EP2318566B1 - Sukzessive korrosionsschützende vorbehandlung von metalloberflächen in einem mehrstufenprozess - Google Patents

Sukzessive korrosionsschützende vorbehandlung von metalloberflächen in einem mehrstufenprozess Download PDF

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Publication number
EP2318566B1
EP2318566B1 EP09781448.7A EP09781448A EP2318566B1 EP 2318566 B1 EP2318566 B1 EP 2318566B1 EP 09781448 A EP09781448 A EP 09781448A EP 2318566 B1 EP2318566 B1 EP 2318566B1
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Prior art keywords
rinse
water
stage
treatment
elements
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EP09781448.7A
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German (de)
English (en)
French (fr)
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EP2318566A1 (de
Inventor
Franz-Adolf Czika
Sophie Cornen
Jens KRÖMER
Michael Frank
Nicole TEUBERT
Jan-Willem Brouwer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL09781448T priority Critical patent/PL2318566T3/pl
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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
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium 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
    • C23C22/05—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
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/77—Controlling or regulating of the coating process
    • 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

Definitions

  • the present invention relates to a method for optimizing the corrosion-protective pretreatment of metal surfaces and to the resource-saving use of rinse water in such a corrosion-protective pretreatment comprising a conversion treatment step with an aqueous composition containing at least 50 ppm of the elements B, Si, Ti, Zr and / or Hf in the form water-soluble compounds at a pH of 3 to 5.5, wherein a minimum proportion of 10 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds in the pre-rinse stage is realized immediately before the actual conversion treatment and a part the aqueous composition of the conversion treatment step is contained in the first post-rinse step.
  • the present invention comprises a metallic component which has been treated according to such a method and its use in a process for applying a multi-layer system, in particular a lacquer system containing an organic binder, in industrial production.
  • a metallic component is suitable for the production of white goods, electronic housings, in the construction and architectural sectors, as well as for the production of bodies in automotive production.
  • Corrosion inhibitors which are an acidic aqueous solution of water-soluble compounds of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds, in particular in the form of fluoro complexes have long been known. They are increasingly used as a replacement for chromating, which are increasingly less used because of the toxicological properties of chromium compounds. As a rule, such contain Solutions of water-soluble compounds of elements B, Si, Ti, Zr and / or Hf further anti-corrosive agents that further improve the corrosion protection and paint adhesion.
  • a common process sequence in the anticorrosive pretreatment is the cleaning and degreasing of the metallic surfaces, followed by one or more rinsing stages with different water quality, before the actual conversion treatment takes place. These in turn are followed by one or more rinsing stages for the removal of adhering to the components components of the conversion treatment solution.
  • the coating follows with the organic binder system, which is typically an electrocoating.
  • Binder systems tolerate only small amounts of foreign ions that are introduced by carryover with the component in the coating. For example, for optimum performance of the organic primary coating in automotive production, it is required that the conductivity in the last rinsing step before the electrodeposition coating does not exceed a value of 30 ⁇ Scm -1 .
  • the German patent application 198 54 431 describes a method for saving rinse water during phosphating.
  • the phosphatizing bath overflow and / or the rinsing water after the phosphating is subjected to a treatment process such as reverse osmosis, ion exchange, nanofiltration, electrodialysis and / or heavy metal precipitation and the water phase depleted in metal ions as rinsing water for rinsing the metal parts to be phosphated their cleaning is used.
  • the German patent application 102 36 293 the object is to return the phosphating solution into the phosphating solution in the cleaning solution and / or in the first rinse water.
  • suitable process management should additionally preferably a further saving of Rinse water are made possible, so that the phosphating can be operated almost wastewater-free.
  • the prior art thus contains numerous suggestions for saving rinsing water and for recycling valuable substances from the rinsing water after phosphating in the phosphating solution.
  • active ingredients of the conversion treatment solution reach the first rinse water or the cleaning solution.
  • German application 10 2007 006 450 a method just for the separation of active components from the rinse water of a corrosion protection pretreatment presented in which water-soluble fluorocomplexes of zirconium are removed via a precipitate with a lime solution from the rinse water and thus freed of active components rinse water is fed back into the rinse water system.
  • a multi-stage corrosion protection process is in the WO 2004/101850 in which one of zinc phosphating containing small amounts of dissolved titanium or zirconium and a subsequent rinse based on hexafluorotitanates and / or hexafluorozirconates is disclosed.
  • the object of the present invention is now to the corrosion-protective effect of an aqueous pretreatment containing the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds at a pH of 3 to 5.5 in a procedure for pretreatment optimize and thereby establish a resource-saving process as possible.
  • Metallic surfaces in the context of the present invention are surfaces of zinc, galvanized and alloy-galvanized steel, aluminum and its alloys, and steel or iron.
  • effective corrosion protection can be achieved with minimal consumption of rinse water.
  • steel and iron surfaces results in the process sequence according to the invention significantly improved corrosion protection compared to a method without cascading the rinse water.
