EP3676419A1 - Procédé amélioré de phosphatation sans nickel de surfaces métalliques - Google Patents

Procédé amélioré de phosphatation sans nickel de surfaces métalliques

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Publication number
EP3676419A1
EP3676419A1 EP18756454.7A EP18756454A EP3676419A1 EP 3676419 A1 EP3676419 A1 EP 3676419A1 EP 18756454 A EP18756454 A EP 18756454A EP 3676419 A1 EP3676419 A1 EP 3676419A1
Authority
EP
European Patent Office
Prior art keywords
composition
ions
metallic surface
water
phosphating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP18756454.7A
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German (de)
English (en)
Other versions
EP3676419B1 (fr
Inventor
Olaf Dahlenburg
Thomas Kolberg
Lisa SEIDER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
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Chemetall GmbH
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Publication of EP3676419A1 publication Critical patent/EP3676419A1/fr
Application granted granted Critical
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Active legal-status Critical Current
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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
    • C23C22/34—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
    • C23C22/05—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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/105—Nitrates; Nitrites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/16—Phosphates including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/16—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions using inhibitors
    • C23G1/18—Organic inhibitors
    • C11D2111/16—
    • C11D2111/20—

Definitions

  • the present invention relates to a process for substantially nickel-free phosphating of a metallic surface using a specific detergent composition, this detergent composition itself and a process-phosphate-coated metallic surface and their use.
  • Such phosphate coatings are mainly used in the automotive industry and the general industry.
  • KTL cathodically deposited electrodeposition paints
  • phosphate coatings are usually applied by means of a nickel-containing phosphating solution.
  • the elementary or as alloying constituent, e.g. Zn / Ni, deposited nickel ensures a suitable conductivity of the coating in the subsequent electrodeposition coating.
  • nickel ions are no longer desirable as part of treatment solutions because of their high toxicity and environmental toxicity, and should therefore be avoided or at least reduced in content as much as possible.
  • the object of the present invention was therefore to provide a method with which metallic surfaces can be phosphated essentially nickel-free, wherein the aforementioned disadvantages of the prior art are avoided.
  • a metallic surface is treated successively with the following compositions: i) with an alkaline aqueous cleaning composition containing at least one water-soluble silicate and then ii) with an acidic, aqueous, substantially nickel-free phosphating composition comprising zinc ions, manganese ions and phosphate ions.
  • an uncoated metallic surface on the other hand, but also an already conversion coated metallic surface can be treated by the method according to the invention.
  • an already conversion-coated metallic surface should therefore always be included as well, however, it is preferably an uncoated metallic surface.
  • aqueous composition refers to a composition which contains water as solvent / dispersion medium at least in part, preferably for the most part, ie more than 50% by weight It may therefore be, for example, an emulsion, but it is preferably a solution, ie a composition which contains no coarsely dispersed constituents.
  • a silicate is meant that at 25 ° C, a water solubility (in deionized water) of at least 1 mg / l, preferably at least 10 mg / l, more preferably at least 100 mg / l, more preferably at least 1 g / l, more preferably at least 10 g / l, even more preferably at least 100 g / l, more preferably at least 200 g / l, more preferably at least 300 g / l and more preferably at least 350 g / l.
  • the silicate can also be present as a colloidal solution.
  • a composition contains less than 0.3 g / l of nickel ions, it should be considered as "essentially nickel-free" for the purposes of the present invention.
  • the phosphating composition preferably contains less than 0.1 g / l and more preferably less than 0.01 g / l
  • phosphate ions also means hydrogen phosphate, dihydrogen phosphate and phosphoric acid.
  • pyrophosphoric acid and polyphosphoric acid as well as all their partially and completely deprotonated forms should be included.
  • metal ion is understood as meaning either a metal cation, a complex metal cation or a complex metal anion.
  • the metallic surface is preferably steel, a steel alloy, a hot-dip galvanizing, an electrolytic galvanizing, a zinc alloy such as Zn / Fe or Zn / Mg, aluminum or an aluminum alloy.
  • the hot-dip galvanizing and the electrolytic galvanizing in each case are in particular such on steel.
