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EP1433879B1 - Procédé de revêtement de surfaces métalliques avec une solution de phosphate alcalin, concentré aqueux et utilisation des surfaces métalliques ainsi revêtues - Google Patents

Procédé de revêtement de surfaces métalliques avec une solution de phosphate alcalin, concentré aqueux et utilisation des surfaces métalliques ainsi revêtues Download PDF

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Publication number
EP1433879B1
EP1433879B1 EP03028810A EP03028810A EP1433879B1 EP 1433879 B1 EP1433879 B1 EP 1433879B1 EP 03028810 A EP03028810 A EP 03028810A EP 03028810 A EP03028810 A EP 03028810A EP 1433879 B1 EP1433879 B1 EP 1433879B1
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Prior art keywords
alkali
process according
metal
deposition
content
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EP03028810A
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German (de)
English (en)
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EP1433879A1 (fr
Inventor
Detlev Seifert
Franz Dressler
Thomas Willumeit
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Chemetall GmbH
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Chemetall GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • 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
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the invention relates to a process for coating metal surfaces of substrates with an aqueous, acidic, alkali metal and phosphate phosphating solution, which is particularly suitable to deposit a thin electrodeposition coating on the substrates with a pretreatment layer of this Alkaliphosphat, and a corresponding aqueous concentrate and the use the products prepared by the process according to the invention.
  • the fresh, not yet used alkali metal phosphate solutions usually have virtually no or only a very low content of aluminum, iron and zinc.
  • the aqueous acidic alkali metal phosphate solutions contain, in addition to ions of at least one alkali metal or / and ammonium, also phosphate ions and, due to the pickling effect of these solutions on the metallic surfaces, ion contents of the metals dissolved out of the metallic surfaces, e.g. Aluminum, iron or / and zinc as well as traces of alloy components of the recommended metallic materials.
  • the phases mainly formed in the alkali phosphate layer in alkali phosphating are the corresponding phosphates, oxides or / and hydroxides of the metals from the surfaces of the base substrates to be treated.
  • Alkaline phosphate solutions or coatings are also referred to as iron phosphate solutions or coatings when used on iron materials.
  • iron phosphate solutions or coatings when used on iron materials.
  • aluminum or aluminum alloys where aluminum phosphate is used.
  • the most diverse Base metals are coated with the same Alkaliphosphatans, then the ions of the various base metals in the solution can accumulate more.
  • these alkali phosphate layers they are - unlike, for example, the so-called zinc phosphating - often largely or completely amorphous and extremely feinkömig.
  • alkali phosphate coatings are generally also referred to as layers of the so-called "non-layer-forming phosphating". This designation is misleading, since layers are also formed here, but they are significantly thinner than other phosphate layers, such as e.g. the different types of zinc phosphating.
  • the alkali phosphate solution always contains an increased content of at least one alkali metal, e.g. Sodium or / and ammonium.
  • the layers of the Alkaliphosphat mich are often - in contrast to the crystalline layers of the other types of so-called.
  • "Layer-forming phosphating" - mostly X-ray amorphous and show under the scanning electron microscope usually no crystalline grain shapes.
  • the layers of Alkaliphosphatierung are often poor, almost free or entirely free of manganese and zinc, unless manganese or zinc-rich metallic surfaces are treated or pretreated. They are typically poor in being nearly free or wholly free of cobalt, nickel, titanium and / or similar heavy metals.
  • the phases which are predominantly formed during iron phosphating on at least one iron material are iron phosphates, iron oxides and / or iron hydroxides such as Vivianite and / or magnetite.
  • the contents of ions of Fe, Al or Zn dissolved out of the metallic surface and then contained in the alkali metal phosphate solution are comparatively small, since such compounds or cations are generally not added to the bath, but then only or almost exclusively due to the staining effect of the bath Phosphating solution from the Base metal to be coated metallic surface are dissolved out and then deposited on this surface mostly as phosphates, oxides and / or hydroxides.
  • traces or low ion contents from impurities or entrainments and / or due to the staining effect of the phosphating solution on components of the plants may also originate.
