Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
• • 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
  • C23C22/78—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
  • C23C22/82—After-treatment
  • C23C22/83—Chemical 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
  • 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
  • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
  • C23C2222/20—Use of solutions containing silanes

Definitions

• the present invention relates to an improved method for the anticorrosion pretreatment of a metallic surface which contains steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy. It also relates to a composition for improving the anticorrosion pretreatment of such a metallic surface, a concentrate for producing this composition, a correspondingly coated metallic surface and the use of a correspondingly coated metallic substrate.
• the coatings formed make it possible to achieve corrosion protection for the treated metal substrates as well as a certain improvement with regard to the adhesion of further layers such as paints.
• the prior art also includes the addition of certain acid-stable polymers to the compositions mentioned. In this way, the properties of the layers formed can be improved.
• the DE 10 2015 225 185 A1 discloses an acidic aqueous composition for coating metallic surfaces, in particular aluminum materials.
• the composition contains an organoalkoxysilane - or its hydrolysis and / or condensation product (s) - a titanium, zirconium, hafnium or aluminum compound - or silicon complex fluoride - and an acid-stable copolymer of alternating configuration.
• the object of the present invention is to provide an alternative method for anti-corrosive pretreatment for metallic surfaces which contain steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy, with which, in particular, the corrosion protection on steel substrates is simultaneously good Can improve adhesion.
• the object is achieved by a method according to claim 1.
• aqueous composition is also to be understood as one which, in addition to water as a solvent / dispersant, contains less than 50% by weight - based on the total amount of the solvent / dispersant - of other organic solvents / Contains dispersant.
• composition B “calculated as hexafluorozirconic acid” is to be understood as the fiction that all the molecules of component b1) in composition B are hexafluorozirconic acid molecules, that is, H 2 ZrF 6 .
• “Complex fluorides” also mean the respective single or multiple protonated forms in addition to the deprotonated forms.
• the metallic surface is successively brought into contact with a first composition, A, with a composition B and with a second composition A, wherein the first and the second composition A can also be chemically identical.
• the metallic surface preferably contains steel or galvanized steel, particularly preferably galvanized steel and very particularly preferably hot-dip galvanized steel.
• the at least one copolymer a) in composition A is preferably stable at least in a partial range where the pH is below 6. This is necessary if, as described above, the metallic surface is to be brought into contact with a single composition, which is an acidic aqueous composition which contains all components a), b1) and, if appropriate, b2).
• the addition according to the invention of the at least one copolymer a) enables the properties of the coatings formed, in particular the corrosion protection, to be significantly improved.
• the surface is pickled and, as a result, a pH gradient is formed with increasing pH towards the surface.
• the copolymers used according to the invention contain acid groups which at least partially dissociate at the increased pH at the surface. This leads to negative charges on the copolymer, which in turn lead to electrostatic attachment of the copolymer to the metallic surface and / or to the metal oxides - from component b1) and optionally on component b2) - and optionally on component b3).
• the copolymer deposited in this way increases the barrier effect of the deposited layers against the diffusion or migration of corrosive salts to the metallic ones Surface. The properties of the coatings formed are thereby improved.
• the monomer units i) of the at least one copolymer a) in composition A which contain at least one carboxylic acid group, phosphonic acid group and / or sulfonic acid group, are, for example, (meth) acrylic acid, vinylacetic acid, itaconic acid, maleic acid, vinylphosphonic acid and / or vinylsulfonic acid.
• These monomer units preferably each have at least one carboxylic acid group. More preferably, they each have at least two carboxylic acid groups. They particularly preferably each have exactly two carboxylic acid groups. Maleic acid is very particularly preferred here.
• composition A has maleic acid as the monomer unit, this can partly be in the form of the anhydride. This is the case when the copolymer added to composition A or the concentrate for producing this composition contains maleic anhydride and complete hydrolysis to maleic acid has not yet taken place in composition A or in the concentrate.
• the monomer units ii) of the at least one copolymer a) in composition A, which contain no acid group, can either be non-polar or polar.
• the at least one copolymer a) can also have a mixture of non-polar and polar monomer units as monomer units which contain no acid group.
• Particularly suitable non-polar monomer units are alkylenes, such as, for example, ethylene, propylene and / or butylene, and / or styrene.
• polar monomer units there are in particular vinyl alcohol and / or vinyl acetate and / or vinyl ethers, such as, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and / or butyl vinyl ether, and / or alkylene oxides, such as, for example Ethylene oxide, propylene oxide and / or butylene oxide, and / or ethyleneimine and / or (meth) acrylic acid ester and / or (meth) acrylamide are suitable.