  • the metallic surface is at least partially galvanized.
  • the inventive method is particularly suitable for multi-metal applications, in particular for metallic surfaces, which in addition to a galvanizing on steel, preferably a hot dip galvanizing and an electrolytic galvanizing, aluminum and / or an aluminum alloy, preferably an aluminum alloy.
  • the metallic surface is, according to the invention, first cleaned (step i), in particular degreased, in an alkaline, aqueous cleaning composition.
  • an acidic or neutral pickling composition may also be used for this purpose.
  • the detergent composition may be obtained from a concentrate by dilution with a suitable solvent, preferably with water, preferably by a factor between 1.5 and 1000, more preferably between 50 and 200, and if necessary adding a pH modifying substance.
  • the at least one water-soluble silicate contained in the detergent composition causes a better cleaning action and reduces the pickling attack in the cleaning bath (inhibiting effect).
  • the at least one water-soluble silicate in this case preferably comprises at least one water glass, in particular a lithium water glass, a soda water glass and / or a potassium silicate, more preferably a soda water glass and / or a potassium silicate, and / or at least one metasilicate such as disodium metasilicate (Na 2 SiO 3).
  • the at least one water-soluble silicate comprises a soda water glass or a potassium silicate glass.
  • the soda water glass is preferably one having a molar Na 2 O: SiO 2 ratio in the range from 1 to 4.
  • the potassium silicate glass is likewise preferably one having a molar K 2 O: SiO 2 ratio in the range from 1 to 4 ,
  • the at least one water-soluble silicate is preferably present in a total concentration in the range from 0.01 to 15 g / l, more preferably from 0.2 to 13 g / l and particularly preferably from 0.5 to 10 g / l.
  • the detergent composition may contain, in addition to the at least one water-soluble silicate, at least one cationic, nonionic and / or anionic surfactant and / or other additives, in particular complexing agents, oxidizing agents, oils and / or auxiliaries, e.g. Solvent, borate and / or carbonate included.
  • at least one water-soluble silicate at least one cationic, nonionic and / or anionic surfactant and / or other additives, in particular complexing agents, oxidizing agents, oils and / or auxiliaries, e.g. Solvent, borate and / or carbonate included.
  • complexing agents cause a complexation of water hardness and dissolved cations, which by the pickling attack in the cleaner bath go into solution or present.
  • Preferred complexing agents are on the one hand phosphorus-containing complexing agent.
  • phosphate-based complexing agents preferably in turn condensed phosphates such as e.g. Pyrophosphates, tripolyphosphates and other polyphosphates - as well as phosphonic acids, e.g. 1-Hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and its salts.
  • condensed phosphates such as e.g. Pyrophosphates, tripolyphosphates and other polyphosphates - as well as phosphonic acids, e.g. 1-Hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and its salts.
  • HEDP 1-Hydroxyethane- (1, 1-diphosphonic acid)
  • the phosphorus-containing, in particular the phosphate-based complexing agents are preferably in a total concentration in the range of 0.01 to 15 g / l, more preferably from 0.05 to 13 g / l and particularly preferably from 0.1 to 10 g / l (calculated as Tetrapotassium pyrophosphate).
  • preferred complexing agents are hydroxycarboxylic acids which have at least one hydroxyl group and at least one carboxyl group, and their salts, in particular sugar acids and their salts, particularly preferably heptonate and gluconate. Very particular preference is given to gluconate.
  • Such complexing agents are preferably present in a total concentration in the range of from 0.01 to 6 g / l, more preferably from 0.05 to 5 g / l, and most preferably from 0.1 to 4 g / l (calculated as sodium gluconate).
  • the cleaning composition contains at least one phosphorus-containing complexing agent, in particular a pyrophosphate and / or a tripolyphosphate, and at least one hydroxycarboxylic acid or its salt, in particular gluconate.
  • phosphorus-containing complexing agent in particular a pyrophosphate and / or a tripolyphosphate
  • hydroxycarboxylic acid or its salt in particular gluconate.