  • An essential difference of the alkali phosphating to processes of so-called zinc, zinc-manganese or zinc-manganese-nickel phosphating is that the cation of necessary for layer formation phosphates, oxides or / and hydroxides in the alkali phosphating always essential component dissolved out of the Base substrates is, while in the so-called zinc, zinc-manganese or zinc-manganese-nickel phosphating depending on the composition of the base material, which is coated, and depending on the cation content of the phosphating a comparatively high zinc content of usually more than 0.4 g / L or often more than 1 g / L is contained in the phosphating solution, which is partially or completely formed by appropriate additions to the phosphating solution, and wherein usually the predominantly zinc and / or manganese-containing phosphates Huréaulith, phosphophyllite, Scholzite or / and Hopeit be formed in a clearly crystalline form.
  • the layers of the alkali phosphating have significantly different properties than those of the zinc phosphating: they are usually only in a layer thickness in the range of 0.1 to 0.8 microns or only a layer weight in the range of 0.2 to 9.3 g / m 2 .
  • the much thinner alkali phosphate layers are mostly iridescent and / or translucent, often bluish iridescent.
  • the alkali phosphate layers usually show the colors of "higher order" and are also slightly yellowed, greenish or violet iridescent with slightly changed layer thickness, whereas layers with higher Layer weight (about 0.7 to 1.3 g / m 2 ) and possibly also corresponding accelerator content in the phosphating rather a gray-haired appearance can show.
  • Alkaliphosphat füren on aluminum or aluminum alloys may also have a silvery iridescent appearance.
  • the alkali phosphate layers can be applied as treatment layers without following e.g. at least one lacquer layer is applied. They may also be used as pretreatment layers over at least one subsequent coating, such as e.g. with a primer, paint and / or a different organic coating or serve with an adhesive or adhesive carrier.
  • alkali phosphate coatings are prepared as pre-treatment layers prior to painting by contact with an acidic aqueous mono- and / or orthophosphate-containing phosphating and then by electrocoating the entire metal surface and often by subsequent powder coating of the readily accessible from the outside surface lots. These procedures are being exploited ever more today. The aim is to make these processes always more process-safe and cost-effective.
  • an unnecessarily thick electrodeposition coating layer is applied to the easily accessible and therefore easily paintable parts of the metal parts. It would be sufficient if in each case a continuous, namely a so-called stratified electrodeposition coating layer would be achieved.
  • DE-A1-100 06 338 describes a similar process for this purpose, in which the addition of a copper compound or a compound of an even more noble, electrically conductive metal is added to the iron phosphating solution, wherein the additive ensures the formation of locally installed local elements in the layer, which, in the case of the Belz attack of the acid phosphating solution, result in a faster film formation reaction from the iron phosphate solution, thereby permitting a denser layer to be formed.
  • the addition of the copper compound is difficult to dissolve in the solution at the commonly used pH of the phosphating solution for the spraying process.
  • the optimization of iron phosphating for thin electrodeposition coating layers occasionally encountered difficulties that made it difficult to apply the electrodeposition paint sparingly.
  • No. 4,522,892 teaches a method for coating steel strip which has on one side an electrolytic zinc coating and a phosphate layer based on alkali metal phosphate / ammonium phosphate, the phosphating being applied electrolytically.
  • EP 0 261 704 A1 describes zinc phosphations which, as electrolessly produced, so-called “layer-forming phosphatizations”, have distinctly different expressions have as the electroless generated, so-called “non-film-forming phosphatizations”, which include alkali phosphations.
  • EP 0 312 176 A1 relates to methods for applying tin phosphate-containing conversion coatings which can be generated electrolessly or electrolessly.
  • the paint deposition in the inventive method is significantly better than in comparison to a sulfate-richer Phosphatierbad. This has an effect, in particular, when the sulphate content can be reduced to less than 50 mg sulphate per liter or maintained at about this level due to the addition of precipitant.
  • a sulphate content can be regarded as a source of interference which can originate in particular from the low sulphate contents of the water used (mostly city water) and the partially increased sulphate contents from impurities of the substrate surfaces to be coated.
  • the latter sulphate contents can be derived, in particular, from anticorrosive oils and forming aids, which were previously based on the metallic Surface, can be detached and left in the bath solution.
  • the object of the invention is to propose an alkali phosphating process in which it is possible to apply the subsequently applied electrodeposition coating layer as a whole thinner than with a phosphating bath containing more sulphate ions and most prior art processes without thereby impairing the corrosion protection. It is also the task to propose a process which is also well suited for the application of the phosphating solution in spraying. The method should be used easily and safely in the series.
