EP2318566B1 - Successive corrosion-protecting pre-treatment of metal surfaces in a multi-step process - Google Patents
Successive corrosion-protecting pre-treatment of metal surfaces in a multi-step process Download PDFInfo
- 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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- European Patent Office
- Prior art keywords
- rinse
- water
- stage
- treatment
- elements
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- 238000002203 pretreatment Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 92
- 229910052726 zirconium Inorganic materials 0.000 claims description 54
- 229910052796 boron Inorganic materials 0.000 claims description 50
- 229910052719 titanium Inorganic materials 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 48
- 229910052710 silicon Inorganic materials 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000002609 medium Substances 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 239000012736 aqueous medium Substances 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000003134 recirculating effect Effects 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 6
- 239000010936 titanium Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 25
- 230000007797 corrosion Effects 0.000 description 21
- 238000005260 corrosion Methods 0.000 description 21
- 238000004064 recycling Methods 0.000 description 21
- 239000008237 rinsing water Substances 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- -1 iron ions Chemical class 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
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- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
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- 239000011230 binding agent Substances 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
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- 238000007598 dipping method Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GAAKALASJNGQKD-UHFFFAOYSA-N LY-165163 Chemical compound C1=CC(N)=CC=C1CCN1CCN(C=2C=C(C=CC=2)C(F)(F)F)CC1 GAAKALASJNGQKD-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
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- 150000001845 chromium compounds Chemical class 0.000 description 1
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- 230000008595 infiltration Effects 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000000108 ultra-filtration Methods 0.000 description 1
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- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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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Description
Die vorliegende Erfindung betrifft ein Verfahren zur Optimierung der korrosionsschützenden Vorbehandlung von Metalloberflächen sowie zum ressourcenschonenden Einsatz von Spülwasser in einer solchen korrosionsschützenden Vorbehandlung umfassend eine Konversionsbehandlungsstufe mit einer wässrigen Zusammensetzung enthaltend zumindest 50 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen bei einem pH-Wert von 3 bis 5,5, wobei ein Mindestanteil von 10 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen in der Vorspülstufe unmittelbar vor der eigentlichen Konversionsbehandlung realisiert ist und ein Teil der wässrigen Zusammensetzung der Konversionsbehandlungsstufe in der ersten Nachspülstufe enthalten ist. Der ressourcenschonende Einsatz des Spülwassers wird erfindungsgemäß über eine kaskadierende Rückführung von Spülwasser aus der letzten Spülstufe bis in die erste Spülstufe realisiert. Des Weiteren umfasst die vorliegende Erfindung ein metallisches Bauteil, das gemäß einem solchen Verfahren behandelt wurde und dessen Verwendung in einem Prozess zur Auftragung eines Mehrschichtensystems, insbesondere eines Lacksystems enthaltend ein organisches Bindemittel, in der industriellen Fertigung. Ebenso eignet sich ein solches metallisches Bauteil für die Herstellung von Weißer Ware, elektronischen Gehäusen, im Baugewerbe und Architekturbereich, sowie für die Herstellung von Karosserien in der automobilen Fertigung.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 resource-saving use of the rinse water is realized according to the invention via a cascading recycling of rinse water from the last rinse stage to the first rinse stage. Furthermore, 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. Likewise, such 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.
Korrosionsschutzmittel, die eine saure wässrige Lösung von wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen, insbesondere in Form von Fluorokomplexen darstellen, sind seit langem bekannt. Sie werden zunehmend als Ersatz für Chromatierverfahren eingesetzt, die wegen der toxikologischen Eigenschaften von Chromverbindungen zunehmend weniger verwendet werden. In der Regel enthalten derartige Lösungen von wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf weitere korrosionsschützende Wirkstoffe, die die Korrosionsschutzwirkung und Lackhaftung weiter verbessern.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.
Auf dem für die vorliegende Erfindung besonders relevanten Gebiet der automobilen Fertigung werden im zunehmenden Maße verschiedene metallische Werkstoffe eingesetzt und in Verbundstrukturen zusammengefügt. Im Karosseriebau werden dabei nach wie vor überwiegend verschiedenste Stähle wegen ihrer spezifischen Materialeigenschaften verwendet, aber auch zunehmend Leichtmetalle, die für eine erhebliche Gewichtsreduzierung der gesamten Karosserie besonders bedeutend sind. Um dieser Entwicklung Rechnung zu tragen, gilt es Verfahren für die Applikation dieser chromfreien Vorbehandlungslösungen speziell für den Karosserieschutz zu entwickeln oder bestehende Verfahren weiter zu entwickeln.In the field of automotive production, which is particularly relevant to the present invention, various metallic materials are increasingly being used and joined together in composite structures. In body construction, a wide variety of steels are still used because of their specific material properties, but also increasingly light metals, which are particularly significant for a significant weight reduction of the entire body. In order to take this development into account, it is necessary to develop methods for the application of these chromium-free pretreatment solutions especially for the body protection or to further develop existing processes.
Eine übliche Verfahrensabfolge in der korrosionsschützenden Vorbehandlung besteht in der Reinigung und Entfettung der metallischen Oberflächen, der eine oder mehrere Spülstufen mit unterschiedlicher Wasserqualität folgen, bevor die eigentliche Konversionsbehandlung erfolgt. Dieser wiederum sind eine oder mehrere Spülstufen nachgeschaltet zur Entfernung von auf den Bauteilen anhaftenden Bestandteilen der Konversionsbehandlungslösung. Nach dem letzten Spülschritt, der grundsätzlich mit vollentsalztem Wasser (κ < 5 µScm-1) gespeist wird, folgt die Beschichtung mit dem organischen Bindemittelsystem, die typischerweise eine Elektrotauchlackierung darstellt.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. After the last rinsing step, which is basically fed with demineralized water (κ <5 μScm -1 ), the coating follows with the organic binder system, which is typically an electrocoating.