  • Methods are therefore particularly preferred those metal surfaces or joined metallic components, which represent or have at least partially surfaces of steel and / or iron, particularly preferably those which represent or have exclusively surfaces of steel and / or iron.
  • the process sequence associated with the method according to the invention which consists in the fact that the metallic component to be treated passes successively at least the treatment stages (C), (D) and (E), requires in each case one part of the aqueous composition of the respective treatment stage in the respectively following one Treatment level is abducted.
  • This so-called drag-over is based on the fact that the liquid film adhering to the treated metallic component reaches the respective subsequent treatment stage.
  • this transfer of aqueous adhering medium to the next treatment step may vary depending on the shape and nature of the components to be treated.
  • car bodies have complex geometries that tend to carry more treatment than pure breathable water.
  • a carry-over value typical for the pretreatment of automobile bodies is approximately 100 ml of aqueous medium per m 2 of the treated component.
  • the execution of the preferred method according to the invention with cascading recycling of the rinsing water is therefore ensured by a continuous operation of the same process, in which the respective proportions of the aqueous composition of the previous treatment stage are carried off into the respective subsequent one.
  • baths of the treatment stages can also be applied once according to the method according to the invention, so that already during the commissioning of a process chain for anticorrosion pretreatment and in the treatment of a first series of metallic Components that are present technical conditions according to the method according to the invention.
  • the treatment of a first series of metallic components in a process sequence and in a processing as in the method according to the invention can initially be used to delay the respective aqueous compositions of the treatment stages in cascading recycling of the rinse water until all technical parameters of the inventive method with respect Compositions of the treatment steps fulfilled.
  • Such a first series of pretreated components will, as long as the required composition of the treatment stage (C) of the process according to the invention has not yet been achieved, have a poorer corrosion protection, especially on steel and / or iron surfaces.
  • the minimum concentration of active components in the pre-rinse (C) in cascaded operation without carryover by treated metallic components by continuously adding a corresponding amount of water-soluble compounds of the elements B, Si, Ti, Zr and / or Hf to preset either to the last pre-rinse (C) and the first Vietnamese Meetingtret (E) or exclusively to the first Nachêtmaschinench (E).
  • treatment step for the application of an aqueous composition to a metallic component for a defined technical purpose.
  • the upstream treatment stages serve the degreasing and cleaning of the components as well as the liberation of residues from the purification stage and the conventional conversion treatment (D) preparatory treatment in the pre-rinse (C).
  • the treatment stages downstream of the conventional conversion treatment which effect a post-treatment in the first post-rinse (E) and at the same time the release of the metal surface from residues from the conversion treatment.
  • each treatment stage can independently of one another have one of these two types of application.
  • a method according to the invention is preferred in which the metallic component is brought into contact with the respective aqueous compositions in all the treatment stages in the dipping process.
  • the cascading recycling of aqueous medium from the last rinsing stage to the first rinsing stage carried out in the preferred process according to the invention involves the discharge of a portion of the aqueous medium from the respective treatment stage into the respective treatment stage upstream of the process sequence, but the treatment stage (D) containing the composition (1) is excluded from cascading for a conventional conversion treatment.
  • the cascading according to the invention therefore relates only to rinse water with different composition and function. In the treatment stage (D) so no rinse water is actively fed.
  • An optional feed of aqueous composition (1) from the treatment stage (D) into the pre-rinse stage (C) merely serves to adapt and maintain the concentration of the active components in the pre-rinse stage according to the invention, in particular when the method according to the invention is put into operation.
  • Cascading in contrast to the unavoidable drag-over of liquid parts according to process sequence (A) to (F), is a special technical measure for active recycling of volumes from the Vietnamese Singhstinum in the Vor Hughesworkn thus opposite to the process sequence according to the invention.
  • such a cascaded recycling of aqueous medium from the last rinsing stage to the first rinsing stage is preferred, which takes place continuously and in particular with a constant volume flow.
  • the rinsing water recirculated via the cascading, which accumulates in the first rinsing stage, can preferably either be discharged into the sewage system by means of an overflow or be treated from the overflow by means of upstream ultrafiltration and subsequent ion exchange and / or reverse osmosis and fed back into the final rinsing stage , so that there is a closed rinse water cycle for this case.
  • An advantage of the preferred method according to the invention is therefore that due to the cascading recycling of rinse water from the last rinse stage in the first rinse stage less wastewater discharged from the individual treatment stages for metal surface treatment and correspondingly less fresh water must be supplied. This saves resources and increases profitability.
  • a content of conversion treatment solution which is built up by carryover and cascaded recycling mainly in the first post-rinse step (E) and the pre-rinse step (C), has an advantageous effect on the formation of the conversion coating, so that both the anti-corrosive effect and the paint adhesion, especially on steel and / or iron surfaces, are significantly improved.
  • a total of at least 20 ppm, preferably at least 50 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds in the pre-rinse step (C) are included.