• vinyl alcohol and / or vinyl acetate and / or vinyl ethers such as, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and / or butyl vinyl ether
• alkylene oxides such as, for example Ethylene oxide, propylene oxide and / or butylene oxide, and / or ethyleneimine and / or (meth) acrylic acid ester and / or (meth) acrylamide
• the length of the hydrocarbon chains in the monomer units ii) which do not contain an acid group is limited only by the resulting hydrophobicity of these monomers and thus by the water solubility of the resulting copolymer.
• the monomer units ii) which do not contain an acid group are preferably vinyl ethers.
• Methyl vinyl ether and / or ethyl vinyl ether is more preferred here, particularly preferably methyl vinyl ether.
• the composition A contains as copolymer a) poly (methyl vinyl ether alt- maleic acid).
• the at least one copolymer a) in composition A preferably has a degree of polymerization based on two monomer units in alternating configuration of 25 to 5700, more preferably from 85 to 1750, particularly preferably from 170 to 1300 and very particularly preferably from 225 to 525. Its number average molecular weight is preferably from 5,000 to 1,000,000 g / mol, more preferably from 15,000 to 300,000 g / mol, particularly preferably from 30,000 to 225,000 g / mol and very particularly preferably from 40,000 to 90,000 g / mol.
• the composition A contains as the at least one copolymer a) poly (methyl vinyl ether- alt- maleic acid) with a number average molecular weight in the range from 40,000 to 60,000 g / mol, preferably from approx. 48,000 g / mol.
• the composition A contains as the at least one copolymer a) poly (methyl vinyl ether alt- maleic acid) having a number average molecular weight ranging from 70,000 to 90,000 g / mol, preferably from about 80,000 g / mol.
• alternating copolymers can be obtained, for example, from Ashland (Gantrez 119 AN) or Sigma-Aldrich.
• the metallic surface i) is brought into contact first with the composition A and then with the composition B, the concentration of the at least one copolymer a) in the composition A in the range from 0.01 to 0.5 g / l, preferably from 0.05 to 0.3 g / l calculated as added solids.
• the composition B preferably has a pH in the range from 0.5 to 5.5, more preferably from 2 to 5.5, particularly preferably from 3.5 to 5.3 and very particularly preferably from 4.0 to 5, 0 on.
• the pH is preferably adjusted with nitric acid, ammonium and / or sodium carbonate.
• composition B preferably additionally comprises b2) at least one compound selected from the group consisting of organoalkoxysilanes, organosilanols, polyorganosilanols, organosiloxanes and polyorganosiloxanes.
• organo- means at least one organic group which is connected directly to a silicon atom via a carbon atom and is consequently not hydrolytically split off from this.
• polyorganosiloxanes are understood to mean those compounds which can be condensed from at least two organosilanols and do not form a polydimethylsiloxane.
• the concentration of b2) is preferably in the range from 1 to 200 mg / l, more preferably 5 to 100 mg / l, particularly preferably 20 to 50 mg / l and very particularly preferably 25 to 45 mg / l calculated as Silicon.
• the concentration of b1) is preferably in the range from 0.05 to 4 g / l, more preferably 0.1 to 1.5 g / l, more preferably 0.15 to 0.57 g / l, particularly preferably 0.20 to 0.40 g / l and very particularly preferably about 0.25 g / l, calculated as hexafluorozirconic acid.
• components b1), b2) and b3) can be monitored during the treatment of the metallic surfaces by means of ICP-OES (optical emission spectrometry with inductively coupled plasma) or approximately photometrically so that individual or multiple components can be topped up if necessary can be.
• ICP-OES optical emission spectrometry with inductively coupled plasma
• composition B preferably contains as component b2) at least one organoalkoxysilane, organosilanol, polyorganosilanol, organosiloxane and / or polyorganosiloxane each with at least one amino group, urea group, imido group, imino group and / or ureido group per organoalkoxysilane / Organosilanol unit.
• Component b2) is more preferably at least one organoalkoxysilane, organosilanol, polyorganosilanol, organosiloxane and / or polyorganosiloxane each with at least one, in particular with one to two amino groups per organoalkoxysilane / organosilanol unit.
• 2-aminoethyl-3-aminopropyltrimethoxysilane 2-aminoethyl-3-aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine or bis (triethoxysilylpropyl) amine or a combination of these as an organoalkoxysilane / organosilanol unit.