  • Very particularly preferred combinations are: i) tetrapotassium pyrophosphate and gluconate,
  • a preferred oxidizing agent is nitrite.
  • the oxidizing agents are preferably in a total concentration in the range of 10 to 100 mg / l, more preferably from 20 to 50 mg / l (calculated as nitrite) before.
  • the cleaner composition is preferably added no iron ions, in particular no iron (III) ions. If necessary, iron ions present in the cleaning bath originate in this case exclusively from the treated metallic Surface.
  • the pH of the cleaner composition is preferably in the range of 9.5 to 13, in particular in the range of 10.5 to 12, more preferably in the range of 10.7 to 12.0, more preferably of 1 1, 0 to 12, 0, more preferably from 1 1, 3 to 12.0 and particularly preferably in the range of 1 1, 5 to 12.0.
  • the detergent composition preferably has a temperature in the range of from 35 to 70, more preferably from 40 to 65, and most preferably from 45 to 60 ° C.
  • the treatment of the metallic surface with the detergent composition is preferably carried out for 30 to 600, more preferably for 60 to 480 and most preferably for 90 to 360 seconds, preferably by means of dipping or spraying, or the combination of both.
  • the metallic surface is first sprayed with the detergent composition for 30 to 90 seconds and then immersed in it for 100 to 300 seconds.
  • the cleaning / pickling and before the treatment of the metallic surface with the phosphating composition takes place advantageously at least one rinsing of the metallic surface with water, wherein the water optionally also dissolved in water additive such.
  • water additive such as a nitrite or surfactant may be added.
  • the activation composition serves to deposit a plurality of ultrafine phosphate particles as seed crystals on the metallic surface. These help in the subsequent process step, in contact with the phosphating - preferably without interim rinsing - form a particular crystalline phosphate layer with the highest possible number of densely arranged fine phosphate crystals or a substantially closed phosphate layer.
  • alkaline compositions based on titanium phosphate or zinc phosphate are suitable as activating compositions.
  • activating agents in particular titanium phosphate or zinc phosphate, already to the cleaner composition, ie to carry out purification and activation in one step.
  • the acidic, aqueous, substantially nickel-free phosphating composition includes zinc ions, manganese ions, and phosphate ions.
  • the phosphating composition may be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor between 1.5 and 100, preferably between 5 and 50, and if necessary adding a pH modifying substance.
  • the phosphating composition preferably comprises the following components in the following preferred and particularly preferred concentration ranges:
  • a concentration in the range from 0.3 to 2.5 g / l has already been found to be advantageous with regard to the free fluoride, a concentration in the range from 10 to 250 mg / l.
  • the complex fluoride is preferably tetrafluoroborate (BF 4 _ ) and / or hexafluorosilicate (SiF 6 2 ⁇ ).
  • Al 3+ is a bad poison in phosphating systems and can be removed from the system by complexation with fluoride, eg as cryolite.
  • fluoride eg as cryolite.
  • Complex fluorides become the bath fluoride also helps to improve paint adhesion and corrosion protection, and complex fluoride on galvanized material helps to prevent defects such as sticking ,
  • the phosphating composition has a content of iron (III) ions.
  • the iron (III) ions are preferably added to the phosphating composition.
  • an addition amount of iron (III) ions in the range from 0.001 to 0.2 g / l, more preferably from 0.001 to 0.1 g / l, more preferably from 0.005 to 0.1 g / l, particularly preferably from 0.005 to 0.05 g / l and most preferably from 0.005 to 0.02 g / l.
  • the phosphating composition preferably contains at least one accelerator selected from the group consisting of the following compounds in the following preferred and particularly preferred concentration ranges:
  • the at least one accelerator is H2O2.
  • the phosphating composition preferably contains less than 1 g / l, more preferably less than 0.5 g / l, more preferably less than 0.2 g / l and most preferably less than 0.1 g / l of nitrate.
  • the nitrate in the phosphating causes an additional acceleration of Stratification reaction, which leads to lower coating weights but mainly reduces the incorporation of manganese in the crystal.
  • the manganese content of the phosphate coating is too low, this is at the expense of its alkali resistance.
