EP2358922B1 - Couches de conversion pour surfaces contenant du zinc - Google Patents

Couches de conversion pour surfaces contenant du zinc Download PDF

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Publication number
EP2358922B1
EP2358922B1 EP09760833.5A EP09760833A EP2358922B1 EP 2358922 B1 EP2358922 B1 EP 2358922B1 EP 09760833 A EP09760833 A EP 09760833A EP 2358922 B1 EP2358922 B1 EP 2358922B1
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EP09760833.5A
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German (de)
English (en)
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EP2358922A1 (fr
Inventor
Björn Dingwerth
Andreas Noack
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to PL09760833T priority Critical patent/PL2358922T3/pl
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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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • 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
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the invention relates to the corrosion protection of metallic materials, in particular of those which are provided with a conversion layer.
  • the coating of the metallic workpiece to be protected with a coating of another metal is a widely used and established method in the art.
  • the coating metal can behave in the corrosive medium either electrochemically nobler or less noble than the material base metal alone. If the coating metal behaves less noble, it acts as a sacrificial anode in the corrosive medium in the sense of cathodic protection against the base metal. Although this is associated with the formation of corrosion products of the coating metal protection function is indeed desirable, but the corrosion products of the coating often lead even to undesirable decorative and often to functional impairments of the workpiece.
  • so-called conversion layers are often used especially on cathodically protective base coating metals such as zinc and its alloys. These are reaction products of the base metal which are insoluble in aqueous media over a wide pH range with the reaction solution.
  • conversion layers are, for example, so-called phosphating and chromating.
  • phosphating the layer to be protected is dipped in an acidic solution containing phosphate ions.
  • the acidic medium leads to the partial dissolution of zinc from the coating.
  • the liberated Zn 2+ cations form a sparingly soluble zinc phosphate layer on the surface with the phosphate ions of the reaction solution. Since zinc phosphate layers themselves form only a comparatively poor corrosion protection, but an excellent primer for this applied paints and paints are their main application in the function as a primer for coatings and paints.
  • the surface to be treated is dipped in an acidic solution containing chromium (VI) ions.
  • chromium (VI) ions For example, if it is a zinc surface, some of the zinc will dissolve.
  • chromium (VI) is reduced to chromium (III), which in the hydrogenation more alkaline surface film u.a. as chromium (III) hydroxide or as sparingly soluble ⁇ -oxo or ⁇ -hydroxo-bridged chromium (III) complex is deposited.
  • sparingly soluble zinc chromate (VI) is formed. Overall, a tightly closed, very well protects against corrosion attack by electrolytes conversion coating on the zinc surface.
  • chromium (VI) compounds are distinguished by their high carcinogenic potential, so that it is necessary to replace the processes associated with these compounds.
  • chromating processes with hexavalent chromium compounds a large number of processes have now been established which use different complexes of trivalent chromium compounds.
  • a decisive step in the course of the deposition is a reaction by which the pH at the interface of the zinc surface or zinc-containing surface to the solution increases to such an extent that the deposition of the conversion layer takes place.
  • Chromium (III) is not suitable in the sense described above as an oxidizing agent for zinc. Reduction to chromium (II) is possible due to redox potential, but does not increase the pH at the interface. It is therefore necessary, in order to build up a conversion layer from an aqueous acidic solution of chromium (III) ions, to additionally add a suitable oxidizing agent which increases the concentration of zinc ions as well as the pH at the zinc or zinc alloy interface in that the components of the conversion layer which are soluble in the inside of the solution in solution on the metal surface are converted into a sparingly soluble hydrolysis form.
  • Nitrate is first reduced to nitrite under the usual reaction conditions of the treatment solutions.
  • nitrite is in the acidic medium of the treatment solutions, the pH is usually between pH 1 and pH 3.5, not stable but tends to disproportionation in nitrate and nitrogen monoxide: 3NO 2 - + 2H 3 O + ⁇ NO 3 - + 2NO + 3H 2 O
  • Nitrogen oxides are toxic gases and must be extracted by suction above the surface of the solution.
  • the patent EP 1 816 234 A1 describes an aqueous reaction solution and a process for passivating zinc and zinc alloys.
  • the reaction solutions contain nicotinic acid, its salts or their derivatives. From such reaction solutions, colored passivation layers are produced on zinc and zinc alloys. Nicotinic acid is not suitable as an oxidizing agent in chromium (III) -containing treatment solutions for producing conversion coatings on zinc-containing surfaces.