Im Vordergrund steht bei diesen Verfahren stets ein ressourcenschonender Umgang sowohl mit der Vorbehandlungslösung als auch mit dem Spülwasser, das für die Entfernung von löslichen Rückständen der Vorbehandlungslösung auf der behandelten Oberfläche benötigt wird, bei gleichzeitig hohen Qualitätsanforderungen an die korrosionsschützende Vorbehandlung. Die Spülwasserreinigung der metallischen Bauteile ist insbesonders für die nachfolgende Beschichtung mit dem organischen Bindemittelsystem essentiell. Die organischen Bindemittelsysteme tolerieren lediglich geringe Mengen an Fremdionen, die durch Verschleppung mit dem Bauteil in das Beschichtungsbad eingetragen werden. Beispielsweise wird für eine optimale Performance der organischen Erstbeschichtung in der automobilen Fertigung verlangt, dass die Leitfähigkeit im letzten Spülschritt vor der Elektrotauchlackierung einen Wert von 30 µScm-1 nicht überschreitet. Dies erfordert die kontinuierliche Einspeisung von vollentsalztem Wasser in die Spülstufen der Vorbehandlung, wobei ein wirtschaftliches und ökologisches Interesse darin besteht, diese Einspeisung zu minimieren und gleichzeitig die damit verbundenen Risiken für eine ständige Betriebsfähigkeit der Anlage und für eine Gewährleistung einer gleich bleibenden hohen Qualität der korrosionsschützenden Konversionsbehandlung kontrollierbar zu gestalten.At the forefront of these processes is always a resource-friendly handling both with the pretreatment solution and with the rinse water, which is required for the removal of soluble residues of the pretreatment solution on the treated surface, at the same time high quality requirements for the anticorrosion pretreatment. The rinsing water purification of the metallic components is essential in particular for the subsequent coating with the organic binder system. The organic ones 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 μScm -1 . This requires the continuous feeding of demineralised water into the pretreatment rinsing stages, with an economic and ecological interest in minimizing this feed-in, and at the same time the associated risks to the plant's continued operability and to ensuring a consistently high quality of the anti-corrosive Conversion treatment to make controllable.
Dem Fachmann im Bereich der korrosionsschützenden Phosphatierung sind verschiedene Strategien zum Spülwassermanagement bekannt, die zum einen die Einsparung von vollentsalztem Wasser und zum anderen die Wertstoffrückgewinnung aus in die Spülstufen verschleppten Anteilen der Phosphatierlösung betreffen.The expert in the field of anti-corrosive phosphating various strategies for flushing water management are known, on the one hand, the saving of demineralized water and on the other hand, the recovery of recyclables from entrained into the rinsing stages portions of the phosphating.
Die deutsche Patentanmeldung
Die deutsche Patentanmeldung
Die Rückgewinnung von entionisiertem und von Schwermetallionen befreitem Spülwasser für Spülwassersysteme mit kaskadierter Rückführung von Spülwasser aus der letzten in die erste Spülstufe ist ebenfalls in der deutschen Anmeldung
Der Stand der Technik enthält also zahlreiche Anregungen zum Einsparen von Spülwasser und zum Rückführen von Wertstoffen aus dem Spülwasser nach der Phosphatierung in die Phosphatierungslösung. Durch allgemeine Verschleppung während des praktischen Betriebs und insbesondere durch die kaskadenartige Überführung von Spülwasser aus nachfolgenden Spülstufen in vorgelagerte Spülstufen und bis in die Reinigungslösung gelangen jedoch Wirkstoffe der Konversionsbehandlungslösung bis in das erste Spülwasser oder bis in die Reinigungslösung.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. However, due to general carry-over during practical operation and in particular due to the cascading transfer of rinsing water from subsequent rinsing stages into upstream rinsing stages and into the cleaning solution, active ingredients of the conversion treatment solution reach the first rinse water or the cleaning solution.
Bezüglich der nicht-kristallinen Konversionsschichtbildung, beispielsweise in chromfreien Behandlungslösungen basierend auf wasserlösliche Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf, sind derartige Verfahren mit kaskadierter Rückführung von Spülwasser weder erprobt noch hinsichtlich des Einflusses von Wirkkomponenten im Spülwasser auf die Schichtqualität untersucht worden.
Aus der wissenschaftlichen Veröffentlichung von Stromberg et. al in der
Konsequenterweise wird in der deutschen Anmeldung
From the scientific publication by Stromberg et. al in the
Consequently, in the German application
Ein mehrstufiges korrosionsschützendes Verfahren ist in der
Die Aufgabe der vorliegenden Erfindung besteht nunmehr darin, die korrosionsschützende Wirkung einer wässrigen Vorbehandlung enthaltend die Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen bei einem pH-Wert von 3 bis 5,5 in einem Verfahrensablauf zur Vorbehandlung zu optimieren und dabei ein möglichst ressourcenschonendes Verfahren zu etablieren.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.
Überraschenderweise wurde gefunden, dass in einem Verfahren zur korrosionsschützenden Vorbehandlung von Metalloberflächen umfassend eine Konversionsbehandlungsstufe (D) mit einer wässrigen Zusammensetzung (1) enthaltend insgesamt zumindest 50 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen bei einem pH-Wert von 3 bis 5,5 ein optimierter Korrosionsschutz erzielt wird, wenn die metallische Oberfläche nacheinander zumindest folgende Behandlungsstufen durchläuft:
- (C) Vorspüle mit Wasser enthaltend insgesamt zumindest 10 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen
- (D) Konversionsbehandlung mit der wässrigen Zusammensetzung (1)
- (E) Nachspüle mit Wasser enthaltend einen Teil der wässrigen Zusammensetzung (1) der Behandlungsstufe (D)
- (C) pre-rinsing with water containing in total at least 10 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds
- (D) Conversion treatment with the aqueous composition (1)
- (E) rinsing with water containing part of the aqueous composition (1) of treatment stage (D)
Des Weiteren kann das erfindungsgemäße Verfahren in einer bevorzugten Verfahrensabfolge, die zusätzlich einen minimiertem Einsatz von Spülwasser gewährleistet, derart durchgeführt werden, dass das Spülwasser aus der letzten Spülstufe in die erste Spülstufe zurückkaskadiert wird, wobei sich aufgrund der Verschleppung von Teilen der wässrigen Zusammensetzung (1) in die nachfolgenden Spülstufen bei gleichzeitiger kaskadenartiger Rückführung von Spülwasser in die Vorspülstufen ein stationärer Zustand bezüglich der Konzentration der Wirkkomponenten in den Nach- und Vorspülstufen einstellt. Ein solche Kaskadierung ist derart einzustellen, dass im stationären Zustand in der Vorspülstufe (C) die erfindungsgemäße Konzentration an Wirkkomponenten von nicht weniger als 10 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen realisiert wird.