  • the object is achieved by a method for coating metallic surfaces with an aqueous acid Alkaliphosphat istssell, in particular prior to the deposition of a thin electrodeposition coating layer, wherein a layer of an aqueous, sulfate ion-containing Alkaliphosphat istsaims and deposited essentially based on phosphates / oxides / hydroxides of the mainly in the metallic surface metals such as Aluminum, iron or / and zinc is formed, wherein the aqueous solution for the deposition of the alkali metal phosphate layer has a content of manganese or / and nickel of less than 0.2 g per liter and wherein the alkali metal phosphating at least one cation and / or at least one Compound is added as precipitant based on barium, calcium or / and strontium for the precipitation of sulfate ions at a pH in the range of more than 3.5 to 7.
  • alkali metal phosphate layer according to the invention can therefore also be carried out well in the spray process, because stable solution ratios can be adjusted.
  • the phosphating solution according to the invention is preferably precipitated with an initial content in the range of at least 0.001 to 2 g / L, more preferably in the range of at least 0.01 or 1 g / L, in particular in the range of at least 0.02 or at least 0 , 1 g / L, added or / and held in this concentration range in the phosphating solution.
  • a higher content of precipitant may also be added or contained in the phosphating solution, but it does not have a correspondingly beneficial effect. Due to the precipitation, a low content of the phosphating solution of precipitant may possibly reduce rapidly.
  • the precipitant may be present in a content in the range of 0.001 to 2 g / L in the phosphating solution, more preferably in the range of at least 0.01 or up to 1 g / L or up to 0.8 g / L , in particular in the range of at least 0.02 or of at least 0.1 g / L.
  • the process of the present invention preferably uses an aqueous acidic solution for the deposition of the alkaline phosphate layer containing at least one cation, at least one chelate, at least one complex, at least one polyelectrolyte and / or at least one polymer, such as, for example, to precipitate the sulfate contained in the alkaline phosphating solution.
  • an aqueous acidic solution for the deposition of the alkaline phosphate layer containing at least one cation, at least one chelate, at least one complex, at least one polyelectrolyte and / or at least one polymer, such as, for example, to precipitate the sulfate contained in the alkaline phosphating solution.
  • the phosphating solution is an addition of ions of barium, calcium and / or strontium in the range of 0 to 1 g per liter, in particular of at least 0.005 or up to 0.8 g per liter, preferably of at least 0.01 in total or up to 0.5 g per liter, more preferably of at least 0.05 or up to 0.3 g per liter, very particularly preferably of a total of 0.02 or up to 0.2 g per liter added ,
  • an addition to at least one type of ions or / and compounds selected from the group of barium ions, barium compounds, strontium ions, strontium compounds, calcium ions, calcium compounds and polyelectrolyte (s) is particularly advantageous.
  • the level of the addition of precipitant can be adapted to the sulfate content of the solution.
  • the at least one precipitant is added to the phosphating solution in a content of 0.03 to 0.25 g / L or / and is contained in this concentration range in the phosphating solution.
  • the content of phosphate phosphating solution may preferably be in the range of 1 to 30 g P 2 O 5 per liter, more preferably in the range of 2 to 25 g P 2 O 5 per liter, most preferably in the range of 3.5 to 20 g P 2 O 5 per liter.
  • the addition of the phosphate, in particular to a concentrate, is preferably carried out by addition of orthophosphoric acid or the corresponding hydrogen phosphates, when added as a powder, for example as disodium hydrogen orthophosphate, only rarely as a polyphosphate.
  • the phosphating solution may have a content of iron in particular in the range of 0.01 to 1 g Fe per liter, especially in the range of 0.08 to 0.8 g Fe per liter.
  • the iron content in the iron phosphating solution is comparatively low because a large part of the iron content is precipitated.
  • the phosphating solution may have a content of manganese, nickel, zinc and / or other heavy metals. Some of these contents are dependent on the coated surfaces and on the equipment and raw materials used.
  • the content of manganese, nickel or / and zinc is in each case not more than 0.2 g per liter, more preferably not more than 0.1 g per liter.
  • the phosphating solution preferably has a content of ions of at least one alkali metal, in particular sodium, in the range of 0.3 to 10 g per liter, more preferably in the range of 0.6 to 9 g per liter, of individual ions, in particular Sodium, preferably in the range of 0.001 to 8.5 g per liter.