  • Alkali resistance in turn plays a crucial role in subsequent cathodic electrodeposition.
  • an electrolytic splitting of water occurs at the substrate surface: Hydroxide ions are formed. This causes the pH at the interface of the substrate to increase. It is true that only then can the electrocoating be agglomerated and separated. However, the increased pH can also damage the crystalline phosphate layer.
  • the phosphating composition preferably has a temperature in the range of 30 to 55 ° C.
  • the phosphating composition can be characterized by the following preferred and particularly preferred parameter ranges:
  • FS stands for free acid
  • FS (verd.) For free acid (diluted)
  • GSF for total acid according to Fischer
  • GS for total acid
  • S value for acid value
  • a suitable vessel for example a 300 ml Erlenmeyer flask. If the phosphating composition contains complex fluorides, 2-3 g of potassium chloride are added to the sample. Then, using a pH meter and an electrode, it is titrated with 0.1 M NaOH to a pH of 3.6. The amount of 0.1 M NaOH consumed in ml per 10 ml of the phosphating composition gives the value of the free acid (FS) in points.
  • the free acid (diluted) 10 ml of the phosphating composition are pipetted into a suitable vessel, for example into a 300 ml Erlenmeyer flask. Subsequently, 150 ml of deionized water are added. Using a pH meter and an electrode, titrate with 0.1 M NaOH to a pH of 4.7. The consumed amount of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition gives the value of the free acid (diluted) (FS (dil.)) In points. About the difference to the free acid (FS) the content of complex fluoride can be determined. If this difference is multiplied by a factor of 0.36, the content of complex fluoride is SiF6 2 ⁇ in g / l.
  • the dilute phosphating composition is titrated to pH 8.9 after addition of potassium oxalate solution using a pH meter and electrode with 0.1 M NaOH.
  • the consumption of 0.1 M NaOH in ml per 10 ml of the diluted phosphating composition hereby gives the total Fischer acid (GSF) in points. If this value is multiplied by 0.71, the total content of phosphate ions is calculated as P2O5.
  • the total acid (GS) is the sum of the divalent cations present as well as free and bound phosphoric acids (the latter being phosphates). It is determined by the consumption of 0.1 M NaOH using a pH meter and an electrode. For this purpose, 10 ml of the phosphating composition are pipetted into a suitable vessel, for example a 300 ml Erlenmeyer flask and diluted with 25 ml of deionized water. It is then titrated with 0.1 M NaOH to a pH of 9. The consumption in ml per 10 ml of the diluted phosphating composition corresponds to the total acid score (GS).
  • S value stands for the ratio FS: GSF and is given by Divide the value of the free acid (FS) by the value of the total acid according to Fischer (GSF).
  • a temperature of the phosphating of less than 45 ° C, preferably in the range between 35 and 45 ° C leads to further improved corrosion and paint adhesion values.
  • the treatment of the metallic surface with the phosphating composition is preferably carried out for 30 to 480, particularly preferably for 60 to 300 and very particularly preferably for 90 to 240 seconds, preferably by means of dipping or spraying.
  • the metallic surface is rinsed after treatment with the phosphating composition, more preferably rinsed with demineralized water or city water.
  • the already treated with the phosphating, ie phosphate-coated, metallic surface is still treated with an aqueous Nach Whyzusammen experience.
  • the metallic surface is optionally dried before treatment with the Nach Whyzusammen experience.
  • the rinse-off composition can be obtained from a concentrate by dilution with a suitable solvent, preferably with water, by a factor between 1.5 and 1000, preferably between 5 and 700, and if necessary adding a pH modifying substance.
  • the treatment with the post-rinse composition makes it possible to adjust the electrical conductivity of the phosphate-coated metal surface in a targeted manner by producing defined pores in the phosphate layer.
  • the conductivity may be either greater than, equal to, or smaller than that of a corresponding metal surface provided with a nickel-containing phosphate coating.
  • the adjusted electrical conductivity of the phosphate-coated metal surface can be influenced by varying the concentration of a given metal ion or polymer in the post-rinse composition.
