Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
  • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also 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
  • C23C22/73—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
  • C23C22/76—Applying the liquid by spraying
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/78—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/78—Pretreatment of the material to be coated
  • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/12—Light metals
  • C23G1/125—Light metals aluminium

Definitions

• the invention relates to a process for the pretreatment of workpieces having a surface of aluminum or aluminum alloys for noncutting forming and/or joining by welding or adhesive bonding to similarly pretreated or optionally otherwise precoated workpieces or to optionally pretreated parts composed of steel and/or galvanized and/or alloy-galvanized steel and also for a subsequent corrosion-protecting treatment by phosphating, by means of a chromium-free conversion treatment, by application of primer or by surface coating.
• Processes of the abovementioned type employ, for example, an aqueous solution which comprises hexavalent chromium, trivalent chromium, alkali metal ions and silicon dioxide in particular ratios and produces coatings for electrical insulation, for anticorrosion and as adhesion base for surface coatings and the like (DE-B 17 69 582).
• the joining of the parts is normally followed by a corrosion-protecting treatment which, depending on the nature of the joined parts, can consist of a phosphating treatment, a chromium-free conversion treatment, application of a primer or a surface coating.
• a corrosion-protecting treatment which, depending on the nature of the joined parts, can consist of a phosphating treatment, a chromium-free conversion treatment, application of a primer or a surface coating.
• EP-B-700 452 provides for surfaces of aluminum or alloys thereof to be brought into contact with an aqueous solution comprising complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium either individually or in admixture with one another in total concentrations of the fluoro anions of from 100 to 4000 mg/l and having a pH of from 0.3 to 35 to effect pretreatment before a second permanent corrosion-protecting treatment.
• the parts composed of aluminum or alloys thereof are subjected to a noncutting and/or cutting shaping process and/or joined together or to parts composed of steel and/or galvanized and/or alloy-galvanized steel by adhesive bonding and/or welding.
• the application of the solution optionally comprising polymers of a particular nature can be effected by spraying, dipping or no-rinse methods, with in the case of the no-rinse method the amount of wet film preferably being in the range from 2 to 10 ml/m 2 , preferably from 4 to 6 ml/m 2 , of metal surface.
• the parts composed of aluminum or alloys thereof are cleaned under acidic or alkali conditions before the first conversion treatment, with preference being given to carrying out further cleaning steps and intermediate rinses with water and/or with activating rinsing baths before the permanent corrosion-protecting treatment.
• the process of the invention should preferably lead to good temporary anticorrosion values and be largely insensitive to contamination of the bath by aluminum ions.
• the object is achieved firstly by the process of the type mentioned at the outset being configured according to the invention so that the workpieces are
• the aqueous, acidic solution in step c) for application by dipping or spraying preferably comprises Zr and Mo in a weight ratio of from 15:1 to 5:1, particularly preferably from 13:1 to 7:1 and very particularly preferably from 11:1 to 9:1.
• the application by dipping or spraying preferably results, after drying, in a layer weight of in each case from 2 to 12 mg/m 2 , particularly preferably from 2 to 10 mg/m 2 and very particularly preferably from 2 to 8 mg/m 2 , of Zr and Mo.
• the aqueous solution for application by dipping or spraying preferably comprises from 250 to 700 mg/l of Zr and from 30 to 80 mg/l of Mo, particularly preferably from 400 to 600 mg/l of Zr and from 40 to 60 mg/l of Mo and very particularly preferably from 475 to 525 mg/l of Zr and from 45 to 55 mg/l of Mo.
• the aqueous solution for application by dipping or spraying preferably has a pH of from 3.1 to 4.3 and particularly preferably from 3.6 to 4.0 and also preferably has a temperature of from 20 to 50° C. and particularly preferably from 20 to 30° C.
• the object is achieved by the process of the type mentioned at the outset being configured according to the invention so that the workpieces are
• the aqueous, acidic solution in step c) for application by the roller application method preferably comprises Zr and Mo in a weight ratio of from 1.7:1 to 1:1.7, particularly preferably from 1.4:1 to 1:1.4 and very particularly preferably from 1.1:1 to 1:1.1.
