EP3448938A1 - Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée - Google Patents

Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée

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Publication number
EP3448938A1
EP3448938A1 EP17723944.9A EP17723944A EP3448938A1 EP 3448938 A1 EP3448938 A1 EP 3448938A1 EP 17723944 A EP17723944 A EP 17723944A EP 3448938 A1 EP3448938 A1 EP 3448938A1
Authority
EP
European Patent Office
Prior art keywords
composition
compound
formula
range
diol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17723944.9A
Other languages
German (de)
English (en)
Inventor
Anna Verena MOHR
Michael DRÖGE
Daniel SCHATZ
Marc RITTMEYER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP3448938A1 publication Critical patent/EP3448938A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/12—Wash primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/62—Treatment of iron or alloys based thereon
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular 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
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals
    • 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
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • 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 invention relates to a method for corrosion-protective treatment of a metallic surface and to an aqueous composition for reducing pickling in the corrosion-protective treatment of metallic surfaces.
  • the acidic or alkaline pH initially serves to remove oxide films and impurities from the metallic surface.
  • the oxidative proton attack on the metallic surface itself causes the metal cations necessary for the formation of the conversion coating to be dissolved out of it (so-called anodic metal dissolution).
  • the object of the invention was therefore to avoid the disadvantages of the prior art and a method for corrosion-protective treatment of a To provide metallic surfaces with reduced pickling and a composition for reducing pickling in the anti-corrosive treatment of metallic surfaces.
  • This object is achieved by a method according to claim 1, a composition according to claim 20, a concentrate according to claim 21 and a use according to claim 22.
  • Advantageous embodiments are each described in the dependent claims.
  • the surface is contacted successively with the following aqueous compositions: i) an alkaline or acidic cleaner composition,
  • compositions comprising a (meth) acrylate and / or epoxide-based KTL, wherein at least one of the compositions i) to v) at least one compound of the formula I.
  • R 1 is O- (CH 2 ) x Z- (CH 2 ) y-OR 2 (I), and wherein R 1 and R 2 are each independently H or an HO- (CH 2 ) W group with w> 2 , x and y are each independently 1 to 4, and Z is an S atom or a CC triple bond.
  • an "aqueous composition” is to be understood as meaning that, for the most part, ie more than 50% by weight, as the solvent / dispersant, water is contained Composition of a solution, more preferably a solution containing only water as a solvent.
  • That the metallic surface is successively contacted with the aqueous compositions i) to vi) does not exclude that it is brought into contact with one or more further compositions before and / or after this sequence. Also, it is not excluded that the metallic surface between the contacting with the different compositions i) to vi) is brought into contact with one or more further compositions.
  • the at least one compound of formula I acts as a physical corrosion inhibitor which is adsorbed by van der Waals forces on the metallic surface, forming a monomolecular, homogeneous, densely packed layer thereon. By means of said layer, the metallic surface is physically shielded from a proton or hydroxide ion attack and thus the pickling of the surface is prevented or at least reduced.
  • the detergent composition i) contains at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the detergent composition i) is preferably in the range from 6 to 625 mg / l, particularly preferably in the range from 31 to 313 mg / l (calculated as 2-butin-1, 4-diol ).
  • the first rinsing composition ii), the second rinsing composition iii) and / or the third rinsing composition v) comprises at least one compound of the formula I.
  • the use of the at least one compound of formula I in one or more of the rinse compositions has the advantage of reducing the formation of flash rust on steel and / or galvanized steel.
  • the concentration of the at least one compound of the formula I is in the first rinsing composition ii), in the second rinsing composition iii) and in the third rinsing composition v) preferably in the range of 1 to 100 mg / l, particularly preferably in the range of 6 to 60 mg / l (calculated as 2-butyne-1, 4-diol).
  • the conversion composition iv) comprises at least one compound of the formula I.
  • concentration of the at least one compound of the formula I in the conversion composition iv) is in the range from 1 to 100 mg / l, preferably in the range from 3 to 100 mg / l and more preferably in the range 30 to 100 mg / l (calculated as 2-butyne-1,4-diol).
  • the metallic surface is contacted between contacting with the first rinse composition ii) or optionally the second rinse composition iii) and the conversion composition iv) with an aqueous pickle composition vii) and then with a fourth rinse composition viii).
