Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
  • B05D3/107—Post-treatment of applied coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • 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
  • C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
  • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/73—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
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment

Definitions

• the present invention relates to the corrosion-protective treatment of composite metal structures containing metallic surfaces of aluminum, zinc and possibly iron in a multi-stage process.
• the process of the present invention allows selective zinc phosphating of the zinc and iron surfaces of the composite metal structure without depositing significant amounts of zinc phosphate on the aluminum surfaces.
• the aluminum surface is available for passivation with conventional acidic treatment solutions which generate a homogeneous, corrosion-protecting thin conversion layer.
• the formation of phosphate crystal nests on the aluminum surfaces and, on the other hand, the formation of specks on zinc surfaces is prevented.
• the present invention also relates to a zinc phosphating solution containing water-soluble inorganic compounds of silicon in an amount sufficient to suppress speckling, but which does not exceed values for which the zinc phosphating loses its selectivity to the zinc and iron surfaces of the composite metal structure.
• the German patent application DE 19735314 proposes a two-stage process in which first a selective phosphating of the steel and galvanized steel surfaces of a body also having aluminum surfaces takes place and then treatment of the body with a passivation solution for corrosion-protective treatment of the aluminum parts of the body.
• the selective phosphating is achieved by decreasing the pickling effect of the phosphating solution.
• the prior art discloses other two-stage pretreatment methods which also conceptually follow the deposition of a crystalline phosphate layer on the steel and optionally zinc-plated and alloy-galvanized steel surfaces in the first step and the passivation of the aluminum surfaces in a further subsequent step.
• These procedures are in the scriptures WO 99/12661 and WO 02/066702 disclosed.
• the processes disclosed therein are carried out in such a way that, in a first step, selective phosphating of the steel or galvanized steel surfaces takes place, which is also retained in the post-passivation in a second process step, while no phosphate crystals are formed on the aluminum surfaces.
• the selective phosphating of the steel and galvanized steel surfaces is achieved by a temperature-dependent limitation of the proportion of free fluoride ions in the phosphating solutions, the free acid contents are set in a range of 0 to 2.5 points.
• phosphate crystal nests By phosphate crystal nests the skilled person understands the isolated and localized deposition of phosphate crystals on metal surfaces (here: aluminum surfaces). Such "crystal nests" are trapped by a subsequent coating primer and are inhomogeneities in the coating, which can both disturb the uniform visual impression of the painted surfaces and also cause punctiform paint damage.
• speckling one skilled in the phosphating art understands the phenomenon of local deposition of amorphous white zinc phosphate in an otherwise crystalline phosphate layer on the treated zinc surfaces or on the treated galvanized or alloy galvanized steel surfaces.
• the speckling is caused by a locally increased pickling rate of the substrate.
• Such point defects in the phosphating can be the starting point for the corrosive delamination of subsequently applied organic coating systems, so that the occurrence of specks in practice is largely to be avoided.
• the material aluminum also means its alloys.
• the material zinc also comprises galvanized steel and alloy-galvanized steel, while the inclusion of iron also includes iron alloys, in particular steel. Alloys of the aforementioned materials have a Fremdatomanteil of less than 50 atomic%.
• step (I) of the process according to the invention zinc phosphate layers having a surface coating weight of preferably at least 1.0 g / m 2 , more preferably at least 2.0 g / m 2 , but preferably not more than 4, 0 g / m 2 deposited.
• the coating of zinc phosphate is determined for all surfaces of the composite metal construction by means of gravimetric differential weighing on test plates of the individual metallic materials of the respective composite metal construction.
• steel sheets are brought into contact immediately after a step (I) for 15 minutes with an aqueous 5 wt .-% strength CrO 3 solution at a temperature of 70 ° C and freed in this way from the zinc phosphate layer.
• a corresponding test sheet is brought into contact with an aqueous 5% by weight CrO 3 solution at a temperature of 25 ° C. immediately after a step (I) for 5 minutes, and in this way removed from the zinc phosphate layer.
• step (I) aluminum sheets are brought into contact with an aqueous 65% strength by weight HNO 3 solution at a temperature of 25 ° C. for 15 minutes immediately after step (I) and are freed from zinc phosphate portions accordingly.