  • the total content of alkali metal ions in the bath can be from 1 to 8.8 g / L, in particular from 1.2 to 6.5 g / L, especially at least 1.5 g / L or up to 4 g / L.
  • a sodium content which is preferably 1 to 4.5 g / L, especially at least 1.5 g / L or up to 4 g / L.
  • the addition of sodium ions helps to adjust the pH and is preferably bound to the phosphoric acid.
  • the sodium ions can be introduced, for example, by adding sodium hydroxide.
  • other alkaline earth metal ions such as magnesium ions can occur, which develop only a relatively weak or no effect as a precipitant for sulfate. Therefore Magnesium ions or compounds are less suitable as precipitant.
  • the phosphating solution preferably has a content of ammonium ions in the range of 1 to 200 mg per liter, more preferably in the range of 3 to 150 mg per liter, most preferably in the range of 5 to 120 mg per liter.
  • the phosphating solution preferably has a content of free fluoride ions in the range of 0 to 500 mg per liter, more preferably in the range of 1 to 350 mg per liter, most preferably in the range of 50 to 300 mg per liter.
  • the addition of fluoride is preferably carried out by adding hydrofluoric acid.
  • the phosphating solution preferably has a content of molybdenum ions / molybdate or / and tungsten ions / tungstate in the range from 0 to 1.5 g per liter, in particular at least 5 mg per liter, preferably from 15 to 500 mg per liter, particularly preferably from 30 to 200 mg per liter, calculated as MoO 3 or WO 3 .
  • the ammonium ions can, if appropriate in combination with molybdate / molybdenum ions or tungstate / tungsten ions or as molybdate / molybdenum ions or tungstate / tungsten ions, have an accelerating effect.
  • the phosphating solution may also contain (other) oxidizing agents.
  • the phosphating solution preferably has a nitrate ion content in the range of 0 to 12 g per liter, more preferably in the range of 0.001 to 10 g per liter, most preferably in the range of 0.002 to 8 g per liter, especially at least 0.2 g per liter or at most 6 g per liter.
  • the content of nitrate ions allows an enhancement of the pickling attack and a homogenization of the phosphate layer formation and, moreover, can have an accelerating effect on the film formation.
  • Nitrate can also provide a contribution to the training of thin closed layers. Therefore, addition of nitrate is particularly preferred.
  • the phosphating solution preferably has a content of at least one accelerator other than nitrate, in particular an accelerator selected from the group of chlorate, nitrite, nitroguanidine, nitrobenzenesulfonate (NBS, eg with sodium as SNBS;) and other nitro group-containing accelerators, in the range of, respectively 0 to 6 g per liter, preferably in the range of 0.2 to 4.5 g per liter, more preferably in the range of 0.3 to 3 g per liter.
  • This accelerator (s) acts in a broader pH range, so that you can work in a wider pH range.
  • the sum of the contents of these accelerators without nitrate is preferably in the range of 0 to 10 g per liter, in particular in the range of 0.5 to 8 g / L, preferably of at least 1 g / L or up to 6 g / L.
  • nitrate can additionally occur in addition to at least one of these accelerators, but it does not have to.
  • the phosphating solution preferably has a content of at least one nonionic and / or anionic surfactant in the range from 0.05 to 15 g per liter, preferably from 0.1 to 6 g per liter, more preferably from 0.2 to 3 g per liter.
  • These surfactants provide better wetting of the metal surface and thus more uniform removal of organic contaminants on the metal surface, more uniform pickling attack on the metal surface, and more uniform phosphate layer formation on the metal surface.
  • the phosphating solution preferably has a content of at least one organic solubilizer in the range from 0 to 1 g per liter, preferably from 10 to 800 mg per liter, more preferably from 20 to 500 mg per liter.
  • Solubilizers can serve to surfactants one-component to obtain in the aqueous solution. They are important for the stability of surfactants in the concentrate according to the invention.