  • the pickling composition vii) preferably contains at least one compound selected from the group consisting of phosphonates, condensed phosphates and citrate and / or at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, more preferably it contains at least one mineral acid selected from the group consisting of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid, most preferably it contains sulfuric acid.
  • the pickling composition vii) contains at least one compound of the formula I.
  • the concentration of the at least one compound of the formula I in the mordant composition vii) is in the range from 31 to 620 mg / l, preferably in the range from 31 to 310 mg / l (calculated as 2-butyne-1, 4-diol).
  • the use of the at least one compound of the formula I in the pickling composition has the advantage of particularly effectively reducing pickling.
  • the detergent composition is i) alkaline, more preferably has a pH of 9.5 or greater.
  • the first rinsing composition ii), the second rinsing composition iii) and the third rinsing composition v) preferably have a pH in the range from 2 to 10, more preferably in the range from 3 to 10.
  • the first rinse composition is preferably weakly acidic, slightly alkaline or neutral. Particularly preferably, it has a pH in the range from 6 to 9.
  • the second rinse composition is preferably weakly alkaline or neutral. Most preferably, it has a pH in the range of 7 to 9.
  • the third rinse composition preferably has a pH in the range of 4 to 9, more preferably it is slightly acidic, slightly alkaline or neutral. Most preferably, it has a pH in the range of 6 to 8.
  • the conversion composition iv) is a passivating composition containing a titanium, zirconium and / or hafnium compound.
  • the passivating composition iv) is substantially free of manganese.
  • essentially manganese-free is meant that less than 10 mg / l of manganese is contained in the four pass composition.
  • the titanium, zirconium and / or hafnium compound is preferably the corresponding hexafluoro complex, most preferably hexafluorozirconate.
  • the passivating composition iv) preferably contains copper ions and / or a compound which releases copper ions and / or zinc ions and / or a compound which liberates zinc ions.
  • the passivating composition iv) preferably contains an organoalkoxysilane and / or a hydrolysis and / or a condensation product thereof.
  • the organoalkoxysilane preferably has at least one amino group. Particularly preferably it is one which can be hydrolyzed to an aminopropylsilanol and / or to 2-aminoethyl-3-amino-propyl-silanol and / or a bis (trimethoxysilylpropyl) amine.
  • the passivating composition may also contain a polymer and / or copolymer.
  • the at least one compound of the formula I is a mixture of a compound of the formula I in which R 1 and R 2 are both H, and a compound of the formula I in which R 1 and R 2 are each independently one HO- (CH 2 ) w group with w> 2.
  • the at least one compound of formula IR 1 and R 2 are both H or an HO- (CH 2 ) 2 group, the sum of x and y is 2 to 5 and Z is a CC triple bond.
  • the at least one compound of the formula I is 2-butyne-1,4-diol and / or 2-butyne-1,4-diol bis (2-hydroxyethyl ether).
  • the at least one compound of the formula I is particularly preferably a mixture of 2-butyne-1,4-diol and 2-butyne-1,4-diol bis (2-hydroxyethyl ether), the mixing ratio based on wt Range of 0.5: 1 to 2: 1, preferably in the range of 0.75: 1 to 1, 75: 1 and particularly preferably in the range 1: 1 to 1, 5: 1.
  • the metallic surface treated with the method according to the invention is preferably the surface of a metal strip or a metallic component, for example a body.
  • the metallic surface may include bare steel, electrolytically galvanized and / or hot-dip galvanized steel, aluminum and / or an aluminum alloy.
  • the metallic surface in addition to bare steel and / or galvanized steel, the metallic surface also contains aluminum or an aluminum alloy (so-called multimetal capability).
  • the process according to the invention has proved to be advantageous in the case of acrylate- and / or epoxide-based cathodic electrocoating paint (EPC) in terms of improved paint adhesion and improved corrosion protection.
  • EPC cathodic electrocoating paint
  • a topcoat is optionally applied to the KTL-coated metallic surface.
  • the present invention further relates to an aqueous composition for reducing pickling in the anti-corrosive treatment of metallic surfaces, which contains at least one compound of the formula I as described above.
  • aqueous composition according to the invention in addition, it relates to a concentrate from which the aqueous composition according to the invention can be obtained by dilution with a suitable solvent and / or dispersion medium, preferably with water, and optionally adjusting the pH.
  • the dilution factor is preferably in the range from 1:10 to 1: 10,000, more preferably in the range from 1:50 to 1: 200.
  • the present invention also relates to the use of the metallic surface treated by the method according to the invention.
  • the present invention is to be illustrated by the following - not to be limited - embodiments.
  • the system is brought out of equilibrium by applying an external potential.
  • the cathodic substream represents the cathodic reaction. At pH values of 4 or higher, oxygen reduction is dominant here.