  • the post-rinse composition contains at least one kind of metal ion selected from the group consisting of the ions of the following metals in the following preferred, most preferred and most preferred concentration ranges (all calculated as corresponding metal): Mo 1 to 500 mg / l 10 to 250 mg / l 20 to 150 mg / l
  • the metal ions contained in the post-rinse composition are deposited either in the form of a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
  • a salt which preferably contains the corresponding metal cation (eg molybdenum or tin) in at least two oxidation states - in particular in the form of an oxide hydroxide, a hydroxide, a spinel or a defect spinel - or elementally on the surface to be treated (eg copper, silver, gold or palladium).
  • the metal ions are molybdenum ions. These are preferably added as molybdate, more preferably as ammonium heptamolybdate and more preferably as ammonium heptamolybdate x 7 H2O to the post-rinse composition.
  • the molybdenum ions can also be added as sodium molybdate.
  • molybdenum ions may also be added to the post-rinse composition in the form of at least one molybdenum cation-containing salt, such as molybdenum chloride, and then oxidized to molybdate by a suitable oxidizing agent, for example by the accelerators described above.
  • a suitable oxidizing agent for example by the accelerators described above.
  • the post-rinse composition itself contains a corresponding oxidizing agent.
  • the post-rinse composition contains molybdenum ions in combination with copper ions, tin ions or zirconium ions.
  • molybdenum ions in combination with zirconium ions and optionally a polymer or copolymer, in particular selected from Group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethylenimines, polythiophenes and polypryrenes and mixtures and copolymers thereof and polyacrylic acid, wherein the content of molybdenum ions and zirconium ions is in each case in the range from 10 to 500 mg / l (calculated as metal) ,
  • the content of molybdenum ions is preferably in the range from 20 to 150 mg / l, particularly preferably from 25 to 100 mg / l and very particularly preferably from 30 to 75 mg / l and the content of zirconium ions in the range from 50 to 300 mg / l, more preferably from 50 to 150 mg / l.
  • the metal ions are copper ions.
  • the rinsing solution then contains these in a concentration of 100 to 500 mg / l, more preferably from 150 to 225 mg / l.
  • the rinse-off composition according to the invention comprises at least one polymer selected from the group consisting of the polymer classes of the polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and also their mixtures and copolymers.
  • the at least one polymer is preferably in a concentration in the range of 0.1 to 5 g / l, more preferably from 0.1 to 3 g / l, more preferably from 0.3 to 2 g / l and particularly preferably in the range from 0.5 to 1.5 g / l (calculated as pure polymer).
  • the polymers used are preferably cationic polymers, in particular polyamines, polyethyleneamines, polyimines and / or polyethyleneimines. Particular preference is given to using a polyamine and / or polyimine, very particularly preferably a polyamine.
  • the rinse-off composition according to the invention comprises at least one kind of metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium and at least one polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythiophenes and polypryrenes and their Mixtures and copolymers, in each case in the following preferred, particularly preferred and very particularly preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the corresponding metal).
  • metal ion selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin, antimony, titanium, zirconium and hafnium
  • polymer selected from the group consisting of the polymer classes of polyamines, polyethyleneamines, polyanilines, polyimines, polyethyleneimines, polythi
  • the at least one polymer is a cationic polymer, in particular a polyamine and / or polyimine, and the metal ions are copper ions, molybdenum ions and / or zirconium ions, in each case in the following preferred, particularly preferred and very particular preferred concentration ranges (polymer calculated as pure polymer and metal ions calculated as the corresponding metal).
  • the post-rinse composition comprises, in particular, when the metallic surface is aluminum or an aluminum alloy, preferably additionally 20 to 500 mg / l, more preferably 50 to 300 mg / l and particularly preferably 50 to 150 mg / l of Ti, Zr and / or Hf in complexed form (calculated as metal). These are preferably fluoro complexes.
  • the post-rinse composition preferably comprises 10 to 500 mg / l, more preferably 15 to 100 mg / l, and most preferably 15 to 50 mg / l of free fluoride.