• the application by the roller application method preferably results, after drying, in a layer weight of in each case from 2 to 12 mg/m 2 , particularly preferably from 2 to 10 mg/m 2 and very particularly preferably from 2 to 8 mg/m 2 , of Zr and Mo.
• the aqueous solution for application by the roller application method preferably comprises from 1.0 to 6.0 g/l of Zr and from 1.0 to 6.0 g/l of Mo, particularly preferably from 2.0 to 4.0 g/l of Zr and from 2.0 to 4.0 g/l of Mo and very particularly preferably from 2.8 to 3.2 g/l of Zr and from 2.8 to 3.2 g/l of Mo.
• the aqueous solution for application by the roller application method preferably has a pH of from 1.4 to 2.7 and particularly preferably from 1.8 to 2.5.
• the defined layer weight of zirconium and molybdenum (from 2 to 15 mg/m 2 ) to be set in each case, it is of critical importance that, depending on the manner of application, namely application by spraying or dipping or application by the roller application method, aqueous, acidic solutions which differ in respect of concentration and ratio of the fluorozirconate and molybdate anions and the pH are used in step c).
• the aqueous, acidic solution in step c) can be provided by prior dilution of an appropriate concentrate, preferably by a factor of from 1:30 to 1:100, more preferably by a factor of about 1:50, preferably with water and optionally setting of the pH.
• the workpieces are also important for the workpieces to be pickled by means of an aqueous, acidic solution comprising a mineral acid by dipping or spraying.
• Alkali cleaning results, for example, in the formation of zirconium/molybdenum layers having poor volume resistances.
• the joining of the workpieces which have been pretreated according to the invention can be to similarly pretreated or optionally otherwise precoated, e.g. phosphated, workpieces, to surfaces of aluminum or alloys thereof. If joining to parts composed of steel and/or galvanized and/or alloy-galvanized steel is intended, these parts can have bare or precoated surfaces.
• One suitable precoat can be, for example, a phosphate layer having a layer weight of not more than 2 g/m 2 or a layer of a conductive primer.
• the pickling process should be preceded by a cleaning/degreasing step or the pickling process should be carried out in such a way that simultaneous cleaning/degreasing occurs.
• the latter can be achieved by addition of surfactant to the pickling solution.
• processes for phosphating treatment processes which work with solutions based on zinc phosphate, in particular corresponding to the low-zinc technology, or with alkali metal phosphate are in the foreground.
• the solutions can have been modified by addition of further small amounts of polyvalent cations such as calcium, magnesium, nickel, copper or manganese.
• chromium-free conversion treatment use is made in particular of acidic solutions of the fluoro complexes of titanium, zirconium, hafnium or else silicon, optionally with a content of an organic polymer.
• These acidic solutions can additionally comprise at least one organosilane and/or at least one hydrolysis product thereof and/or at least one condensation product thereof.
• the at least one organosilane preferably has at least one amino group. Particular preference is given to a bis(trimethoxysilylpropyl)amine or an organosilane which can be hydrolyzed to an aminopropylsilanol and/or to 2-aminoethyl-3-aminopropylsilanol.
• the pretreatment according to the invention of the workpieces ensures satisfactory, temporary anticorrosion for relative long storage times. During this time, no adverse effects on the weldability, in particular for electric resistance welding, or the adhesive bondability occur. In addition, in respect of the weldability, it is ensured that the volume resistance is virtually identical on all surface regions of the workpiece.
• Workpieces for the purposes of the present invention are strip, sheet and individual parts such as profiles.
• the application of the solution as per step c) can be effected by spraying or dipping, in each case with or without rinsing with water.
• the workpiece is dried or the solution is evaporated.
• Object temperatures of from 30 to 90° C. are particularly advantageous.
• the molybdate is advantageously introduced as ammonium heptamolybdate and/or sodium heptamolybdate, preferably as ammonium heptamolybdate and particularly preferably as ammonium heptamolybdate ⁇ 7H 2 O.