  • the patent EP 1 970 470 A1 describes chromium (VI) -free black passivations for zinc-containing surfaces, which can contain as complexing agents carboxylic acid derivatives of pyridine. Such carboxylic acid derivatives of pyridine can not act as oxidizing agents in such solutions.
  • the patents EP 1 005 578 B1 and GB 715,607 describe methods for producing phosphating layers.
  • the accelerators used here are organic nitro compounds and organic N-oxides.
  • the phosphating layers described here are porous and therefore offer no corrosion protection.
  • These criteria are met by the organic oxidizing agents of the invention selected from aliphatic nitro compounds, aromatic nitro compounds, N-oxides and quinones. Substitution of nitrates by water-soluble, organic oxidants does not result in gaseous, toxic reaction products.
  • nitrate ions can be present in the solution without the negative properties being problematic.
  • the solution does not contain nitrate.
  • Suitable classes of compounds are e.g. Nitrobenzoic acids, nitrosalicylic acids, nitrophenols, dinitrophenols, trinitrophenols, nitropropionic acid, pyridine N-oxides, morpholine N-oxides and benzoquinones.
  • Suitable compounds in the meaning of the invention are therefore, e.g. m-nitrobenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3,5-dinitrosalicylic acid, 2,4-dinitrophenol, m-nitrobenzenesulfonic acid, N-methylmorpholine N-oxide, pyridine N-oxide and p-benzoquinone.
  • Equation 1 Examples of reduction reactions of suitable organic oxidants in an acidic medium.
  • Another advantage of the components of the invention is that they have no free nitrate and thus can be used in solutions for the production of conversion layers containing dyes with amino groups.
  • the disadvantage of the use of nitrate ions known in the art for producing the conversion layer is that the nitrate is reduced to nitrite. This nitrite can undergo diazotization reactions in the strongly acidic solution to form the conversion layer with amino-containing dyes, which react to undefined dye products, which no longer give the desired surface color of the conversion layer. Such reactions go organically bound NO groups according to the formulas I. - III. not a.
  • Aqueous treatment solutions according to the invention contain between 0.2 g / l and 20 g / l chromium (III), preferably between 0.5 g / l and 15 g / l chromium (III) ions and more preferably between 1 g / l and 5 g / l chromium (III) ions.
  • no Cr (VI) salts are added to the solution.
  • anions for example, methanesulfonate, sulfate, hydrogen sulfate, borates, and the anions of acidic boric acid esters, phosphate, hydrogen phosphate, dihydrogen phosphate, nitrate, nitrite, chloride, iodide, fluoride, hexafluorosilicate, hexafluorotitanate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, phosphate, hydrogen phosphate, dihydrogen phosphate or contain corresponding anions of esters of phosphoric acid.
  • Chromium (III) may be added to the solutions either in the form of a chromium (III) salt, e.g. basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, potassium chromium (III) sulfate, or chromium (III) salts of organic acids, e.g. Chromium (III) methanesulfonate, chromium (III) citrate are added.
  • a chromium (III) salt e.g. basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, potassium chromium (III) sulfate, or chromium (III) salts of organic acids, e.g. Chromium (III) methanesulfon
  • complexing agents can be used, such as polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, aminocarboxylic acids or hydroxyphosphonic acids.
  • carboxylic acids are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, sebacic, maleic, phthalic, terephthalic, tartaric, citric, malic, ascorbic, ethylenedinitrilotetraacetic, tetrahydrofuran-2-carboxylic, maleic, ethylenediaminetetraacetic, diethylenediaminepentaacetic acid , Nitrilotriacetic acid, lactic acid, adipic acid, 4-aminohippuric acid, 4-aminobenzoic acid, 5-aminoisophthalic acid, L-aspartic acid, L-glutamine, L-glutamic acid, alanine, beta-alanine, L-arginine
  • the concentration of complexing agents in The treatment solutions may be between 0.05 g / l and the solubility limit of the complexing agents.
  • the treatment solutions may further comprise one or more surfactants such as e.g. Oxo-alcohol ethoxylates (eg Lugalvan ON110, BASF), fatty alcohol ethoxylates (eg Ethylan CPG 660, Julius Hoesch GmbH), or surfactants with fluorinated radicals (eg Novec FC-4432, 3M) and between 0.01 g / l and 10 g / l of another Metal ions or metalloidion such as Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P.
  • surfactants such as e.g. Oxo-alcohol ethoxylates (eg Lugalvan ON110, BASF), fatty alcohol ethoxylates (eg Ethylan CPG 660, Julius Hoesch GmbH), or surfactants with fluorinated radicals (eg Novec FC-4432, 3M) and between 0.01
  • An aqueous treatment solution is prepared which contains 3.0 g / l Cr 3+ (from chromium (III) chloride hexahydrate), 2 g / l Co 2+ (from cobalt sulfate heptahydrate) and 8 g / l PO 4 3- (from ortho Phosphoric acid) and 2.5 g / l Fe 2+ (from iron (III) sulfate heptahydrate) and a compound of the invention or nitrate according to Comparative Example shown in Table 1 contains.
  • the treatment solution is adjusted to a pH of 1.6 with nitric acid / sodium hydroxide.