Daher umfasst die vorliegende Erfindung in einer bevorzugten Ausführungsform ein Verfahren zur korrosionsschützenden Vorbehandlung von Metalloberflächen in einer Verfahrensabfolge umfassend eine Konversionsbehandlungsstufe (D) mit einer wässrigen Zusammensetzung (1) enthaltend insgesamt zumindest 50 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen bei einem pH-Wert von 3 bis 5,5, wobei die wässrige Zusammensetzung (1) der Konversionsbehandlungsstufe (D) einen Anteil an Fluor gebunden in Form von Fluorokomplexen der Elemente B, Si, Ti, Zr und/oder Hf oder im Überschuss und ungebunden in Form von freiem Fluorid enthält, dadurch gekennzeichnet, dass die metallische Oberfläche nacheinander folgende Behandlungsstufen durchläuft:
- (A) ggf. Entfettung- und Reinigung
- (B) ggf. Spüle mit Brauchwasser enthaltend ggf. einen Teil der wässrigen Zusammensetzung der Entfettungs- und Reinigungsstufe (A)
- (C) Vorspüle mit Wasser mit einem pH-Wert von 5 bis 7,0 enthaltend insgesamt zumindest 10 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen und ggf. einen Teil der wässrigen Zusammensetzung der Spülstufe (B)
- (D) Konversionsbehandlung mit der wässrigen Zusammensetzung (1) enthaltend einen Teil der wässrigen Zusammensetzung der Vorspülstufe (C)
- (E) erste Nachspüle mit Wasser enthaltend einen Teil der wässrigen Zusammensetzung der Behandlungsstufe (D)
- (F) ggf. zweite Nachspüle mit Wasser enthaltend einen Teil der wässrigen Zusammensetzung der Nachspülstufe (E),
Therefore, in a preferred embodiment, the present invention comprises a process for the corrosion-protective pretreatment of metal surfaces in a process sequence comprising a conversion treatment step (D) with an aqueous composition (1) containing in total at least 50 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds at a pH of from 3 to 5.5, wherein the aqueous composition (1) of the conversion treatment step (D) contains a proportion of fluorine bound in the form of fluorocomplexes of elements B, Si, Ti, Zr and / or Hf or in excess and contains unbound in the form of free fluoride, characterized in that the metallic surface successively passes through the following treatment steps:
- (A) if necessary degreasing and cleaning
- (B) if necessary, rinse with hot water containing possibly a part of the aqueous composition of the degreasing and cleaning stage (A)
- (C) pre-rinsing with water having a pH of 5 to 7.0, containing in total at least 10 ppm of the elements B, Si, Ti, Zr and / or Hf in the form of water-soluble compounds and optionally a part of the aqueous composition of the rinsing step ( B)
- (D) Conversion treatment with the aqueous composition (1) containing a part of the aqueous composition of the pre-rinse step (C)
- (E) first rinse with water containing part of the aqueous composition of treatment stage (D)
- (F) optionally second rinsing with water containing a part of the aqueous composition of the rinsing step (E),
Metallische Oberflächen im Sinne der vorliegenden Erfindung sind Oberflächen von Zink, verzinktem und legierungsverzinktem Stahl, Aluminium und seinen Legierungen sowie Stahl oder Eisen. Für diese metallischen Oberflächen oder metallischen Bauteile, die aus diesen Materialien zusammengefügt sind, kann ein wirksamer Korrosionsschutz bei minimalem Verbrauch an Spülwasser erzielt werden. Insbesondere für Stahl- und Eisenoberflächen resultiert in der erfindungsgemäßen Verfahrensabfolge ein signifikant verbesserter Korrosionsschutz gegenüber einem Verfahren ohne Kaskadierung des Spülwassers. Im erfindungsgemäßen Verfahren sind daher insbesondere solche Metalloberflächen oder zusammengefügte metallische Bauteile bevorzugt, die zumindest teilweise Oberflächen von Stahl und/oder Eisen darstellen oder aufweisen, besonders bevorzugt solche die ausschließlich Oberflächen von Stahl und/oder Eisen darstellen oder aufweisen.
Die mit dem erfindungsgemäßen Verfahren verbundene Verfahrensabfolge, die darin besteht, dass das zu behandelnde metallische Bauteil nacheinander zumindest die Behandlungsstufen (C), (D) und (E) passiert, bedingt das jeweils ein Teil der wässrigen Zusammensetzung der jeweiligen Behandlungsstufe in die jeweils nachfolgende Behandlungsstufe verschleppt wird. Diese sogenannte Verschleppung ("drag-over") beruht darauf, dass der an dem behandelten metallischen Bauteil anhaftende Flüssigkeitsfilm in die jeweils nachfolgende Behandlungsstufe gelangt. Dieser Übertrag von wässrigem anhaftendem Medium in die jeweils nächste Behandlungsstufe kann jedoch in Abhängigkeit von der Form und Art der zu behandelnden Bauteile variieren. So weisen Automobilkarosserien zusätzlich komplexe Geometrien auf, die tendenziell mehr Behandlungslösung verschleppen als es durch reines Haftwasser der Fall ist. Allgemein spricht der Fachmann, der eine solche Prozesskette betreut und die jeweiligen Badparameter kontrolliert, von stark und schwach schöpfenden Bauteilen. Ein für die Vorbehandlung von Automobilkarosserien typischer Wert für die Verschleppung liegt bei ca. 100 ml an wässrigem Medium pro m2 des behandelten Bauteils.
Die Ausführung des bevorzugten erfindungsgemäßen Verfahrens mit kaskadierender Rückführung des Spülwassers wird also durch einen kontinuierlichen Betrieb desselben Verfahrens gewährleistet, bei dem die jeweiligen Anteile der wässrigen Zusammensetzung der vorausgegangenen Behandlungsstufe in die jeweils nachfolgende verschleppt werden. Selbstverständlich können die Bäder der Behandlungsstufen auch entsprechend dem erfindungsgemäßen Verfahren einmalig angesetzt werden, so dass bereits bei der Inbetriebnahme einer Prozesskette zur korrosionsschützenden Vorbehandlung und bei der Behandlung einer ersten Serie von metallischen Bauteilen, die technischen Bedingungen entsprechend des erfindungsgemäßen Verfahrens vorliegen.