• molybdate also comprises protonated forms such as, in particular, molybdic acid.
• the pickling of the workpieces is effected using an aqueous, acidic solution comprising mineral acid. It can be carried out electrolytically or chemically. In the case of electrolytic pickling, phosphoric acid is particularly suitable as mineral acid. Pickling by a chemical route, which is generally preferred because of the simpler mode of operation in terms of apparatus, can be carried out using nitric acid or nitric acid/hydrofluoric acid.
• the workpieces are pickled by spraying or dipping using a solution comprising surfactant, sulfuric acid and a compound selected from the group consisting of hydrofluoric acid, phosphoric acid and iron(III) sulfate, preferably hydrofluoric acid, with solutions comprising from 3 to 8 g/l of sulfuric acid, from 50 to 150 mg/l of uncomplexed, free fluoride and from 1 to 3 g/l of nonionic surfactant having been found to be particularly suitable.
• Ethylene oxide adducts with fatty alcohols and, for example, abietic acid are particularly suitable as nonionic surfactants.
• Measurement of the free fluoride was carried out using a fluoride-sensitive electrode, with calibration of the electrode being carried out using solutions whose pH was identical to that of the solution to be tested.
• the pickling process should be carried out so that a removal of metal of from about 0.1 to 0.6 g/m 2 of workpiece service is obtained.
• the rinsing with water following the pickling of the workpieces, corresponding to step b), is preferably carried out in a plurality of rinsing stages, and it is particularly advantageous to convey the rinsing water in a cascade-like manner in countercurrent to the workpiece.
• the last rinsing stage should be carried out using deionized water.
• the treatment as per step c) following the pickling and rinsing step prevents renewed growth of an oxide layer occurring on the workpieces having a surface of aluminum or aluminum alloy.
• the solution used in step c) additionally comprises at least one polymer selected from the group consisting of poly(meth)acrylic acid, (meth)acrylic acid copolymers, polyvinylphosphonic acid, vinylphosphonic acid copolymers and maleic acid copolymers.
• (meth)acrylic acid-maleic acid copolymers as (meth)acrylic acid copolymers and vinylphosphonic acid-acrylic acid copolymers as vinylphosphonic acid copolymers.
• Particularly suitable polymers are polyacrylic acid and acrylic acid copolymers and in the case of the latter especially acrylic acid-maleic acid copolymers.
• the poly(meth)acrylic acid used preferably has a number-average molecular weight (MW) in the range from 4000 to 300 000 g/mol, particularly preferably from 50 000 to 250 000 g/mol and very particularly preferably from 100 000 to 250 000 g/mol.
• MW number-average molecular weight
• the (meth)acrylic acid copolymer used preferably has a number-average molecular weight (MW) in the range from 4000 to 100 000 g/mol and particularly preferably from 60 000 to 80 000 g/mol.
• MW number-average molecular weight
• the polyvinylphosphonic acid used or the vinylphosphonic acid copolymer used preferably has a number-average molecular weight (MW) in the range from 4000 to 70 000 g/mol and particularly preferably in the range from 10 000 to 30 000 g/mol.
• MW number-average molecular weight
• the concentration of the at least one polymer is in the range from 100 to 600 mg/l, preferably from 100 to 400 mg/l, particularly preferably from 135 to 290 mg/l and very particularly preferably from 170 to 180 mg/l.
• the use of the at least one polymer makes it possible to achieve a layer weight of Zr and Mo in the target range from in each case 2 to 15 mg/m 2 in application by spraying, relatively independently, preferably largely independently, of the spraying time. This is advantageous especially because similar layer weights can be achieved even at different strip speeds. Adverse effects on the volume resistance due to the polymer content are, on the other hand, not observed.
• a further advantageous embodiment of the invention provides for a lubricant to be applied to the workpieces.
• lubricants are, in particular, forming oils based on mineral oil, which can be fully synthetic or of natural origin, or dry lubricants based on polyethylene/polyacrylate.
• the process of the invention normally gives workpieces having layers which allow defect-free forming and/or adhesive bonding or, as a result of the low electrical volume resistance which is uniform over the workpiece surface, defect-free and problem-free welding.