  • the anodic substream must be set equal to the anodic reaction or the metal oxidation. From this, partial current density-potential curves can be derived:
  • anodic and cathodic partial currents are equal in magnitude at a potential. This point is the resting potential. From the above equations for the cathodic and anodic substream, it is finally possible to determine the corrosion potential E kor r and the corrosion current density Ikon, from which conclusions can be drawn about the corrosion behavior of the sample.
  • E k0 rr describes the rest potential.
  • Ikon- corresponds to the cathodic and anodic partial current density, which are the same at the resting potential.
  • the respective partial flows are plotted as a straight line.
  • the logarithm of the currents is plotted against the potential, which results in straight lines.
  • the corrosion potential E kor r and the corrosion current density Ikon- can be read on the basis of the intersection of the logarithmic partial flows. The evaluation is carried out in the linear part of the curve.
  • Beizenabtrag indicates by what percentage of the weight loss of the metal by the addition of an inhibitor is reduced.
  • a defined test sheet is dipped in the appropriate test solution.
  • the mass loss on the surface is determined gravimetrically before and after each.
  • test panels were first cleaned with petroleum benzine. The residual carbon content after purification was less than 10 mg / m 2 .
  • the mass of each 105 x 190 mm sized and cleaned hot dip galvanized steel test plate was determined on the analytical balance. Immediately following the determination of the mass, the test panels were each hung in a 3 liter beaker with an appropriate test solution. It was stirred with a 40 mm magnetic stir bar. The stirring speed was 400 rpm at the bottom of the beaker. After 3 minutes, the test panels were each removed from the solution, rinsed with distilled water and dried with compressed air. Subsequently, the mass of each test sheet was again determined with the analytical balance.
  • the inhibition value indicates by what percentage the attack on the workpiece by the inhibitor (s) can be reduced. The higher this inhibition value compared to the non-inhibited solution A, the greater the corrosion-protecting properties within the pretreatment process.
  • the reduction of the material loss is necessary in order to remove as little as possible of the galvanizing within the process and to reduce associated zinc phosphate sludge in the corresponding cleaner zones of a pretreatment plant.
  • Blank steel (CRS) test panels were sprayed in sequence with each other for 180 seconds and 45 ° C. with a strong alkaline multi-metal cleaner, city water (first rinse composition) for 30 seconds, and deionized water (second rinse composition) for 20 seconds , They were then treated for 120 s at 30 ° C (conversion composition A ', see below) or 40 ° C (conversion composition B' and C, see below) with a conversion composition (see Table 3) and then for 20 s with VE Water (third rinse composition) sprayed. Finally, the test panels were dried with compressed air, coated with an acrylate-based KTL and subjected to crosshatch, stone chip and NSS tests.
  • the conversion composition A ' is an acidic aqueous solution of 0.2 g / l zirconium, 0.1 g / l each of zinc and manganese, 0.3 g / l of total fluoride and 30 mg / l of free fluoride at pH 5 ; 2.
  • the conversion composition B ' is an acidic aqueous solution of 0.1 g / L zirconium, 0.4 g / L zinc, 0.1 g / L total fluoride, 2 mg / L copper and 30 mg / L free Fluoride at pH 4.9, which additionally contains 3.1 mg / l but-2-yn-1,4-diol and 2.5 mg / l 2-butyne-1,4-diol bis (2-hydroxyethyl ether) ,
  • the conversion composition C is an acidic aqueous solution of 0.1 g / l zirconium, 0.4 g / l zinc, 0.1 g / l total fluoride, 5 mg / l Copper and 30 mg / l free fluoride at pH 4.9, which additionally contains 31 mg / l but-2-yn-1,4-diol and 25 mg / l 2-butyne-1,4-diol-bis (2- hydroxyethyl ether).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention concerne un procédé de traitement anticorrosion d'une surface métallique, selon lequel la surface concernée est mise successivement en contact avec les compositions aqueuses suivantes :i) une composition nettoyante alcaline ou aqueuse, ii) une première composition de rinçage, iii) éventuellement une deuxième composition de rinçage, iv) une composition de conversion acide, v) éventuellement une troisième composition de rinçage et vi) une composition d'agent d'électrodéposition cationique à base de (méth)acrylate et/ou d'époxy, au moins une des compositions i) à v) contenant au moins un composé de formule (I) et R1 et R2 désignant chacun indépendamment l'un de l'autre H ou un groupe HO- (CH2)w, w ≥ 2, x et y valant chacun indépendamment l'un de l'autre entre 1 et 4, et Z désignant un atome de S ou une liaison triple C-Ct, ainsi qu'une composition aqueuse pour réduire l'enlèvement de matière décapée lors du traitement anticorrosion de surfaces métalliques.
EP17723944.9A 2016-04-29 2017-04-28 Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée Withdrawn EP3448938A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016207431 2016-04-29
PCT/EP2017/060229 WO2017186931A1 (fr) 2016-04-29 2017-04-28 Procédé de traitement anticorrosion d'une surface métallique à enlèvement réduit de matière décapée