  • the post-rinse composition contains Zr in complexed form (calculated as metal) and at least one kind of metal ions selected from the group consisting of the ions of molybdenum, copper, silver, gold, palladium, tin and antimony, preferably molybdenum.
  • the pH of the post-rinse composition is preferably in the acidic range, more preferably in the range of 3 to 5, particularly preferably in the range of 3.5 to 5.
  • the pH is preferably 3.5 to 4.5, and more preferably 3.5 to 4.0.
  • the post-rinse composition is essentially nickel free. It preferably contains less than 0.1 g / l and more preferably less than 0.01 g / l of nickel ions.
  • the post-rinse composition preferably has a temperature in the range of 15 to 40 ° C.
  • the treatment of the metallic surface with the post-rinse composition is preferably carried out for 10 to 180, particularly preferably for 20 to 150 and very particularly preferably for 30 to 120 seconds, preferably by means of dipping or spraying.
  • the metallic surface is first rinsed after the treatment with the Nach Whyzusammen GmbH, preferably with deionized water, and optionally dried.
  • the present invention further relates to the alkaline aqueous cleaning composition described above, which contains at least one water-soluble silicate, as well as to the correspondingly described concentrate from which this cleaning composition is obtainable.
  • the invention additionally relates to a phosphate-coated metallic surface obtainable by the process according to the invention.
  • the invention still relates to the use of the coated with the inventive method metallic surfaces in the field of automotive, automotive suppliers or general industry.
  • cleaning bath A By mixing the components in demineralized water, optionally adjusting the pH with phosphoric acid (cleaning bath A) and then diluting the mixture by a factor of 50 to 70, the following cleaning baths were prepared:
  • the cleaning bath F and the cleaning bath G were also used.
  • the cleaning bath F was identical to the cleaning bath B except for the pH of 10.5
  • the cleaning bath G was identical to the cleaning bath E except for the pH of 10.5.
  • the pH was adjusted both in the cleaning bath F and G with phosphoric acid.
  • Hot dip galvanized steel (EA), electrolytically galvanized steel (G) and aluminum alloy AA 6014 (AI) test plates were immersed in one of the cleaning baths A to D at 60 ° C for 300 seconds and then in an activating bath at 25 ° C for 30 seconds containing 0.6 g / l zinc phosphate.
  • the test panels were then immersed for 180 seconds at 45 ° C in one of the phosphating baths A ' to C and then for 30 seconds at 25 ° C in the rinse described above. After thorough rinsing with demineralized water, the test panels were also coated with a cathodic electrodeposition paint and a standard auto paint finish (filler, basecoat, clearcoat).
  • test plates made of electrolytically as well as hot-dip galvanized steel were subjected to a VDA test (VDA 621-415, 10 rounds), whereby the undercoat (U) was determined in mm and the lacquer removal after rockfall (DIN EN ISO 20567-1, Verf. C) was determined.
  • U undercoat
  • DIN EN ISO 20567-1, Verf. C lacquer removal after rockfall
  • the lattice cutting results of Table 1 clearly show the deterioration of the paint adhesion in nickel-free versus nickel-containing phosphating on hot-dip galvanized and electrolytically galvanized steel (compare VB2 vs. VB1, VB4 vs. VB3).
  • VB2 vs. VB1, VB4 vs. VB3 By using a cleaning bath according to the invention, it is possible to achieve a paint adhesion in the nickel-free variant which almost corresponds to that of the nickel-containing variant (compare B1 vs. VB1 and B2 vs. VB3).

Abstract

La présente invention concerne un procédé de phosphatation sensiblement sans nickel d'une surface métallique, selon lequel une surface métallique est traitée successivement avec les compositions suivantes : i) une composition de nettoyage aqueuse alcaline contenant au moins un silicate hydrosoluble et ii) une composition de phosphatation sensiblement sans nickel, aqueuse et acide, contenant des ions de zinc, des ions de manganèse et des ions de phosphate. L'invention concerne également la composition de nettoyage susmentionnée ainsi qu'une surface métallique revêtue de phosphate par le procédé susmentionné et son utilisation.