Ebenso kann die Behandlung einer ersten Serie von metallischen Bauteilen in einer Verfahrensabfolge und bei einer Prozessierung wie im erfindungsgemäßen Verfahren zunächst dazu genutzt werden, die jeweiligen wässrigen Zusammensetzungen der Behandlungsstufen bei kaskadierender Rückführung des Spülwassers soweit zu verschleppen, bis sämtliche technischen Parameter des erfindungsgemäßen Verfahrens bezüglich der Zusammensetzungen der Behandlungsstufen erfüllt vorliegen. Eine solche erste Serie an vorbehandelten Bauteilen wird solange die erforderliche Zusammensetzung der Behandlungsstufe (C) des erfindungsgemäßen Verfahrens noch nicht erreicht ist, einen schlechteren Korrosionsschutz, insbesondere auf Stahl- und/oder Eisenoberflächen aufweisen. Grundsätzlich ist es für die Ausführung des erfindungsgemäßen Verfahrens von Vorteil bereits vor der Behandlung einer ersten Serie von Bauteilen die Mindestkonzentration an Wirkkomponenten in der Vorspüle (C) im kaskadierenden Betrieb ohne Verschleppung durch behandelte metallische Bauteile mittels kontinuierlicher Zugabe einer entsprechenden Menge an wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf entweder zur letzten Vorspülstufe (C) und ersten Nachspülstufe (E) oder ausschließlich zur ersten Nachspülstufe (E) voreinzustellen. Im erfindungsgemäßen Betrieb ist dann lediglich der Anteil der Wirkkomponenten in der Vorspülstufe (C) zu kontrollieren und ggf. durch Anpassung der Zudosierung einer Zusammensetzung entsprechend der Konversionsbehandlungsstufe (D) wie zuvor beschrieben vorzunehmen. Im Regelfall wird aufgrund der zusätzlich eintretenden Verschleppung von Konversionsbehandlungslösung die erfindungsgemäße Konzentration der Wirkkomponenten in der Spülstufe (C) jedoch erreicht.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. For these metallic surfaces or metallic components assembled from these materials, effective corrosion protection can be achieved with minimal consumption of rinse water. In particular for 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. In the invention 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. However, 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. In addition, car bodies have complex geometries that tend to carry more treatment than pure breathable water. In general, the person skilled in the art, who supervises such a process chain and controls the respective bath parameters, speaks of strong and weakly scooping components. 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. Of course, the 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.
Likewise, 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. In principle, it is advantageous for the execution of the method according to the invention before the treatment of a first series of components, 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 Nachspülstufe (E) or exclusively to the first Nachspülstufe (E). In the operation according to the invention, only the proportion of the active components in the pre-rinsing stage (C) is then to be controlled and, if appropriate, adjusted by adjusting the metered addition of a composition corresponding to the conversion treatment stage (D) as described above. As a rule, however, due to the additionally occurring carryover of conversion treatment solution, the concentration of the active components according to the invention in the rinsing stage (C) is achieved.
Unter Behandlungsstufe ist gemäß der vorliegenden Erfindung im weitesten Sinne ein Verfahrensschritt zur Applikation einer wässrigen Zusammensetzung auf ein metallisches Bauteil für einen definierten technischen Zweck zu verstehen. Während in der Behandlungsstufe (D) die konventionelle Konversionsbehandlung enthaltend als Wirkkomponenten wasserlösliche Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf erfolgt, so dienen die vorgeschalteten Behandlungsstufen der Entfettung und Reinigung der Bauteile sowie der Befreiung von Rückständen aus der Reinigungsstufe und einer die konventionelle Konversionsbehandlung (D) vorbereitenden Behandlung in der Vorspüle (C). Ähnliches gilt für die der konventionellen Konversionsbehandlung nachgeschalteten Behandlungsstufen, die eine nachbereitende Behandlung in der ersten Nachspüle (E) und gleichzeitig die Befreiung der Metalloberfläche von Rückständen aus der Konversionsbehandlung bewirken.
In den jeweiligen Behandlungsstufen ist dabei die Applikation im Tauch- oder Spritzverfahren bevorzugt, wobei jede Behandlungsstufe unabhängig voneinander eine dieser beiden Applikationsarten aufweisen kann. Insbesondere ist jedoch ein erfindungsgemäßes Verfahren bevorzugt, in dem das metallische Bauteil in sämtlichen Behandlungsstufen im Tauchverfahren mit den jeweiligen wässrigen Zusammensetzungen in Kontakt gebracht wird.Under treatment step is to be understood according to the present invention in the broadest sense, a process step for the application of an aqueous composition to a metallic component for a defined technical purpose. While in the treatment step (D) the conventional conversion treatment containing as active components water-soluble compounds of the elements B, Si, Ti, Zr and / or Hf takes place, 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 same applies to 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.
In the respective treatment stages, the application in the dipping or spraying method is preferred, wherein each treatment stage can independently of one another have one of these two types of application. In particular, however, 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.
Die im bevorzugten erfindungsgemäßen Verfahren vorgenommene kaskadierende Rückführung von wässrigem Medium von der letzten Spülstufe in die erste Spülstufe beinhaltet das Ausspeisen eines Teils des wässrigen Mediums aus der jeweiligen Behandlungsstufe in die jeweils entsprechend der Verfahrensfolge vorgeschaltete Behandlungsstufe, wobei jedoch die Behandlungsstufe (D) enthaltend die Zusammensetzung (1) für eine konventionelle Konversionsbehandlung von der Kaskadierung ausgenommen ist. Die Kaskadierung betrifft demnach erfindungsgemäß lediglich Spülwasser mit unterschiedlicher Zusammensetzung und Funktion. In die Behandlungsstufe (D) wird also kein Spülwasser aktiv eingespeist. Eine gegebenenfalls vorgenommene Ausspeisung von wässriger Zusammensetzung (1) aus der Behandlungsstufe (D) in die Vorspülstufe (C) dient lediglich der Anpassung und Einhaltung der erfindungsgemäßen Konzentration der Wirkkomponenten in der Vorspülstufe, insbesondere bei Inbetriebnahme des erfindungsgemäßen Verfahrens. Die Kaskadierung ist im Gegensatz zur unvermeidbaren Verschleppung ("drag over") von Flüssigkeitsteilen gemäß der Verfahrensabfolge (A) bis (F) eine spezielle technische Maßnahme zur aktiven Rückführung von Volumina von den Nachspülstufen in die Vorspülstufen also entgegengesetzt zur erfindungsgemäßen Verfahrensabfolge.
Für das erfindungsgemäße Verfahren ist eine solche kaskadierte Rückführung von wässrigem Medium von der letzten Spülstufe bis zur ersten Spülstufe bevorzugt, die kontinuierlich und insbesondere mit einem konstanten Volumenstrom erfolgt.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 Nachspülstufen in the Vorspülstufen thus opposite to the process sequence according to the invention.
For the method 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.
Das über die Kaskadierung zurückgeführte Spülwasser, das in der ersten Spülstufe aufläuft, kann vorzugsweise entweder wiederum über die Einrichtung eines Überlaufs in das Abwassersystem abgegeben werden oder aus dem Überlauf mittels vorgeschalteter Ultrafiltration und nachfolgendem lonenaustauscherverfahren und/oder Umkehrosmose aufbereitet und in die letzte Spülstufe zurückgespeist werden, so dass für diesen Fall ein geschlossener Spülwasserkreislauf vorliegt.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.