• the difference in weight of the dry metal sheets after this respective treatment to weight the same dry untreated metal sheet immediately before the step (I) corresponds to the zinc phosphate layer coating according to this invention.
• step (II) not more than 50% of the crystalline zinc phosphate layer is dissolved on the steel and galvanized and / or alloy-galvanized steel surfaces can also be determined by test sheets of the individual metallic materials of the respective Composite metal construction to be understood.
• the test plates of steel, galvanized or alloy-galvanized steel phosphated according to step (I) of the process according to the invention are blown dry with compressed air after a rinsing step with deionized water and then weighed.
• the same test sheet is then brought into contact with the acidic treatment solution according to step (II) of the method according to the invention, then rinsed with deionized water, blown dry with compressed air and then weighed again.
• step (II) of the method according to the invention is now determined.
• the free acid of the zinc phosphating solution in points is determined in step (I) of the method according to the invention by diluting 10 ml sample volume of the phosphating solution to 50 ml and titrating with 0.1 N sodium hydroxide solution to a pH of 3.6. The consumption of ml of sodium hydroxide gives the score of free acid.
• the concentration of free fluoride in the zinc phosphating solution is determined in the method according to the invention by means of a potentiometric method.
• a sample volume of the zinc phosphating solution is taken and the activity of the free fluoride ions is determined with any commercial fluoride-selective potentiometric combination electrode after calibration of the combination electrode using fluoride-containing buffer solutions without pH buffering. Both the calibration of the combination electrode and the measurement of the free fluoride are carried out at a temperature of 20 ° C.
• water-soluble inorganic compounds containing silicon causes the suppression of speck formation on the zinc surfaces, for which purpose at least 0.025 g / l of these compounds must be present as SiF 6 in the phosphating bath, but only less than 1 g / l, preferably only less than 0 , 9 g / l may be included.
• the upper limit is on the one hand due to the economic viability of the process and on the other hand, that the process control is significantly impeded by such high concentrations of water-soluble inorganic compounds containing silicon, since the formation of phosphate crystal on the aluminum surfaces are pushed back on an increase in the free acid content only insufficient can.
• the crystal nests in turn can represent local surface defects, which are starting points for the corrosive delamination of the subsequently applied dip.
• such crystal nests after the completion of the paint system require punctual elevations, which always have to be ground back for a customer-desired optically uniform coating of the composite metal construction, for example an automobile body.
• the ratio of the ion product from the concentration of silicon in the form of water-soluble inorganic compounds and free fluoride to the free acid score in the phosphating solution is critical the success of the method according to the invention. If this quotient is exceeded, the formation of at least individual zinc phosphate crystal nests on the aluminum surfaces already takes place. If this critical parameter is exceeded further, the aluminum surfaces in the process according to the invention are coated with a full-coverage crystalline zinc phosphate layer. Both scenarios must be avoided for successful corrosion protection pretreatment.
• step (I) of the method according to the invention zinc phosphating solutions are used whose product (Si / mM).
• (F / mM) is selected from the concentration of silicon [Si in mM] in the form of water-soluble inorganic compounds and the concentration of free fluoride [F in mM] divided by the score of the free Acid is 4.5, more preferably does not exceed 4.0.
• the proportion of silicon according to the invention in the form of water-soluble inorganic compounds to prevent the formation of specks on the parts of zinc treated according to the invention is sufficient.
• water-soluble inorganic compounds containing silicon are preferred fluorosilicates, particularly preferably H 2 SiF 6, (NH 4) 2 SiF 6, Li 2 SiF 6, Na 2 SiF 6 and / or K 2 SiF. 6
• the water-soluble fluorosilicates are also suitable as a source of free fluoride and therefore serve the complexation of introduced into the bath solution trivalent aluminum cations, so that the phosphating remains guaranteed on the surfaces of steel and galvanized and / or alloy-galvanized steel.
• step (I) of the process according to the invention When using fluorosilicates in phosphating in step (I) of the process according to the invention is of course always pay attention that the ion product of silicon in the form of water-soluble inorganic compounds and free fluoride in proportion to the score of the free acid according to claim 1 of the present invention does not exceed becomes.