Publications (1)

Publication Number Publication Date
EP3448938A1 true EP3448938A1 (fr) 2019-03-06

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BR (1) BR112018071503A2 (fr)
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WO2018050506A1 (fr) 2016-09-15 2018-03-22 Chemetall Gmbh Procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, un alliage d'aluminium, du magnésium et/ou un alliage de zinc et de magnésium
EP3724371A1 (fr) 2017-12-12 2020-10-21 Chemetall GmbH Composition sans acide borique pour éliminer des dépôts contenant de la cryolithe
KR20200086171A (ko) 2019-01-08 2020-07-16 주식회사 엘지화학 배터리 셀의 전극 리드 가접 지그
BR112021019237A2 (pt) * 2019-04-04 2021-11-30 Chemetall Gmbh Concentrado de agente de limpeza alcalino à base de água, agente de limpeza alcalino à base de água, processo para tratamento anticorrosivo de uma superfície metálica, superfície metálica, e, uso da superfície metálica
JP2023530923A (ja) * 2020-06-10 2023-07-20 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング 水性酸洗い組成物及びその使用方法

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RU2018141059A3 (fr) 2020-09-23
JP7034090B2 (ja) 2022-03-11
US20220119650A9 (en) 2022-04-21
US20210222013A1 (en) 2021-07-22
MX2018013229A (es) 2019-02-13
JP2019515134A (ja) 2019-06-06
KR20190002469A (ko) 2019-01-08
RU2754070C2 (ru) 2021-08-25
KR102373768B1 (ko) 2022-03-15
CN109071973A (zh) 2018-12-21
WO2017186931A1 (fr) 2017-11-02
BR112018071503A2 (pt) 2019-02-19
RU2018141059A (ru) 2020-05-29
DE102017207237A1 (de) 2017-11-02

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