Ein Vorteil des bevorzugten erfindungsgemäßen Verfahrens besteht also darin, dass aufgrund der kaskadierenden Rückführung von Spülwasser von der letzten Spülstufe in die erste Spülstufe weniger Abwasser aus den einzelnen Behandlungsstufen zur Metalloberflächenbehandlung ausgeschleust und entsprechend weniger Frischwasser zugeführt werden muss. Dies schont Ressourcen und erhöht die Wirtschaftlichkeit.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.
Gemäß der vorliegenden Erfindung zeigt sich zudem überraschenderweise, dass sich ein Gehalt an Konversionsbehandlungslösung, der durch Verschleppung und kaskadierter Rückführung vornehmlich in der ersten Nachspülstufe (E) und der Vorspülstufe (C) aufgebaut wird, vorteilhaft auf die Ausbildung der Konversionsbeschichtung ausübt, so dass sowohl die korrosionsschützende Wirkung als auch die Lackhaftung, insbesondere auf Stahl- und/oder Eisenoberflächen, deutlich verbessert werden.In addition, according to the present invention, it is surprisingly found that 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.
Hierfür ist es bevorzugt, dass im erfindungsgemäßen Verfahren insgesamt zumindest 20 ppm, vorzugsweise zumindest 50 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen in der Vorspülstufe (C) enthalten sind. Dies kann wie bereits zuvor erwähnt, dadurch erzielt werden, dass die kaskadierte Rückführung von Spülwasser bei gleichzeitig vorliegender Verschleppung von Teilen der Konversionsbehandlungslösung in die Nachspülstufen entsprechend eingestellt ist. Liegt der Gehalt an Elementen B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen insgesamt unterhalb von 10 ppm ist keine Verbesserung der Korrosionseigenschaften der behandelten metallischen Bauteile feststellbar und lediglich die Einsparung erheblicher Mengen an Spülwasser zu verzeichnen. Oberhalb eines Gehaltes von insgesamt 20 ppm bezogen auf die zuvor genannten Elemente, und insbesondere oberhalb von insgesamt 50 ppm ist die korrosionsschützende Wirkung, die im erfindungsgemäßen Verfahren erreicht wird, erheblich verbessert gegenüber einer Verfahrensabfolge, die lediglich die kaskadierende Rückführung bis zur ersten Nachspülstufe (E) vollzieht.For this purpose it is preferred that in the process according to the invention 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. As already mentioned above, 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. Above a total content of 20 ppm based on the aforementioned elements, and in particular above a total of 50 ppm, 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.
Wiederum ist es bevorzugt, dass der Anteil der Elemente B, Si, Ti, Zr und/oder Hf in Form von wasserlöslichen Verbindungen in der Vorspülstufe (C) nicht mehr als 20 %, vorzugsweise nicht mehr als 10 % bezogen auf den Anteil des jeweiligen Elements in der Konversionsbehandlungsstufe (D) beträgt, da anderenfalls die Neigung zur Schlammbildung in der Spülstufe (C) erhöht wird, der mit weiteren technischen Maßnahmen entgegengewirkt werden muss, wobei diese durch keine deutliche Verbesserung im Korrosionsschutzes und in der Lackhaftung der im erfindungsgemäßen Verfahren behandelten metallischen Bauteile gerechtfertigt werden würden.Again, it is preferable that 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.
Der Gehalt an Wirkkomponenten bestehend aus den Bestandteilen der wässrigen Zusammensetzung (1) der Behandlungsstufe (D) in der ersten Nachspülstufe (E) ist im erfindungsgemäßen Verfahren aufgrund der stetigen Verschleppung von Konversionsbehandlungslösung mittels der behandelten metallischen Bauteile und der gleichzeitig vorliegenden kaskadierenden Rückführung von Spülwasser aus dieser Nachspülstufe (E) zumindest gleich groß dem Gehalt an diesen Wirkkomponenten in der letzten Vorspülstufe (C). Aufgrund der tendentiell höheren pH-Werte in der letzten Vorspülstufe (C) liegt der Anteil an wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf jedoch meist etwas niedriger als in der ersten Nachspülstufe (E).
Die im Vergleich zur ersten Nachspülstufe tendentiell höheren pH-Werte in der letzten Vorspülstufe (C) beruhen auf der Verschleppung von Bestandteilen der Reinigungs- und Entfettungsstufe, die vorzugsweise aus einem alkalischen Reinigersystem besteht. Umgekehrt werden in die erste Nachspülstufe (E) vornehmlich Bestandteile der sauren wässrigen Zusammensetzung (1) verschleppt.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 Nachspülstufe (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. Conversely, components of the acidic aqueous composition (1) are mainly carried off into the first post-rinse stage (E).
Die wässrige Zusammensetzung der Konversionsbehandlungsstufe (D) enthält für einen schnellere und effektivere vor Korrosion schützende Konversion der Metalloberfläche bevorzugt insgesamt mehr als 100 ppm, besonders bevorzugt insgesamt mehr als 400 ppm, aber vorzugsweise insgesamt nicht mehr als 1500 ppm, besonders bevorzugt insgesamt nicht mehr als 1000 ppm der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen.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.
Die Schlammbildung, die aufgrund des zurückgeführten Spülwassers auch durch beträchtliche Mengen an Eisen-Ionen und gegebenenfalls auch Zink- und Aluminium-Ionen mit verursacht wird, die wiederum über den Beizangriff auf das metallische Bauteil während der Konversionsbehandlung in die Behandlungsstufe (D) gelangen und von dort in die Nachspülstufen verschleppt werden, kann in einer bevorzugten Ausführungsform auch weitgehend unterdrückt werden. Hierzu ist es bevorzugt, die kaskadierte Rückführung von wässrigen Medium von der letzten Spülstufe bis zur ersten Spülstufe derart vorzunehmen, dass man zumindest einen Teil des die Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen enthaltenden und zurückzuführenden Mediums von der Nachspülstufe (E) in die Vorspülstufe (C) nicht unmittelbar zurückspeist, und man diesen Teil des zurückzuführenden Mediums
- a) auf einen pH-Wert von größer als 5,0, vorzugsweise größer als 5,5 einstellt,
- b) einen sich bildenden Niederschlag aus dem Spülwasser abgetrennt, und
- c) ggf. das im Schritt b) von dem Niederschlag befreite Spülwasser entweder einem Ionenaustauschverfahren oder einer Umkehrosmose unterwirft,
- a) to a pH greater than 5.0, preferably greater than 5.5,
- b) separating a forming precipitate from the rinse water, and
- c) optionally subjecting the rinse water freed from the precipitate in step b) to either an ion exchange process or a reverse osmosis,
Die Abtrennung von unlöslichen Metallhydroxiden aus dem zurückzuführenden Medium der Nachspülstufen erlaubt auf diese Weise eine genaue Einstellung des Anteils der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen in der Vorspülstufe (C).The separation of 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).