EP18756454.7A 2017-08-31 2018-08-28 Procédé amélioré de phosphatage sans nickel des surfaces métalliques Active EP3676419B1 (fr)

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PCT/EP2018/073056 WO2019042951A1 (fr) 2017-08-31 2018-08-28 Procédé amélioré de phosphatation sans nickel de surfaces métalliques

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KR (1) KR20200045487A (fr)
CN (1) CN111065761A (fr)
BR (1) BR112020002882A2 (fr)
ES (1) ES2966844T3 (fr)
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US11643731B2 (en) * 2017-08-31 2023-05-09 Chemetall Gmbh Method for nickel-free phosphating metal surfaces
TW202330890A (zh) 2021-09-27 2023-08-01 德商開麥妥公司 用於清潔及處理金屬基材之無硼酸鹽水性組合物

Family Cites Families (19)

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Publication number Priority date Publication date Assignee Title
DE1063873B (de) * 1955-06-15 1959-08-20 Metallgesellschaft Ag Verfahren zur Verfeinerung der Schichtausbildung mit Hilfe von Loesungen schichtbildender Phosphate
DE3325974A1 (de) * 1983-07-19 1985-01-31 Gerhard Collardin GmbH, 5000 Köln Verfahren und universell anwendbare mittel zum beschleunigten aufbringen von phosphatueberzuegen auf metalloberflaechen
DE3635343A1 (de) * 1986-10-17 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen
JPH0672311B2 (ja) * 1987-04-08 1994-09-14 トヨタ自動車株式会社 リン酸亜鉛化成処理方法
DE4012795A1 (de) * 1990-04-21 1991-10-24 Metallgesellschaft Ag Aktivierungsmittel fuer die phosphatierung
DE4216405A1 (de) * 1992-05-18 1993-11-25 Henkel Kgaa Pumpfähige alkalische Reinigerkonzentrate
WO1994003571A1 (fr) * 1992-07-31 1994-02-17 Henkel Corporation Procede et composition aqueuse pour degraisser les surfaces metalliques
CA2169927A1 (fr) * 1993-09-17 1995-03-23 Kevin Brown Pre-rincage destine a la phosphatation de surfaces metalliques
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19854431A1 (de) * 1998-11-25 2000-05-31 Henkel Kgaa Phosphatierverfahren mit Spülwasser-Einsparung
DE10110834B4 (de) * 2001-03-06 2005-03-10 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate
DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
US6929705B2 (en) * 2001-04-30 2005-08-16 Ak Steel Corporation Antimicrobial coated metal sheet
JP4173753B2 (ja) * 2002-03-13 2008-10-29 本田技研工業株式会社 アルミ自動車車体の塗膜形成方法、該塗膜形成方法に用いる化成液、プライマーサーフェーサー、および複層塗膜
CN101363125B (zh) * 2008-09-24 2011-12-21 南京利民机械有限责任公司 一种碱性水基清洗剂
WO2016162423A1 (fr) * 2015-04-07 2016-10-13 Chemetall Gmbh Procédé de phosphatation sans nickel de surfaces metalliques
CN105369271B (zh) * 2015-12-10 2017-11-17 重庆永林机械设备有限公司 一种涂装前金属表面处理方法
DE102017208802A1 (de) 2016-05-25 2017-11-30 Chemetall Gmbh Verfahren zur korrosionsschützenden Phosphatierung einer metallischen Oberfläche mit vermindertem Beizabtrag
US11643731B2 (en) * 2017-08-31 2023-05-09 Chemetall Gmbh Method for nickel-free phosphating metal surfaces

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JP2021501829A (ja) 2021-01-21
MX2020002343A (es) 2020-07-13
US20200199758A1 (en) 2020-06-25
RU2020111711A3 (fr) 2022-02-02
JP7279019B2 (ja) 2023-05-22
WO2019042951A1 (fr) 2019-03-07
KR20200045487A (ko) 2020-05-04
EP3676419B1 (fr) 2023-10-11
US11643731B2 (en) 2023-05-09
ES2966844T3 (es) 2024-04-24
BR112020002882A2 (pt) 2020-10-06
CN111065761A (zh) 2020-04-24

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