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

Claims (10)

  1. Utilisation d'au moins un composé organique, choisi dans le groupe contenant :
    Figure imgb0016
    Figure imgb0017
     R1 à R5 représentant, indépendamment les uns des autres
    a) un atome d'hydrogène ou un groupe alkyle comprenant 1 à 10 atomes de carbone, linéaire ou ramifié ou
    b) un groupe -NR2, -NO2, -COOR, -OR, -SO3R avec R = -H ou un groupe alkyle comprenant 1 à 5 atomes de carbone, linéaire ou ramifié,
    et à condition que 0 à 2 radicaux R1 à R5 soient choisis dans le groupe b)
    dans une solution aqueuse de traitement, contenant des ions Cr3+ pour générer des couches de conversion pratiquement exemptes de chrome (VI) sur des couches de zinc ou des couches d'alliage de zinc pour éviter la formation d'oxydes d'azote lors du dépôt des couches de conversion.
  2. Utilisation selon la revendication 1, caractérisée en ce que le composé organique est choisi dans le groupe comprenant
    Figure imgb0018
    Figure imgb0019
     R1 à R5 représentant, indépendamment les uns des autres
    a) un atome d'hydrogène ou un groupe alkyle comprenant 1 à 10 atomes de carbone, linéaire ou ramifié ou
    b) un groupe -NR2, -NO2, -COOR, -OR, -SO3R avec R = -H ou un groupe alkyle comprenant 1 à 5 atomes de carbone, linéaire ou ramifié,
    et à condition que 0 à 2 radicaux R1 à R5 soient choisis dans le groupe b).
  3. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le composé organique est choisi dans le groupe comprenant
    Figure imgb0020
     R1 à R5 représentant, indépendamment les uns des autres
    a) un atome d'hydrogène ou un groupe alkyle comprenant 1 à 10 atomes de carbone, linéaire ou ramifié ou
    b) un groupe -NR2, -NO2, -COOR, -OR, -SO3R avec R = -H ou un groupe alkyle comprenant 1 à 5 atomes de carbone, linéaire ou ramifié,
    et à condition que 0 à 2 radicaux R1 à R5 soient choisis dans le groupe b).
  4. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le composé organique est choisi dans le groupe contenant l'acide m-nitrobenzoïque, l'acide 2-hydroxy-5-nitrobenzoïque, l'acide 3,5-dinitrosalicylique, le 2,4-dinitrophénol, l'acide m-nitrobenzènesulfonique, le N-méthylmorpholin-N-oxyde, le pyridin-N-oxyde et la p-benzoquinone.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la concentration en composés organiques I.-V. est située entre 30 mg/l et 30 g/l de substance.
  6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la solution de traitement contient entre 0,2 g/l et 20 g/l d'ions de chrome (III).
  7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la solution de traitement contient au moins un anion choisi dans le groupe contenant le méthanesulfonate, le sulfate, l'hydrogénosulfate, le borate, les esters acides de l'acide borique, le phosphate, l'hydrogénophosphate, le dihydrogénophosphate, le chlorure, l'iodure, le fluorure, le nitrate, l'hexafluorosilicate, l'hexafluorotitanate, le tétrafluoroborate, l'hexafluoroantimonate, l'hexafluorophosphate, le phosphate, l'hydrogénophosphate, le dihydrogénophosphate et les anions d'esters de l'acide phosphorique.
  8. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la solution de traitement aqueuse contient en outre au moins un métal ou métalloïde, choisi dans le groupe contenant Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si, P en une concentration entre 0,01 et 10 g/l.
  9. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la solution de traitement contient entre 0,05 g/l et 20 g/l d'au moins un complexant choisi dans le groupe contenant les acides polycarboxyliques, les acides hydroxycarboxyliques, les acides hydroxypolycarboxyliques, les acides aminocarboxyliques ou les acides hydroxyphosphoniques.
  10. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que la solution de traitement présente un pH entre pH 0,1 et pH 7.
EP09760833.5A 2008-11-27 2009-11-23 Couches de conversion pour surfaces contenant du zinc Not-in-force EP2358922B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09760833T PL2358922T3 (pl) 2008-11-27 2009-11-23 Powłoki konwersyjne dla powierzchni zawierających cynk