Im erfindungsgemäßen Verfahren werden in der Konversionsbehandlungsstufe (D) wässrige Zusammensetzungen (1) mit einem Anteil an Fluor gebunden in Form von Fluorokomplexen der Elemente B, Si, Ti, Zr und/oder Hf oder im Überschuss und ungebunden in Form von freiem Fluorid eingesetzt. Ein Anteil an Fluor im Überschuss und ungebunden in Form von freiem Fluorid bedeutet, dass mehr Fluorid-Ionen in der Lösungen enthalten sind als zur Komplexierung der Elemente B, Si, Ti, Zr und/oder Hf benötigt werden.
Durch die Verwendung fluorhaltiger wasserlöslicher Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf wird ein verstärkter Beizangriff auf das metallische Bauteil ausgeübt, der eine schnellere und vollständigere Konversion der Metalloberfläche zur Folge hat.In the process according to the invention, in the conversion treatment step (D), 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.
The use of 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.
Da Fluor-haltige wässrige Zusammensetzungen Anwendung im erfindungsgemäßen Verfahren finden, sind bestimmte pH-Bereiche für die wässrigen Zusammensetzungen der Vorspülstufe und der ersten Nachspülstufe definiert, für die eine hinreichende Stabilität der die Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen enthaltenden jeweiligen Zusammensetzung der Spülstufe und eine optimale Korrosionsschutzbehandlung der metallischen Bauteile gegeben ist.
So wird in der Vorspülstufe (C) ein pH-Bereich von 5,0 bis 7,0, vorzugsweise von 5,8 bis 6,2 eingestellt, während dieser in der Nachspülstufe (E) vorzugsweise im Bereich von 4,0 und 5,5 und insbesondere im Bereich von 4,8 und 5,2 liegt. Höhere Alkalinitäten in den Spülstufen verursachen entweder die Fällung von Hydroxiden der Schwermetalle, die während der Behandlung des metallischen Bauteils gemäß erfindungsgemäßen Verfahren in die Spülstufen verschleppt werden, beispielsweise Eisen, oder führen dazu, dass die Wirkkomponenten in Form der wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf teilweise oder vollständig mit ausgefällt werden und damit im erfindungsgemäßen Verfahren nicht mehr zur Verfügung stehen.Since fluorine-containing aqueous compositions find application in the process according to the invention, certain pH ranges are defined for the 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.
Thus, in the pre-rinse step (C), 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.
In einer weiteren bevorzugten Ausführungsform des Verfahrens erfolgt zur selektiven Abtrennung von Eisen-Ionen aus dem zurückzuführenden Fluor-haltigen Spülwasser die kaskadierte Rückführung von wässrigen Medium von der letzten Spülstufe bis zur ersten Spülstufe derart, dass man zumindest einen Teil des die Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslichen Verbindungen enthaltenden und zurückzuführenden Mediums von der Nachspülstufe (E) in die Vorspülstufe (C) nicht unmittelbar zurückspeist, und man diesen Teil des zurückzuführenden Mediums
- a) mit einer alkalischen Lösung, die keine Calcium-Ionen enthält, auf einen pH-Wert von größer als 5,0, vorzugsweise größer als 5,5 einstellt,
- b) einen sich bildenden Niederschlag aus dem Spülwasser abtrennt,
- a) with an alkaline solution containing no calcium ions, to a pH greater than 5.0, preferably greater than 5.5,
- b) separating a forming precipitate from the rinse water,
In einer speziellen Ausführungsform des erfindungsgemäßen Verfahrens mit kaskadierter Rückführung von Spülwasser erfolgt die vollständige Fällung der Schwermetalle und der Wirkkomponenten aus einem Teil des in die Vorspülstufe (C) zurückzuführenden Spülwassers, das durch Verschleppung aus der Konversionsbehandlungsstufe (D) einen Anteil an Fluor gebunden in Form von Fluorokomplexen der Elemente B, Si, Ti, Zr und/oder Hf oder im Überschuss und ungebunden in Form von freiem Fluorid enthält, mit Hilfe einer wässrigen Lösung von Ca(OH)2. Hierfür wird ein Teil des zurückzuführenden Mediums von der Nachspülstufe (E), der nicht unmittelbar in die Vorspülstufe (C) zurückgespeist wird,
- a) mit einer solchen Menge einer wässrigen Lösung von Ca(OH)2 versetzt, die nicht mehr als 0,1 Gew.-% ungelöstes Ca(OH)2 enthält, dass der pH-Wert des Spülwassers auf einen Wert im Bereich von größer als 5,0, vorzugsweise größer als 5,5 und nicht größer als 7,0 ansteigt,
- b) ein sich bildender Niederschlag aus dem Spülwasser abgetrennt,
- a) with such an amount of an aqueous solution of Ca (OH) 2 added containing not more than 0.1 wt .-% undissolved Ca (OH) 2 , that the pH of the rinse water to a value in the range of greater increases as 5.0, preferably greater than 5.5 and not greater than 7.0,
- b) separating a forming precipitate from the rinse water,
Ein pH-Wert von etwa 9 bis etwa 11, wie er bei einer klassischen Kalkmilch-Fällung nach Stand der Technik üblich ist, wird also in diesem erfindungsgemäßen Verfahren vermieden. Es hat sich gezeigt, dass trotz dieses geringen pH-Werts im Bereich von 5,0 bis 7,0 und der entsprechend geringen zugegebenen Menge an Calciumhydroxid Schwermetalle, wie Eisen-Ionen, und die Wirkkomponenten im Spülwasser umfassend wasserlösliche Fluorokomplexe der Elemente B, Si, Ti, Zr und/oder Hf, vorzugsweise der Elemente Ti und/oder Zr und insbesondere Zr in einem sich bildenden Niederschlag weitgehend ausfallen. Die Abtrennung des ausgefällten Schlammes vom Spülwasser ist mit konventionellen Techniken wie Filtrieren oder Zentrifugieren und Sedimentationsmethoden möglich. Beispielsweise können hierfür Beutel- oder Kiesfilter eingesetzt werden. Das auf diese Weise von löslichen Schwermetallverbindungen und den Wirkkomponenten befreite Spülwasser kann nun ggf. einem an sich bekannten Verfahren unterzogen werden, das weitgehend salzarmes oder entsalztes Wasser liefert. Dies kann ein lonenaustauschverfahren oder eine Umkehrosmose sein, die als solche im Stand der Technik zum Entsalzen von Wasser bekannt sind.A pH of about 9 to about 11, as is customary in a conventional lime milk precipitation according to the prior art, is thus avoided in this inventive method. It has been found that despite this low pH in the range of 5.0 to 7.0 and the correspondingly small added amount of calcium hydroxide, heavy metals, such as iron ions, and the active components in the rinse water comprising water-soluble fluorocomplexes of elements B, Si , Ti, Zr and / or Hf, preferably the elements Ti and / or Zr and in particular Zr largely precipitate in a precipitate formed. 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. That up this way of soluble heavy metal compounds and the active components freed rinse water can now optionally be subjected to a known method, which provides largely low-salt or desalted water. This may be an ion exchange method or a reverse osmosis known as such in the art for desalting water.