• 2-Aminoethyl-3-aminopropyltrimethoxysilane or bis (trimethoxysilylpropyl) amine or a combination of both as an organoalkoxysilane / organosilanol unit is very particularly preferred.
• composition B preferably contains as component b1) at least one complex fluoride selected from the group consisting of the complex fluorides of titanium, zirconium and hafnium.
• Zirconium complex fluoride is also preferred here.
• Zirconium can also be added as zirconyl nitrate, zirconium carbonate, zirconium acetate or zirconium nitrate, preferably as zirconyl nitrate. This also applies to titanium and hafnium.
• the content of the at least one complex fluoride is preferably in the range from 0.05 to 4 g / l, preferably 0.1 to 1.5 g / l and particularly preferably about 0.25 g / l calculated as hexafluorozirconic acid.
• the composition B contains as component b1) at least two different complex fluorides, in particular complex fluorides of two different metal cations and particularly preferably complex fluorides of titanium and of zirconium.
• the composition B additionally comprises a component b3), which is at least one type of cation selected from the group consisting of cations of cerium and other lanthanides, chromium, iron, calcium, cobalt, copper, magnesium, manganese, molybdenum, Nickel, niobium, tantalum, yttrium, vanadium, lithium, bismuth, zinc and tin and / or at least one corresponding compound is involved.
• a component b3) which is at least one type of cation selected from the group consisting of cations of cerium and other lanthanides, chromium, iron, calcium, cobalt, copper, magnesium, manganese, molybdenum, Nickel, niobium, tantalum, yttrium, vanadium, lithium, bismuth, zinc and tin and / or at least one corresponding compound is involved.
• Composition B further preferably comprises zinc cations, copper cations and / or cerium cations and / or at least one molybdenum compound as component b3).
• Composition B particularly preferably comprises zinc cations as component b3), very particularly preferably zinc cations and copper cations.
• composition B - depending on the specific requirements or circumstances - additionally comprises a component b4).
• This is at least one compound selected from the group consisting of pH influencing substances, organic solvents, water-soluble fluorine compounds and colloids.
• composition B preferably has a content in the range from 0.1 to 20 g / l for component b4).
• the substances influencing the pH value are preferably selected from the group consisting of nitric acid, sulfuric acid, methanesulfonic acid, acetic acid, hydrofluoric acid, ammonium / ammonia, sodium carbonate and sodium hydroxide solution. Nitric acid, ammonium and / or sodium carbonate are also preferred here.
• the organic solvents are preferably selected from the group consisting of methanol and ethanol.
• methanol and / or ethanol are present in the treatment baths as reaction products of the organoalkoxysilane hydrolysis.
• the water-soluble fluorine compounds are preferably selected from the group consisting of fluoride-containing compounds and fluoride anions.
• the content of free fluoride in the composition B is preferably in the range from 0.015 to 0.15 g / l, more preferably 0.025 to 0.1 g / l and particularly preferably in the range from 0.03 to 0.05 g / l.
• the colloids are preferably metal oxide particles, more preferably metal oxide particles selected from the group consisting of ZnO, SiO 2 , CeO 2 , ZrO 2 and TiO 2 .
• the composition B preferably also contains at least one type of cation selected from the group consisting of alkali metal ions, ammonium ions and corresponding compounds. It particularly preferably contains sodium ions and / or ammonium ions.
• the composition B can also contain phosphorus and oxygen-containing compounds such as phosphates and / or phosphonates. It can also contain nitrate.
• the content of sulfur-containing compounds, in particular sulfate, should, however, preferably be kept as low as possible.
• the content of sulfur-containing compounds is particularly preferably below 100 mg / l calculated as sulfur.
• the metallic surface to be treated which may have previously been cleaned and / or pickled, can be sprayed with the composition A and / or with the composition B, dipped into them or flooded with them. It is also possible to apply the respective composition manually by wiping or brushing or with rollers or rollers (coil coating process) to the metallic surface to be treated. Electrolytic deposition of the respective composition on the metallic surface to be treated is also possible.
• the treatment time for the parts treatment is preferably in the range from 15 seconds to 20 minutes, more preferably 30 seconds to 10 minutes and particularly preferably in the range from 45 seconds to 5 minutes.
• the treatment temperature is preferably in the range from 5 to 50 ° C, more preferably from 15 to 40 ° C and particularly preferably in the range from 25 to 35 ° C.