  • the phosphating solution advantageously has no or only a low content of nitrite ions, chromium ions, nickel ions, cobalt ions, manganese ions and cadmium ions. If the bath should have a higher content of at least one of these substances, u.U. a complicated disposal caused. Therefore, it is preferable not to intentionally add these ions to the bath and avoid them as much as possible during operation. Furthermore, the phosphating solution preferably also has no increased content of chloride ions for reasons of corrosion protection of the metal parts to be coated. Certain levels of aluminum in the phosphating solution may u.U. for the precipitation of cryolite, such as calcium u.U. lead to the precipitation of calcium fluoride. Therefore, it is advantageous to keep levels of such ions within limits where possible, in which such precipitations that are not required can be avoided or minimized. For there is a need later to remove and dispose of the resulting sludge.
  • the phosphating solution preferably has a temperature in the range of 30 to 70 ° C, more preferably in the range of 40 to 65 ° C, most preferably in the range of 50 to 60 ° C.
  • the phosphating solution preferably has a pH in the range from 3.6 to 7, particularly preferably in the range from 3.8 to 6.5, very particularly preferably in the range from 4 to 6.0. Above pH 6.2, the pickling reaction may already be very weak. It is recommended to adjust the pH comparatively accurately.
  • the value of the total acid may increase with increasing bath life from the beginning, for example, in the order of about 5 points until later, for example to about 20 points; but at higher or lower acidity, the total acid can also vary in other ranges of values.
  • the phosphating solution preferably has a total acid score in the range of 2 to 30, more preferably in the range of 6 to 27, most preferably in the range of 8 to 22.
  • the total acid score is the number of ml that results when 10 ml of phosphating solution diluted to 50 ml with deionized water is colorless with 0.1N sodium hydroxide solution to a pH of 8.9 at the transition point titrated pink with phenolphthalein.
  • the phosphating solution preferably has a free acid content of 0 to 5 points, more preferably in the range of 0.01 to 4.5 points, most preferably in the range of 0.03 to 3 points.
  • the free acid score is the number of ml that results when titrating 10 ml of phosphating solution diluted to 50 ml with demineralized water to 0.1 with 0.1N sodium hydroxide solution to pH 4.2, wherein the sample to be titrated is then added to KCI to saturation, if in the sample complexed fluoride is contained in order to prevent its dissociation as much as possible.
  • water quality for both the phosphating solution and the aqueous concentrate which can be used to prepare the bath as well as to supplement the phosphating solution, are preferably city water, which is advantageously decarboxylated at higher degrees of hardness, but also purer water qualities, e.g. demineralized water well suited.
  • the step of cleaning and phosphating is preferably with an injection time of 0.5 to 4 minutes, more preferably about 0.8 to 3 minutes, most preferably over 1 to 2 minutes with an injection pressure in the range of 0.3 to 2, 5 bar worked.
  • the metal parts may also be immersed in a bath for a period of 1 to 10 minutes, especially for 1.5 to 6 minutes.
  • the times mentioned refer to the sum of the phosphating times during pre-cleaning / phosphating and cleaning / phosphating.
  • the cleaning and phosphating can be carried out as in c) in two directly successive baths: It is advisable to set a higher total acid score in the first bath than in the second bath and to make sure that the free acid content in both baths is zero is.
  • the rinsing is preferably carried out for 20 to 80 seconds with an injection pressure of 0.3 to 2.5 bar. All you need is an unheated bath with fresh water supply of city water quality. City water quality is preferred to have a larger buffering effect.
  • Rinsing can be carried out for 20 to 80 seconds with an injection pressure of 0.3 to 2.5 bar.
  • this is demineralized water used.
  • the salt load should be reduced as much as possible by appropriate measures such as downstream spray ring with demineralized water.
  • the dripping water should not exceed a value of the electrical conductivity due to the subsequent electrocoating of 50 ⁇ S / cm.
  • the thus pretreated metal parts are moved directly into the electrocoating plant.
  • the drying can then usually be omitted.
  • the inventive method is preferably used for metal parts - especially for those of complex geometry.
  • metal parts made of iron or steel materials, aluminum or aluminum alloys, magnesium alloys or galvanized metal parts are coated, wherein the galvanizing layer can also consist of Al- or / and Zn-rich alloys.
  • the inventive method can be used in particular for simple structural steels such. Apply St 370 well.
  • the alkali phosphate layer may be referred to as a conversion layer, even though ions dissolved out of the metal surface by pickling action participate in the layer structure. It is ideal as a temporary storage protection and as a primer for paintwork.