Vorzugsweise wird der Teil des zurückzuführenden Spülwassers von der Nachspülstufe (E), der nicht unmittelbar in die Vorspülstufe (C) zurückgespeist wird, zur vollständigen Fällung der Schwermetalle und der Wirkkomponenten im Schritt a) mit einer solchen Menge an wässriger Lösung von Ca(OH)2 versetzt, dass die Änderung der elektrischen Leitfähigkeit des Teils des zurückzuführenden Spülwassers nicht mehr als 200 µS/cm, vorzugsweise nicht mehr als 100 µS/cm beträgt. Ist dies der Fall so kann ggf. auf eine weitergehende Entsalzung des Spülwassers verzichtet oder die konventionellen Entsalzungsverfahren wirtschaftlich eingesetzt werden.Preferably, the portion of the rinse water to be recycled from the post-rinse stage (E), which is not fed back directly to the pre-rinse stage (C), to complete precipitation of the heavy metals and the active components in step a) with such an amount of aqueous solution of Ca (OH) 2 , the change of the electric conductivity of the part of the rinse water to be returned is not more than 200 μS / cm, preferably not more than 100 μS / cm. If this is the case, it may be possible to dispense with a further desalination of the rinse water or the conventional desalination be used economically.
Ebenfalls bevorzugt ist, dass die wässrige Lösung von Ca(OH)2 zur vollständigen Fällung der Schwermetalle und der Wirkkomponenten im Schritt a) 0,001 bis 0,14 Gew.-% Ca(OH)2 enthält. Dieser Konzentrationsbereich ist besonders günstig, um bei pH-gesteuerter automatischer Dosierung die erfindungsgemäß angestrebten Grenzwerte von pH-Wert und elektrischer Leitfähigkeit in demjenigen Teil des zurückzuführenden Spülwassers aus der Nachspülstufe (E) einzuhalten, der nicht unmittelbar in die Vorspülstufe (C) zurückgespeist wird.It is likewise preferred that 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 Nachspülstufe (E), which is not fed back directly into the pre-rinse (C) at pH-controlled automatic dosing.
Die vollständige Abtrennung von unlöslichen Schwermetallhydroxiden und Wirkkomponenten aus einem Teil des zurückzuführenden Spülwassers der Nachspülstufen erlaubt durch eine Abstimmung der jeweiligen Anteile des zurückzuführenden Spülwassers, die unmittelbar oder mittelbar in die Vorspülstufe (C) zurückgespeist werden, eine genaue Einstellung des Anteils der Elemente B, Si, Ti, Zr und/oder Hf in Form wasserlöslicher Verbindungen in der Vorspülstufe (C) auf die bevorzugten Maximalwerte von nicht mehr als 20 %, insbesondere nicht mehr als 10 % bezogen auf den Anteil des jeweiligen Elements in der Konversionsbehandlungsstufe (D).The complete separation of 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).
Zur Demonstration des erfindungsgemäßen Verfahrens zur Vorbehandlung von Metalloberflächen und der damit verbundenen Erhöhung des Korrosionsschutzes, sowie der Verbesserung der Lackhaftung wurden Stahlbleche im Labormaßstab in zwei Prozessketten P1 und P2 mit unterschiedlicher Zusammensetzung der einzelnen Behandlungsstufen behandelt, wobei die Prozessketten nicht kaskadiert betrieben wurden und die Verschleppung von Konversionsbehandlungslösung aus der Stufe (D) begrenzt wurde (Tabelle 1). Nach erfolgter Vorbehandlung wurden die Bleche mit einem Elektrotauchlack versehen und bezüglich Korrosion und Lackhaftung untersucht.To demonstrate the method according to the invention for the pretreatment of metal surfaces and the associated increase in corrosion protection, and the improvement of paint adhesion steel plates were treated on a laboratory scale in two process chains P1 and P2 with different composition of the individual treatment stages, the process chains were not operated cascaded and the carryover of conversion treatment solution from step (D) was limited (Table 1). After pretreatment, the sheets were provided with an electrodeposition paint and examined for corrosion and paint adhesion.
Die Prozesskette P1 simuliert dabei einen stationären Zustand des erfindungsgemäßen Verfahrens mit kaskadierender Rückführung von Spülwasser. Demgegenüber simuliert die Prozesskette P2 einen stationären Zustand einer im Überlauf betriebenen ersten Nachspülstufe (E) ohne kaskadierende Rückführung in die Vorspülstufen, bei der gerade soviel Wirkkomponenten im Überlauf pro Zeitintervall entfernt werden wie pro Zeitintervall durch Verschleppung eingebracht werden, wobei der Anteil an wasserlöslichen Verbindungen der Elemente B, Si, Ti, Zr und/oder Hf in der Nachspülstufe (E) vernachlässigbar ist.The process chain P1 simulates a stationary state of the method according to the invention with cascading recycling of rinsing water. In contrast, 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 Nachspülstufe (E) is negligible.
Aus der Tabelle 2 geht nunmehr hervor, dass bei kaskadierender Rückführung von Spülwasser enthaltend Wirkkomponenten der Konversionsbehandlung keine Verschlechterung der Korrosionsschutzes und der Lackhaftung im erfindungsgemäßen Verfahren resultiert (B1-B4). Eine solche Verschlechterung wurde jedoch erwartet, da die bloße Verlängerung der optimierten Behandlungsdauer mit einer Konversionslösung dazu führt, dass zwar höhere Schichtgewichte bezogen auf die Elemente B, Si, Ti, Zr und/oder Hf resultieren, die metallischen Bauteile jedoch aufgrund einer Überätzung in der Konversionsbehandlungslösung üblicherweise Schichtdefekte aufweisen, die die Korrosionsbeständigkeit wiederum herabsetzen. Ähnliches wäre für das erfindungsgemäßen Verfahren zu erwarten, da sowohl in der Vorspülstufe (C) als auch in der Nachspülstufe (E) beträchtliche Mengen an Wirkkomponenten enthalten sind, beispielsweise ca. 75 ppm Zr in Form von H2ZrF6 (siehe Tabelle 1, P1).