• the method according to the invention is also suitable for coating strips (coils).
• the duration of the treatment is preferably in the range from a few seconds to a few minutes, for example in the range from 1 to 1,000 seconds.
• the metallic surface to be treated preferably further contains steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy it preferably contains steel and / or galvanized steel, particularly preferably it contains steel.
• KTL corrosion protection after cathodic electrodeposition coating
• composition A can be prepared from a concentrate by dilution with water and, if necessary, adjusting the pH.
• the treatment bath with the composition A can be prepared by diluting the concentrate with water and / or an aqueous solution, preferably by a factor of 1: 5,000 to 1:10, more preferably 1: 1,000 to 1:10, particularly preferably 1: 300 to 1:10 and are very particularly preferably obtained by a factor of about 1: 100.
• the coatings produced by the process according to the invention serve as corrosion protection and as adhesion promoters for further coatings.
• They can easily be further coated with at least one primer, lacquer, adhesive and / or a lacquer-like organic composition.
• at least one of these further coatings can be cured by heating and / or irradiation.
• the coatings produced with the method according to the invention are preferably rinsed before a further treatment in order to remove excess polymer and disruptive ions from the metallic surface.
• the first further coating can be applied using the wet-on-wet method.
• a cathodic electrodeposition paint (KTL) based on epoxides and / or (meth) acrylates is preferably applied as the paint.
• a metallic substrate coated with the process according to the invention can be used in the automotive industry, for rail vehicles, in the aerospace industry, in apparatus construction, in mechanical engineering, in the construction industry, in the furniture industry, for the production of guard rails, lamps, profiles, cladding or small parts , for the production of bodies or body parts, of individual components, pre-assembled or connected elements, preferably in the automotive or aviation industry, for the production of devices or systems, in particular household appliances, control devices, test devices or construction elements.
• coated metallic substrates for the production of bodies or body parts, of individual components and of preassembled or connected elements in the automobile industry is preferred.
• Sheets (10.5 x 19 cm) made of hot-dip galvanized steel (HDG) were used as substrates.
• Gardoclean® S 5176 (Chemetall; contains phosphate, borate and surfactant) was used as the mildly alkaline immersion cleaner in all examples. For this purpose, 15 g / l were made up in a 50 l bath, heated to 60 ° C. and the substrates were sprayed for 3 min. cleaned at a pH between 10.0 and 11.0. The substrates were then rinsed with city water and deionized water.
• the pre-rinsing of the substrates was carried out for 120 seconds at 20 ° C. with moderate stirring.
• the Oxsilan® additive 9936 (Chemetall; contains fluoride and a zirconium compound) and, if necessary, Oxsilan® AL 0510 (Chemetall; contains 2-aminoethyl-3-aminopropyltrimethoxysilane and bis (trimethoxysilylpropyl) amine, see Tab 1: “Silane”) was added to a 50 l batch in such an amount that a zirconium concentration of 100 mg / l and a silane concentration of 30 mg / l, calculated as Si, resulted.
• the bath temperature was set to 30 ° C.
• the pH was continuously corrected by adding dilute nitric acid.
• the finished bath was left to age for at least 12 hours in order to be able to ensure that a chemical equilibrium was established within the bath.
• the conversion treatment was carried out for 120 seconds with moderate stirring. It was then rinsed with town water and deionized water.
• the layer weights (SG) in mg / m 2 on the pretreated substrates were determined by means of X-ray fluorescence analysis (XRF). The amount of zirconium applied was measured.
• the pretreated substrates were KTL coated. Cathoguard® 800 (BASF) was used for this. A build-up paint was then applied. This was Daimler Black.
• the thickness of the lacquer layer was determined using a layer thickness measuring device according to DIN EN ISO 2808 (version 2007). It ranged from 90 to 110 ⁇ m. For the cataplasma test (see below) no build-up paint was applied. Here the layer thickness of the KTL was between 20 and 25 ⁇ m.
• Tab. 1 shows that when using poly (methyl vinyl ether- alf- maleic acid) in the conversion bath, better corrosion protection results can be achieved than when using it in the pre-wash (VB2 compared to B1 and VB4 compared to B3). Nevertheless, the results in the case of the pre-wash according to the invention are still satisfactory.

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• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Treatment Of Metals (AREA)
• Paints Or Removers (AREA)

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• 2017
  • 2017-06-21 RU RU2019100885A patent/RU2748887C2/ru active
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