• the workpieces are highly suitable for a subsequent permanent anticorrosion treatment.
• sheets composed of aluminum alloys of the grades AA 6111 and AA 5754 were firstly subjected to degreasing pickling at a temperature of 50° C. by dipping or spraying.
• the pickling solution comprised 6 g/l of sulfuric acid (100% strength), 100 mg/l of hydrofluoric acid (100% strength) and 2 g/l of nonionic surfactant consisting of an ethoxylated fatty alcohol and ethoxylated abietic acid in a weight ratio of 1:1.
• the pickling process was carried out in such a way that the removal of material during pickling was from 0.05 to 0.2 g/m 2 in the case of the alloy AA 5754 and was from 0.05 to 0.4 g/m 2 in the case of the alloy AA 6111. Treatment times in the range from 5 to 20 seconds were required for this purpose.
• the workpieces were subsequently rinsed thoroughly with water, in the last stage with deionized water.
• the volume resistances measured on the single sheet were about 60 pohm in the case of the alloy AA 5754, and about 13 pohm in the case of the alloy AA 6111.
• the polymers A to D in Tab. 1 were the following:
• A: Polyacrylic acid, MW about 60 000 g/mol in colloidal solution
• B: Acrylic acid-maleic acid copolymer, MW about 70 000 g/mol
• C: Polyacrylic acid, MW about 250 000 g/mol
• D: Vinylphosphonic acid-acrylic acid copolymer, MW 4000 to 70 000 g/mol.
• volume resistances in pohm obtained in the individual measurements of the metal sheets are shown in column 3 of Tab. 2. Measurement of the volume resistances was carried out immediately after drying/evaporation (in each case first row “0 d”) and after storage for 30 days (in each case second row “30 d”). It was carried out in accordance with leaflet 2929 (of September 2001) of the Deutscher Verbandes für Sch Strukturen and verwandtemaschine e.V. (DSV) using copper electrodes having a diameter of 20 mm.
• the adhesion was determined by means of a modified APGE (Arizona Proving Ground Equivalent) test.
• two test plates (each 56.25 ⁇ 25 ⁇ 0.25 mm) in each case were coated with an industrial dry lubricant and adhesively bonded by means of a suitable industrial adhesive.
• Six such pairs of test plates were then screwed together at their respective ends to form a chain which was subjected to a tensile stress of 2400 N.
• the following program of conditions was used:
• One sequence of the steps 1 to 3 represents, by definition, one cycle.
• a cycle is in each case considered to have been survived when the adhesive bonding between all test plates of the chain stands fast.
• the test overall is counted as having been passed when at least 45 cycles have been survived.
• phosphatability was determined with the aid of scanning electron micrographs.
• “+” in Table 3 means a closed, finely crystalline phosphate layer
• “o” means a closed, coarsened phosphate layer (crystal having an edge length of >20 ⁇ m)
• “ ⁇ ” means a phosphate layer which is not closed through to not present.
• the layer weights obtained are in the desired range, but as a result of the zirconium/molybdenum ratio in the treatment solution for process step c) of 20:1 (see CE4) or 2:1 (see CE5) the volume resistances obtained are unacceptable, especially for AA 6111 (26 and 44 pohm in the case of CE4 and 19 and 22 pohm in the case of CE5).
• examples E1 to E7 show that when the conditions essential to the invention in respect of the type of pickling treatment, the Zr/Mo ratio, the layer weight produced, the respective concentration and the pH ranges of the treatment solutions are adhered to, layers having extremely good volume resistances combined with good adhesion properties are obtained.
• test plates of examples E6 and E7 which have been pretreated according to the invention and also an unpretreated bare test plate CE6 were also subjected to a multistage anticorrosion treatment consisting of the following steps:
• the anticorrosion in the case of E6 and E7 is in each case comparable to that in the case of CE6.
• the pretreatment according to the invention thus does not have an adverse effect on the anticorrosion achieved subsequently by means of an anticorrosion treatment.

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• 2016
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