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DE102008044143A DE102008044143B4 (de) 2008-11-27 2008-11-27 Wässrige Behandlungslösung und Verfahren zur Erzeugung von Konversionsschichten für zinkhaltige Oberflächen
PCT/EP2009/065646 WO2010060883A1 (fr) 2008-11-27 2009-11-23 Couches de conversion pour surfaces contenant du zinc

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EP2358922A1 EP2358922A1 (fr) 2011-08-24
EP2358922B1 true EP2358922B1 (fr) 2016-01-27

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US (1) US20110217476A1 (fr)
EP (1) EP2358922B1 (fr)
JP (1) JP5562347B2 (fr)
KR (1) KR20110089304A (fr)
CN (1) CN102227516B (fr)
DE (1) DE102008044143B4 (fr)
ES (1) ES2565839T3 (fr)
PL (1) PL2358922T3 (fr)
WO (1) WO2010060883A1 (fr)

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US20160348245A1 (en) * 2015-05-28 2016-12-01 Macdermid, Incorporated Method of Pretreatment for Electroless Plating
EP3156518A1 (fr) * 2015-10-14 2017-04-19 Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH Composition inhibitrice de corrosion pour alliages de magnésium ou magnésium
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CN114592186B (zh) * 2022-04-27 2024-03-12 上海库曜新材料有限公司 一种锌粉的无铬钝化方法

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Publication number Publication date
JP5562347B2 (ja) 2014-07-30
EP2358922A1 (fr) 2011-08-24
DE102008044143B4 (de) 2011-01-13
ES2565839T3 (es) 2016-04-07
CN102227516A (zh) 2011-10-26
JP2012509994A (ja) 2012-04-26
PL2358922T3 (pl) 2016-07-29
US20110217476A1 (en) 2011-09-08
KR20110089304A (ko) 2011-08-05
CN102227516B (zh) 2015-07-22
WO2010060883A1 (fr) 2010-06-03
DE102008044143A1 (de) 2010-06-02

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