  • this can be achieved by correspondingly setting the cascaded recycling of rinsing water while at the same time carrying over parts of the conversion treatment solution into the final rinsing stages. If the content of elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds is less than 10 ppm, no improvement in the corrosion properties of the treated metallic components can be ascertained and only considerable amounts of rinsing water can be saved.
  • the anticorrosive effect achieved in the process according to the invention is significantly improved over a process sequence which requires only the cascading recycle to the first post-rinse step (E. ) completes.
  • the proportion of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds in the pre-rinsing step (C) is not more than 20%, preferably not more than 10% based on the proportion of the respective Elements in the conversion treatment step (D), since otherwise the tendency for sludge formation in the rinsing step (C) is increased, which must be counteracted with other technical measures, these by no significant improvement in the corrosion protection and in the paint adhesion of the treated in the process according to the invention metallic components would be justified.
  • the content of active components consisting of the constituents of the aqueous composition (1) of treatment stage (D) in the first post-rinse stage (E) in the process according to the invention due to the continuous carryover of conversion treatment solution by means of the treated metallic components and the concurrent cascading recycling of rinse water this Nachêtstistististi (E) at least equal to the content of these active components in the last pre-rinse (C). Due to the tendentially higher pH values in the last pre-rinse step (C), the proportion of water-soluble However, compounds of elements B, Si, Ti, Zr and / or Hf are usually somewhat lower than in the first post-rinse step (E).
  • the higher pH values in the last pre-rinse step (C), which tend to be higher than the first post-rinse step, are due to the carry-over of components of the cleaning and degreasing stage, which preferably consists of an alkaline cleaner system.
  • components of the acidic aqueous composition (1) are mainly carried off into the first post-rinse stage (E).
  • the aqueous composition of the conversion treatment step (D) preferably contains more than 100 ppm, more preferably totally more than 400 ppm, but preferably not more than 1500 ppm, more preferably not more than altogether, for a faster and more effective corrosion-protecting conversion of the metal surface 1000 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds.
  • insoluble metal hydroxides from the recirculating medium of the post-rinse steps thus allows a precise adjustment of the proportion of elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds in the pre-rinse step (C).
  • aqueous compositions (1) with a proportion of fluorine bound in the form of fluorocomplexes of the elements B, Si, Ti, Zr and / or Hf or in excess and unbound in the form of free fluoride are used.
  • a proportion of fluorine in excess and unbound in the form of free fluoride means that more fluoride ions are contained in the solutions than are needed to complex the elements B, Si, Ti, Zr and / or Hf.
  • fluorine-containing water-soluble compounds of the elements B, Si, Ti, Zr and / or Hf exerts an increased pickling attack on the metallic component, which results in a faster and more complete conversion of the metal surface.
  • aqueous compositions of the pre-rinse stage and the first rinse stage for which a sufficient stability of the elements B, Si, Ti, Zr and / or Hf in the form water-soluble compounds containing respective composition of the rinsing step and an optimal corrosion protection treatment of the metallic components is given.
  • a pH range of 5.0 to 7.0, preferably 5.8 to 6.2 while in the final rinse step (E) preferably in the range of 4.0 and 5, 5 and in particular in the range of 4.8 and 5.2.
  • Higher alkalinity in the rinsing steps either cause the precipitation of hydroxides of the heavy metals, which are entrained during the treatment of the metallic component according to the invention in the rinsing stages, such as iron, or cause the active components in the form of the water-soluble compounds of the elements B, Si , Ti, Zr and / or Hf are partly or completely precipitated with and are thus no longer available in the process according to the invention.
  • the separation of the precipitated sludge from the rinse water is possible with conventional techniques such as filtration or centrifugation and sedimentation methods. For example, bag or gravel filters can be used for this purpose.
  • the aqueous solution of Ca (OH) 2 for complete precipitation of the heavy metals and the active components in step a) contains from 0.001 to 0.14% by weight of Ca (OH) 2 .
  • This concentration range is particularly favorable in order to comply with the inventively sought limits of pH and electrical conductivity in the portion of the recirculating rinse water from the Nach Hughespad (E), which is not fed back directly into the pre-rinse (C) at pH-controlled automatic dosing.
  • insoluble heavy metal hydroxides and active components from a portion of the recirculating rinse water of the rinse steps allows by a vote of the respective portions of the returned rinse water, which are fed back directly or indirectly in the pre-rinsing (C), a precise adjustment of the proportion of elements B, Si , Ti, Zr and / or Hf in the form of water-soluble compounds in the pre-rinse step (C) to the preferred maximum values of not more than 20%, in particular not more than 10% based on the proportion of each element in the conversion treatment step (D).
  • the process chain P1 simulates a stationary state of the method according to the invention with cascading recycling of rinsing water.
  • the process chain P2 simulates a stationary state of an overrun first rinsing stage (E) without cascading return to the pre-rinsing stages, in which just as much active components are removed in the overflow per time interval as are introduced by carryover per time interval, the proportion of water-soluble compounds of the Elements B, Si, Ti, Zr and / or Hf in the Nachêtch (E) is negligible.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP09781448.7A 2008-08-12 2009-08-04 Sukzessive korrosionsschützende vorbehandlung von metalloberflächen in einem mehrstufenprozess Active EP2318566B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09781448T PL2318566T3 (pl) 2008-08-12 2009-08-04 Sukcesywna, przed korozją chroniąca obróbka wstępna powierzchni metalowych w procesie wielostopniowym