  • the alkali phosphate layer preferably has a thickness in the range from 0.05 to 1.4 ⁇ m, in particular in the range from 0.15 to 0.8 ⁇ m, and a layer weight in the range from 0.1 to 1.6 g / m 2 , preferably in the range of 0.15 to 1.4 g / m 2 , more preferably in the range of up to 1.2 g / m 2 , on. Layer thickness or layer weight are determined in the dried and cured state.
  • the phosphate layer is often amorphous or almost amorphous.
  • the alkali phosphate layer has increased contents of phosphates / oxides / hydroxides of the metals mainly present in the metal surface, such as aluminum, iron and / or zinc.
  • Coating layers having a layer thickness in the range from 0.3 to 100 ⁇ m, preferably in the range from 0.5 to 60 ⁇ m, particularly preferably in the range from 1 to 20 ⁇ m, in particular by cathodic or anodic dip coating, and optionally by at least one subsequent coating be applied.
  • the thickness of a dip-coating layer applied to the alkali phosphate layer is preferably only in the range from 4 to 12 ⁇ m, particularly preferably in the range from 6 to 1.0 ⁇ m.
  • the first dip coat layer applied to the alkali phosphate layer often has a coat weight in the range of 18 to 22.5 g / m 2 , assuming a baked layer resist density of 1.5 g / cm 3 of average film thickness in the Range of 12 to 15 microns, or even higher coating weights, while in the inventive method on similar metal parts with hidden areas a coating weight in the range of 10 to 17.5 g / m 2 can be achieved, which assuming a density the baked lacquer layer of 1.5 g / cm 3 corresponds to an average layer thickness in the range from 6.7 to 11.7 ⁇ m.
  • the additional lacquer layer here usually has decorative tasks and improves the corrosion protection slightly or sometimes considerably; it is often applied by powder coating.
  • metal or plastic parts can be glued, which are advantageously also pretreated and / or painted. These glued parts often have the shape of plates, for example, in FlachCloudkörpem.
  • the aqueous concentrate according to the invention may be characterized in that it contains as precipitating agent at least one cation, a chelate, a complex, a polyelectrolyte or / and a polymer which leads to difficultly or / and insoluble compounds with sulfate. It can be used as a precipitant each contain at least one cation and / or a compound selected from barium, calcium, strontium and their compounds.
  • alkaline earth metal ions such as e.g. Magnesium ions occur, but develop only a weak, almost no or no effect as a precipitant for sulfate.
  • the bath solution according to the invention can be adjusted.
  • the coated by the novel metallic body can be used as radiator elements, radiators, racks, plates, panels, angles, components in the vehicle or aircraft interior, components in apparatus and mechanical engineering.
  • the process according to the invention has the advantage over the previously described and practiced pretreatment processes by alkali phosphating that the thickness of the first coating layer can be significantly reduced without the corrosion protection being impaired in any case.
  • the phosphating solution or the effluents thereof are poor or free of dissolved sulfate, because Sulfate contents in waters should be kept as low as possible because of the risk to concrete or because of the wastewater regulation.
  • the thus pretreated parts could be coated with cathodic electrodeposition paint, wherein the pretreated metal parts were painted at about room temperature.
  • the substrates to be coated were sample plates and plates for radiators and convector body of normal structural steel St 370 with a length of 29.0 cm.
  • the concentrate used was an aqueous composition composed as follows: 200 g / LP 2 O 5 10 g / L NO 3 1 g / L molybdate 80 g / L Na 10 g / LK 1 g / L nitrobenzenesulfonate.
  • an aqueous composition was used which, after diluting the concentrate with water, was composed as follows: 20 g / LP 2 O 5 1 g / L NO 3 0.3 g / L SO 4 0.1 g / L molybdate 8th g / L Na 1 g / LK 0,003 g / L Fe 0.1 g / L nitrobenzenesulfonate.
  • This bath contained 0.3 g / L of sulphate before addition of the precipitant, and after addition of 0.5 g / L of precipitant based on BaCl 2 , the sulphate content of the bath dropped to significantly lower values. In this case, an overdose with precipitant was omitted.
  • the precipitate could be adjusted with BaCl 2 so that only about 0.05 g / L sulfate was contained in the bath solution after the sulfate precipitation.