Erstaunlicherweise zeigt sich zudem, dass sowohl der Korrosionsschutz als auch die Lackhaftung in einem erfindungsgemäßen Verfahren speziell auf Stahl- und Aluminiumoberflächen gegenüber einem Verfahren ohne Wirkkomponenten in der Vor- und Nachspüle deutlich verbessert wird (Tabellen 2 und 3).
* nach DIN EN ISO 4628-8
# nach DIN EN ISO 20567-1
* according to DIN EN ISO 4628-8
# according to DIN EN ISO 20567-1
Die besonders ausgeprägte Optimierung der Korrosionsschutzergebnisse auf Stahl bei einer im erfindungsgemäßen Verfahren mit kaskadierender Rückführung gleichzeitig vorliegenden hohen Wassereinsparung zeigt in besonderem Maße die Vorteile des der Erfindung zugrunde liegenden Verfahrens.
+ je 5mm der Ritzspurenden wurden nicht berücksichtigt;
++ nach 42 Tagen
+ each 5mm of the scribe track ends were not considered;
++ after 42 days
Claims (11)
- Method for the corrosion-protective pretreatment of metal surfaces in a process sequence which comprising a conversion treatment stage (D) having an aqueous composition (1) containing overall at least 50 ppm of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds with a pH of 3 to 5.5, wherein the metallic surface passes through at least the following treatment stages in succession:(C) Pre-rinsing with water containing overall at least 10 ppm of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds(D) Conversion treatment with the aqueous composition (1)(E) Post-rinsing with water containing a portion of the aqueous composition (1) of the treatment stage (D),characterized in that
the aqueous composition (1) of the conversion treatment stage (D) contains a portion of fluorine which is bound in the form of fluoro complexes of the elements B, Si, Ti, Zr, and/or Hf or in excess, and a portion of unbound fluorine in the form of free fluoride, and the pH in the pre-rinse stage (C) is in a range of 5 to 7.0. - Method according to Claim 1, characterized in that overall at least 20 ppm, preferably overall at least 50 ppm, of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds are contained in the pre-rinse stage (C).
- Method according to one or both of the preceding claims, characterized in that the proportion of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds in the pre-rinse stage (C) is not greater than 20%, preferably not greater than 10%, based on the proportion of the respective element in the conversion treatment stage (D).
- Method according to one or more of the preceding claims, characterized in that the pH in the pre-rinse stage (C) is in a range of 5.8 to 6.2.
- Method according to one or more of the preceding claims, characterized in that the pH in the post-rinse stage (E) is in a range of 4.0 to 5.5, preferably 4.8 to 5.2.
- Method according to one or more of the preceding claims, characterized in that the metallic surface passes through the following treatment stages in succession:(A) Optional degreasing and cleaning(B) Optional rinsing with service water optionally containing a portion of the aqueous composition of the degreasing and cleaning stage (A)(C) Pre-rinsing with water containing overall at least 10 ppm of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds and optionally a portion of the aqueous composition of the rinse stage (B)(D) Conversion treatment with the aqueous composition (1) containing a portion of the aqueous composition of the pre-rinse stage (C)(E) A first post-rinse with water containing a portion of the aqueous composition of the treatment stage (D)(F) An optional second post-rinse with water containing a portion of the aqueous composition of the post-rinse stage (E),wherein the last rinse stage is fed with deionized water, and a cascaded recirculation of aqueous medium from the last rinse stage to the first rinse stage takes place in such a way that overall at least 10 ppm of the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds are contained in the pre-rinse stage (C), the treatment stage (D) being excluded from the cascaded recirculation, and aqueous medium not being indirectly or directly fed into the treatment stage (D) from the last rinse stage.
- Method according to Claim 6, characterized in that the cascaded recirculation of aqueous medium from the last rinse stage to the first rinse stage takes place in such a way that at least a portion of the medium containing and recirculating the elements B, Si, Ti, Zr, and/or Hf in the form of water-soluble compounds is not directly fed from the post-rinse stage (E) into the pre-rinse stage (C), and this portion of the medium to be recirculateda) is set to a pH of greater than 5.0,b) a precipitate which forms is separated from the rinse water, andc) the rinse water from which the precipitate has been removed in step b) is optionally subjected to either an ion exchange process or a reverse osmosis process,and the rinse water which is treated in this way, as part of the medium to be recirculated, is likewise fed back into the pre-rinse stage (C).
- Method according to Claim 7, wherein the aqueous composition (1) of the treatment stage (D) contains a portion of fluorine which is bound in the form of fluoro complexes of the elements B, Si, Ti, Zr, and/or Hf or in excess, and a portion of unbound fluorine in the form of free fluoride, characterized in that the portion of the medium to be recirculated from the post-rinse stage (E), which is not directly fed into the pre-rinse stage (C), is set in step a) to a pH greater than 5.0 with an alkaline solution which contains no calcium ions, a precipitate which forms is subsequently separated from the rinse water, and the rinse water which is treated in this way, as part of the medium to be recirculated, is fed back into the pre-rinse stage (C).
- Method according to Claim 7, wherein the aqueous composition (1) of the treatment stage (D) contains a portion of fluorine which is bound in the form of fluoro complexes of the elements B, Si, Ti, Zr, and/or Hf or in excess, and a portion of unbound fluorine in the form of free fluoride, characterized in that the portion of the medium to be recirculated from the post-rinse stage (E), which is not directly fed into the pre-rinse stage (C), is combined in step a) with a quantity of an aqueous solution of Ca(OH)2, containing no more than 0.1% by weight of undissolved Ca(OH)2, in such a way that the pH of the rinse water increases to a value in the range of greater than 5.0 and not greater than 7.0.
- Method according to one or more of preceding Claims 6 to 9, characterized in that the cascaded recirculation of aqueous medium from the last rinse stage to the first rinse stage takes place continuously and preferably with a constant volume flow.
- Method according to one or more of the preceding claims, characterized in that the metallic surfaces, at least in part, represent surfaces of iron and/or steel.
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DE102008038653A DE102008038653A1 (en) | 2008-08-12 | 2008-08-12 | Successive anti-corrosive pretreatment of metal surfaces in a multi-stage process |
PCT/EP2009/060063 WO2010018102A1 (en) | 2008-08-12 | 2009-08-04 | Successive corrosion-protecting pre-treatment of metal surfaces in a multi-step process |
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US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
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CN102124144B (en) | 2014-08-06 |
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