• step (I) zinc phosphating solution having a free acid content of more than 0.6 points is preferred in step (I), more preferably of at least 1.0 points, but preferably not more than 2.5 points, particularly preferably not more than 2.0 points. Maintaining the preferred ranges for the free acid ensures on the one hand a sufficient deposition kinetics of the phosphate layer on the selected metal surfaces and on the other hand prevents unnecessary pickling of metal ions, which in turn intensive monitoring or processing of the phosphating to prevent the precipitation of sludge or Disposal of the same in the continuous operation of the method requires.
• the total acid content in the phosphating solution in step (I) of the process according to the invention should be at least 10 points, preferably at least 15 points, but not more than 50 points, preferably not more than 25 points.
• the zinc phosphating solution in step (I) contains a total of not more than 5 ppm, particularly preferably not more than 1 ppm of water-soluble compounds of zirconium and / or titanium based on the elements zirconium and / or titanium ,
• the presence of the water-soluble zirconium and / or titanium compounds in a process according to the invention therefore produces either comparatively lower coating weights of zinc phosphate on steel surfaces or aluminum surfaces on which local defects in the form of phosphate crystal nests prevent a homogeneous paint buildup and potentially promote corrosive paint adhesion.
• zinc phosphating solutions in step (I) of the process according to the invention which are not more than 5 ppm, particularly preferably not more than 1 ppm of water-soluble compounds of zirconium and / or titanium based on the elements zirconium and / or titanium, and more preferably no water-soluble compounds of zirconium and / or titanium.
• the zinc phosphating solution in step (I) of the process according to the invention preferably contains at least 0.3 g / l, more preferably at least 0.8 g / l, but preferably not more than 3 g / l, more preferably not more than 2 g / l zinc ions.
• the proportion of phosphate ions in the phosphating solution is preferably at least 5 g / l, but is preferably not greater than 50 g / l, more preferably not greater than 25 g / l.
• the zinc phosphating solution of the process according to the invention may additionally comprise at least one of the following accelerators: 0.3 to 4 g / l chlorate, 0.01 to 0.2 g / l Nitrite ions, 0.05 to 4 g / l nitroguanidine, 0.05 to 4 g / l N-methyl-N-oxide, 0.2 to 2 g / l m-nitrobenzenesulfonate ions, 0.05 to 2 g / l m-nitrobenzoate ions, 0.05 to 2 g / l p-nitrophenol, 1 to 150 mg / l Hydrogen peroxide in free or bound form, 0.1 to 10 g / l Hydroxylamine in free or bound form, 0.1 to 10 g / l reducing sugars.
• accelerators 0.3 to 4 g / l chlorate, 0.01 to 0.2 g / l Nitrite ions, 0.05 to 4 g / l nitroguanidine
• Such accelerators are known in the art as components of phosphating and fulfill the task of "hydrogen scavengers" by these directly oxidize the resulting from the acid attack on the metallic surface hydrogen and thereby be reduced.
• the formation of a homogeneous crystalline zinc phosphate layer on the steel surfaces as well as on the galvanized and / or alloy-galvanized steel surfaces is substantially facilitated by the accelerator, which reduces the formation of gaseous hydrogen on the metal surface.
• Corrosion protection and paint adhesion of the crystalline zinc phosphate layers produced with an aqueous composition according to the invention are, according to experience, improved if, in addition, one or more of the following cations is present: 0.001 to 4 g / l Manganese (II), 0.001 to 4 g / l Nickel (II), 0.001 to 4 g / l Cobalt (II) 0.002 to 0.2 g / l Copper (II), 0.2 to 2.5 g / l Magnesium (II) 0.2 to 2.5 g / l Calcium (II), 0.01 to 0.5 g / l Iron (II), 0.2 to 1.5 g / l Lithium (I), 0.02 to 0.8 g / l Tungsten (VI).
• Aqueous conversion treatment compositions which contain both manganese and nickel ions in addition to zinc ions are known as trication-phosphating solutions to those skilled in the phosphating art and are also well suited to the present invention. Also, as in the phosphating usual share of up to 5 g / l, preferably up to 3 g / l nitrate facilitates the formation of a crystalline homogeneous and closed phosphate layer on the steel, galvanized and alloy-galvanized steel surfaces.
• the phosphating solutions in step (I) of the process according to the invention generally also contain sodium, potassium and / or ammonium ions, which pass through the addition of the appropriate alkalis to adjust the free acid content in the phosphating solution.