  • the phosphate layers produced with this bath solution showed a layer thickness in the range of 0.1 to 0.4 ⁇ m and a layer weight in the range of 0.2 to 0.8 g / m 2 . They usually showed a bluish iridescent color. Thereafter, a very thin electrodeposition coating was applied. The further investigations were carried out on 4 plates coated with dip lacquer each with 10 Schichtdickenmeßddlingen.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Claims (25)

  1. Procédé de revêtement de surfaces métalliques avec une solution de phosphatation alcaline qui est une solution aqueuse acide, en particulier avant le dépôt d'une mince couche de vernis au trempé électrolytique, procédé dans lequel une couche est déposée à partir d'une solution aqueuse de phosphatation alcaline contenant des ions sulfate et ladite couche est principalement constituée de phosphates/d'oxydes/d'hydroxydes des métaux qui se trouvent majoritairement dans les surfaces métalliques, tels que, par exemple, l'aluminium, le fer et/ou le zinc, lequel procédé est caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration de manganèse et/ou de nickel valant chaque fois moins de 0,2 g par litre, et en ce que l'on ajoute à la solution de phosphatation alcaline au moins un cation et/ou au moins un composé faisant office d'agent de précipitation à base de baryum, de calcium et/ou de strontium, pour faire précipiter les ions sulfate à un pH de plus de 3,5 et valant jusqu'à 7.
  2. Procédé selon la revendication 1, caractérisé en ce que, pour faire précipiter le sulfate que contient la solution de phosphatation alcaline, on introduit chaque fois au moins un cation, un chélate, un complexe, un polyélectrolyte et/ou un polymère, qui forme(nt) des composés peu solubles et/ou insolubles dans l'eau avec le sulfate.
  3. Procédé selon la revendication 2, caractérisé en ce que l'agent de précipitation est introduit au départ à une concentration de 0,001 à 2 g/l dans la solution de phosphatation, et/ou est maintenu dans ce domaine de concentrations au sein de la solution de phosphatation.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration de phosphate correspondant à une valeur de 1 à 30 g de P2O5 par litre.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration de fer correspondant à une valeur de 0,01 à 1 g de Fe par litre.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration de zinc inférieure à 0,2 g par litre.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, dans la solution aqueuse permettant de déposer la couche de phosphate alcalin, la concentration de tous les ions des métaux alcalins vaut de 0,3 à 10 g par litre, et/ou la concentration des ions d'un seul métal alcalin, en particulier le sodium, vaut chaque fois de 0,001 à 8,5 g par litre.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration d'ions ammonium valant de 1 à 200 mg par litre.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration de fluorure libre valant de 0 à 500 mg par litre.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration d'ions molybdène/de molybdate et/ou d'ions tungstène/de tungstate, exprimée en MoO3 et/ou en WO3, valant chaque fois de 0 à 1,5 g par litre.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une concentration d'ions nitrate valant de 0 à 12 g par litre.
  12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin contient au moins un activateur qui n'est pas un nitrate, en particulier un activateur choisi parmi un chlorate, un nitrite, la nitroguanidine, un nitrobenzènesulfonate et au moins un autre activateur contenant des groupes nitro, la somme des concentrations de ces activateurs sans compter le nitrate valant de préférence de 0 à 10 g par litre.
  13. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin contient au moins un tensioactif non ionique et/ou un tensioactif anionique à une concentration valant de 0,05 à 15 g par litre.
  14. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin contient au moins un agent de solubilisation organique à une concentration valant de 0 à 1 g par litre.
  15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une température valant de 30 à 70°C.
  16. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente un pH valant de 3,6 à 7.
  17. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente un nombre de points d'acide total valant de 2 à 30.
  18. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la solution aqueuse permettant de déposer la couche de phosphate alcalin présente une teneur en acide libre représentant de 0 jusqu'à 5 points.
  19. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il permet de revêtir des pièces métalliques, en particulier des pièces métalliques de géométrie complexe, de préférence des pièces métalliques en matériaux ferreux ou sidérurgiques, en aluminium ou en alliages d'aluminium, en alliages de magnésium, ou des pièces métalliques galvanisées.
  20. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, à partir de la solution aqueuse, on dépose des couches de phosphate alcalin dont l'épaisseur, mesurée après séchage, vaut de 0,05 à 1,4 µm.
  21. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, à partir de la solution aqueuse, on dépose des couches de phosphate alcalin sur lesquelles on applique, par vernissage au trempé cathodique ou anodique, des couches de vernis dont l'épaisseur, mesurée après séchage et durcissement, vaut de 0,5 à 60 µm.