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008038653A DE102008038653A1 (de) 2008-08-12 2008-08-12 Sukzessive korrosionsschützende Vorbehandlung von Metalloberflächen in einem Mehrstufenprozess
PCT/EP2009/060063 WO2010018102A1 (de) 2008-08-12 2009-08-04 Sukzessive korrosionsschützende vorbehandlung von metalloberflächen in einem mehrstufenprozess

Publications (2)

Publication Number Publication Date
EP2318566A1 EP2318566A1 (de) 2011-05-11
EP2318566B1 true EP2318566B1 (de) 2015-03-18

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Country Link
US (1) US8679586B2 (es)
EP (1) EP2318566B1 (es)
CN (1) CN102124144B (es)
BR (1) BRPI0914553B1 (es)
CA (1) CA2733977C (es)
DE (1) DE102008038653A1 (es)
ES (1) ES2539576T3 (es)
HU (1) HUE026110T2 (es)
PL (1) PL2318566T3 (es)
WO (1) WO2010018102A1 (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009029334A1 (de) * 2009-09-10 2011-03-24 Henkel Ag & Co. Kgaa Zweistufiges Verfahren zur korrosionsschützenden Behandlung von Metalloberflächen
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CN102124144B (zh) 2014-08-06
DE102008038653A1 (de) 2010-03-25
CA2733977C (en) 2016-06-28
EP2318566A1 (de) 2011-05-11
BRPI0914553B1 (pt) 2019-05-14
CN102124144A (zh) 2011-07-13
WO2010018102A1 (de) 2010-02-18
US20110189401A1 (en) 2011-08-04
PL2318566T3 (pl) 2015-08-31
HUE026110T2 (en) 2016-05-30
CA2733977A1 (en) 2010-02-18
ES2539576T3 (es) 2015-07-02
BRPI0914553A2 (pt) 2015-12-15
US8679586B2 (en) 2014-03-25

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