• step (II) of the method by contacting the composite metal structure with the acidic treatment solution, formation of a conversion layer on the aluminum surfaces occurs according to the invention, the zinc phosphate layer being on the steel surfaces, galvanized and / or alloy-galvanized steel surfaces during contacting is dissolved with the treatment solution to not more than 50%, preferably not more than 20%, more preferably not more than 10%.
• passivating inorganic or mixed inorganic-organic thin layers which are not closed crystalline phosphate layers are considered as the conversion layer on aluminum and therefore have a basis weight of less than 0.5 g / m 2 of phosphate layer determined by differential weighing after contacting the aluminum surfaces with 65% by weight nitric acid for 15 minutes at 25 ° C.
• the pH of the acidic treatment solution in the range of 3.5 to 5.5 substantially already ensures that not more than 50% of the zinc phosphate layer on the steel surfaces, galvanized and / or alloy-galvanized steel surfaces is dissolved, the corresponding conversion layers on the Aluminum surfaces of the composite metal structure typically produced by chromium-free acid treatment solutions containing water-soluble compounds of the elements Zr, Ti, Hf, Si, V and Ce, preferably in a total amount of at least 10 ppm based on the respective elements.
• the acidic treatment solution in step (II) comprises a total of 10 to 1500 ppm fluorocomplexes of zirconium and / or titanium based on the elements zirconium and / or titanium and optionally up to 100 ppm, if appropriate preferably at least Contains 1 ppm of copper (11) ions.
• the inventive method for the anticorrosive treatment of composite metal structures assembled from metallic materials, which at least partly also have aluminum surfaces is carried out after cleaning and activation of the metallic surfaces by first contacting the surfaces with the zinc phosphating solution of step (I), e.g. by spraying or dipping, at temperatures in the range of 20-65 ° C and for a time interval matched to the type of application.
• step (I) the zinc phosphating solution of step (I)
• the phosphating in step (I) of the method according to the invention is particularly suitable for such Phosphatieranlagen that operate on the principle of the dipping process, since the speckling in inventive method is suppressed.
• step (I) Immediately after the application of the phosphating solution in step (I) is usually followed by a rinsing with city water or demineralized water, after workup of enriched with components of the treatment solution rinse water selective recycling of components of the phosphating in the phosphating according to step (I) of the invention Procedure can be made.
• the composite metal construction treated according to step (I) is reacted with the acidic treatment solution in step (II) Immerse or contacted by spraying the solution.
• the composite metal construction can be provided with a basecoat, preferably with an organic dip coating, preferably without prior drying of the component treated according to the invention.
• the protected according to the inventive method from corrosion composite metal construction is used in automotive production in body construction, shipbuilding, construction and for the production of white goods use.
• the zinc phosphating solution (A) according to the invention contains a total of not more than 5 ppm, particularly preferably not more than 1 ppm of water-soluble compounds of zirconium and / or titanium based on the elements zirconium and / or titanium and in particular no water-soluble compounds of zirconium and / or titanium.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical Treatment Of Metals (AREA)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Application Of Or Painting With Fluid Materials (AREA)

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• 2010
  • 2010-06-30 DE DE102010030697A patent/DE102010030697A1/de not_active Ceased
• 2011
  • 2011-06-24 CN CN201180031918.7A patent/CN102959127B/zh active Active
  • 2011-06-24 PL PL11730611T patent/PL2588646T3/pl unknown
  • 2011-06-24 MX MX2012015048A patent/MX336103B/es unknown
  • 2011-06-24 ES ES11730611.8T patent/ES2556138T3/es active Active
  • 2011-06-24 BR BR112012033494A patent/BR112012033494A2/pt not_active Application Discontinuation
  • 2011-06-24 CA CA2802035A patent/CA2802035C/en active Active
  • 2011-06-24 KR KR1020127034254A patent/KR101632470B1/ko active IP Right Grant
  • 2011-06-24 WO PCT/EP2011/060590 patent/WO2012000894A1/de active Application Filing
  • 2011-06-24 HU HUE11730611A patent/HUE025740T2/en unknown
  • 2011-06-24 EP EP11730611.8A patent/EP2588646B1/de active Active
  • 2011-06-24 JP JP2013517208A patent/JP5727601B2/ja active Active
• 2012
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