l'aide d'acides alkyl sulfamiques ou de sels de ceux-ci
WO2018221797A1 (fr) * 2016-06-01 2018-12-06 주식회사 천우테크 Agent de traitement de décapage et de couche de passivation destiné à éliminer les dépôts et la rouille de zones de soudage d'un tuyau et d'une structure en acier inoxydable
WO2019042951A1 (fr) * 2017-08-31 2019-03-07 Chemetall Gmbh Procédé amélioré de phosphatation sans nickel de surfaces métalliques
CN111850534B (zh) * 2020-06-16 2022-03-01 中国石油天然气集团有限公司 一种马氏体不锈钢油管低应力预钝化膜及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923554A (en) * 1974-02-07 1975-12-02 Detrex Chem Ind Phosphate coating composition and method

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB599778A (en) * 1945-11-07 1948-03-19 Pyrene Co Ltd Improvements relating to the production of phosphate coatings on metal
NL102953C (fr) * 1900-01-01
FR1045538A (fr) * 1951-11-28 1953-11-26 Cie D Applic Chimiques A L Ind Perfectionnement à la phosphatation superficielle des métaux ferreux, du zinc et de leurs alliages
DE1219766B (de) * 1961-07-28 1966-06-23 N Izsledovatelski I Mash I Met Verfahren zur kalten Phosphatierung von kohlenstoffarmem Stahl
AT282285B (de) * 1965-12-22 1970-06-25 Plaut Fa J Zinkphosphatüberzüge
FR2110784A5 (fr) * 1970-10-30 1972-06-02 Parker Ste Continentale
JPS506418B1 (fr) * 1971-07-06 1975-03-13
DE2241798C2 (de) * 1972-08-25 1982-03-11 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Phosphatierung von Eisen und Stahl
SU550460A1 (ru) * 1973-12-06 1977-03-15 Предприятие П/Я Г-4347 Вдный раствор дл одновременного обезжиривани , травлени и фосфатировани металлической поверхности
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
US4149909A (en) * 1977-12-30 1979-04-17 Amchem Products, Inc. Iron phosphate accelerator
JPS5811513B2 (ja) * 1979-02-13 1983-03-03 日本ペイント株式会社 金属表面の保護方法
DE3016576A1 (de) * 1980-04-30 1981-11-05 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
US4498935A (en) * 1981-07-13 1985-02-12 Parker Chemical Company Zinc phosphate conversion coating composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923554A (en) * 1974-02-07 1975-12-02 Detrex Chem Ind Phosphate coating composition and method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006024614A1 (de) * 2006-05-26 2007-11-29 Schaeffler Kg Verfahren zum Behandeln einer Wälzlagerkomponente und Wälzlagerkomponente

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FI842886A0 (fi) 1984-07-18
AU567748B2 (en) 1987-12-03
FI842886A (fi) 1985-01-20
AU3078384A (en) 1985-01-24
CA1236952A (fr) 1988-05-24
FI77268C (fi) 1989-02-10
ES534422A0 (es) 1985-10-16
ATE39003T1 (de) 1988-12-15
JPS6039168A (ja) 1985-02-28
ZA845551B (en) 1985-03-27
FI77268B (fi) 1988-10-31
US4680064A (en) 1987-07-14
ES8600972A1 (es) 1985-10-16
EP0134895A1 (fr) 1985-03-27
DE3475412D1 (en) 1989-01-05
DE3325974A1 (de) 1985-01-31
BR8403587A (pt) 1985-06-25

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