  22. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, sur la couche de vernis au trempé, on applique en plus une couche de vernis ou un revêtement d'une autre espèce de produit organique et/ou une couche d'adhésif, en particulier avec des pièces métalliques et/ou des pièces en matière plastique traitées au préalable et/ou vernies.
  23. Concentré aqueux pour la préparation d'une solution aqueuse de phosphatation alcaline destinée au dépôt d'une couche de phosphate alcalin, caractérisé en ce que ce concentré contient :
    - au moins un agent de précipitation pour faire précipiter les ions sulfate, à une concentration valant au total de 0,1 à 20 g/l,
    ledit concentré contenant chaque fois, en tant qu'agent de précipitation, au moins un cation et/ou au moins un élément de l'ensemble constitué par le baryum, le calcium, le strontium et leurs dérivés,
    - des ions phosphate à une concentration correspondant à une valeur de 50 à 300 g/l de P2O5,
    - et au moins un activateur, la concentration totale de ces activateurs sans compter le nitrate valant de 0 à 100 g/l, la concentration d'un seul activateur en l'absence de nitrate valant chaque fois de 0,1 à 50 g/l, et la concentration de nitrate, à la place ou en plus de ces activateurs, valant de 1 à 100 g/l.
  24. Concentré aqueux selon la revendication 23, caractérisé en ce qu'il contient chaque fois, en tant qu'agent de précipitation, au moins un cation, un chélate, un complexe, un polyélectrolyte et/ou un polymère, qui forme(nt) des composés peu solubles et/ou insolubles avec les ions sulfate.
  25. Utilisation de corps métalliques revêtus suivant le procédé conforme aux revendications 1 à 22, comme éléments chauffants, corps de chauffe, supports, panneaux, habillages, cornières, composants dans le domaine des parties internes des véhicules ou des avions, composants dans la construction d'appareils et la construction mécanique.
EP03028810A 2002-12-24 2003-12-15 Procédé de revêtement de surfaces métalliques avec une solution de phosphate alcalin, concentré aqueux et utilisation des surfaces métalliques ainsi revêtues Expired - Lifetime EP1433879B1 (fr)

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DE10261014A DE10261014B4 (de) 2002-12-24 2002-12-24 Verfahren zur Beschichtung von Metalloberflächen mit einer Alkaliphosphatierungslösung, wässeriges Konzentrat und Verwendung der derart beschichteten Metalloberflächen
DE10261014 2002-12-24

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KR101500049B1 (ko) 2012-12-27 2015-03-06 주식회사 포스코 아연 또는 아연계합금도금 강판용 인산염 용액 및 이를 이용한 아연 또는 아연계합금도금 강판
EP2907894B2 (fr) 2014-02-13 2025-03-19 Ewald Dörken Ag Procédé de fabrication d'un substrat avec passivation exempte de chrome VI et de cobalt

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US4149909A (en) * 1977-12-30 1979-04-17 Amchem Products, Inc. Iron phosphate accelerator
JPS58181889A (ja) * 1982-04-17 1983-10-24 Nippon Steel Corp 片面亜鉛系電気メツキ鋼板の製造方法
DE3407513A1 (de) * 1984-03-01 1985-09-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur zink-calcium-phosphatierung von metalloberflaechen bei niedriger behandlungstemperatur
DE3631759A1 (de) * 1986-09-18 1988-03-31 Metallgesellschaft Ag Verfahren zum erzeugen von phosphatueberzuegen auf metalloberflaechen
JPH01100281A (ja) * 1987-10-13 1989-04-18 Nippon Parkerizing Co Ltd 金属表面の皮膜化成処理液
DE3906898A1 (de) * 1989-03-03 1990-09-06 Henkel Kgaa Zink-barium-phosphatierung von metalloberflaechen
DE19718891C2 (de) * 1997-05-03 2001-03-15 Kluthe Gmbh Chem Werke Verfahren und Mittel zur Phosphatierung von Aluminiumoberflächen
DE10006338C2 (de) * 2000-02-12 2003-12-04 Chemetall Gmbh Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile

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DE50302176D1 (de) 2006-04-06
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DE10261014A1 (de) 2004-07-15
EP1433879A1 (fr) 2004-06-30

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