EP0436408B1 - Verfahren und Bad zum Auftragen einer Schutzbeschichtung auf der Basis von sechswertigem Chrom auf Metalloberflächen und Handelsform der Badbestandteilen - Google Patents

Verfahren und Bad zum Auftragen einer Schutzbeschichtung auf der Basis von sechswertigem Chrom auf Metalloberflächen und Handelsform der Badbestandteilen Download PDF

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Publication number
EP0436408B1
EP0436408B1 EP90403105A EP90403105A EP0436408B1 EP 0436408 B1 EP0436408 B1 EP 0436408B1 EP 90403105 A EP90403105 A EP 90403105A EP 90403105 A EP90403105 A EP 90403105A EP 0436408 B1 EP0436408 B1 EP 0436408B1
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Prior art keywords
bath
solvent
type
boiling point
ketonic
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EP90403105A
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English (en)
French (fr)
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EP0436408A1 (de
Inventor
Joseph Schapira
Patrick Droniou
Daniel Bernard
Patrice Pelletier
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Compagnie Francaise de Produits Industriels SA
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Compagnie Francaise de Produits Industriels SA
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    • 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
    • C23C22/74—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 for obtaining burned-in conversion coatings

Definitions

  • the subject of the invention is a method suitable for imparting to a metallic substrate, a protective coating based on hexavalent chromium; it also relates, and this as new industrial products, the bath used in this process and the commercial form of the constituents of the bath.
  • the metal substrates intended to be protected against corrosion by means of the aforesaid process consist in particular of small metal parts and the screwed devices, for example made of steel or cast iron.
  • Document EP-A-177 086 recommends the use of N-methyl-2-pyrrolidone in a bath free of reducing agents, in other words free of a metal in the form of particles.
  • a single layer coating is thus obtained; to obtain a multilayer coating, the treatment is repeated as many times as necessary.
  • the quality of the coating obtained therefore decreases rapidly with the age of the bath.
  • the object of the invention is, above all, to remedy this drawback and to provide a bath of the kind in question whose stability is improved and which, therefore, allows prolonged use.
  • the above bath advantageously comprises one or more surface-active agents and one or more rheological additives.
  • This bath is established by mixing its constituents at the time of its use.
  • the constituents of the bath are grouped into two or possibly three sets, separated from each other, and put on the market advantageously in the form of what is designated in the trade by the expression "kit".
  • the first will include chromic acid and / or its derivatives in the form of powder or concentrated solution while the second will include, in the form of a dispersion or possibly concentrated slurry, the metal in the form of particles, the water-soluble organic solvent and optionally one or more surface-active agents and one or more rheological additives, the first and the second set being arranged respectively in a first and in a second housing of the kit.
  • the third consists of part or all of the surfactants and rheological agents and arranged in a third housing of the kit.
  • the above first set is in the form of a concentrated solution, it will advantageously contain from 1 to 85% by weight of hexavalent chromium ion expressed as chromate.
  • the second set when in the form of a concentrated slurry, it will advantageously contain from 2 to 80% by weight of metallic particles in dispersion in a part of the organic solvent, the third set containing the surface-active agents. active ingredients and rheological additives in an amount of 1 to 70% by weight in another part of the organic solvent.
  • the metal in the form of particles can be chosen from metals, alloys or mixtures of metals or alloys having a negative normal electrode potential, of absolute value at least equal to that of the metal to be protected.
  • said metal is chosen from the group comprising zinc, iron, aluminum, cadmium, magnesium, manganese and their alloys; zinc, aluminum and their mixtures or alloys are particularly preferred.
  • the size of the metal particles must be compatible with the thickness desired for the protective coating.
  • the bath according to the invention is in the form of an aqueous dispersion of metallic particles comprising approximately 5 to 40% of metal.
  • Hexavalent chromium is provided by chromic acid, its alkali or alkaline earth metal salts, its transition metal salts, its ammonium salt, chromic anhydride and, more generally, any substance capable of releasing ions containing hexavalent chromium; it is present in the bath at a rate of approximately 0.5 to 15% by weight, expressed in chromate ions.
  • the water-soluble solvent with a high boiling point of the ketone type and / or of the aprotic polar type is present in the bath in an amount such that the solvent / chromate ion ratio is between 0.5 and 20.
  • the entering water-soluble solvent in its constitution is chosen from the group comprising cyclohexanone, 2,5-hexane-dione, gammabutyrolactone, dimethyl formamide, dimethyl acetamide, N-methyl-pyrrolidone.
  • the surfactants optionally comprising the bath used in accordance with the invention can be chosen from non-ionic surfactants such as polyethoxy ethers of alkylphenol, of alcohol or of optionally substituted amine.
  • the rheological additives optionally comprising the bath used in accordance with the invention can be chosen from thickening agents such as etherified or esterified celluloses, xanthan derivatives, and thixotropic derivatives of silica, montmorillonite or l aluminum such as aluminum stearate.
  • the metallic substrates which can be treated in accordance with the invention are those based on steel, cast iron and sintered steel used in fasteners, bolts and small parts devices; they can also consist of steel strips.
  • the stage of treatment of the substrate by means of the bath in accordance with the invention can be carried out by soaking followed by draining, by spraying, by soaking followed by centrifugation for small pieces of screws, or else by using rollers when it comes to treating flat metal strips.
  • the substrate is subjected to a baking step between 100 and 350 ° C for a few minutes, in particular for 5 to 45 minutes in order to harden the coating by evaporation of volatile materials.
  • a final baking treatment (at a temperature between 200 and 350 ° C) will be used in place of or in addition to the last baking at a temperature between 120 and 200 ° C.
  • the thickness of the coatings obtained in accordance with the invention is generally between 1 and 15 »m.
  • the substrates subjected to the treatment in accordance with the invention must be clean and suitable for receiving the anticorrosion protective coating. Depending on their degree of soiling, they should be pretreated by alkaline and / or solvent-based degreasing, rinsing and, if necessary, mechanical or chemical pickling.
  • One of the important advantages conferred by the invention resides in the fact that it is unnecessary to provide an additional protective layer, for example paint, on the coatings obtained.
  • a bath according to the invention is prepared from a kit according to the invention comprising three sets, one of which, designated by A, is in the form of a slurry containing the metal, including another, designated by B, is in the form of a solution providing the chromium ion and the third of which, designated by C, comprises a rheological agent.
  • Set A consists of 150 g of lamellar zinc (quality referenced ECKA zinc MP 31 129 / G and sold by the company ECKARTWERKE), 15 g of nonylphenol to 10 moles of ethylene oxide (brand CEMULSOL NP 10 marketed by RHONE-POULENC), 150 g of dimethyl formamide and 2 g of hydroxymethyl cellulose.
  • Set B consists of 27.6 g of chromic acid, 17.4 g of magnesium chromate and 223 g of water.
  • Set C which is used to adjust the viscosity of the final mixture, consists of 4 g of hydroxymethyl cellulose in 581 g of water.
  • a conventional formulation is prepared by mixing the solutions A1 and B1 (compositions indicated below), which gives 100 g of ready-to-use bath.
  • Components of solution A1 Components of solution B1 Lamellar zinc 20g Water 51.9 g Dipropylene glycol 10 g Chromic acid 3 g Ethyl glycol acetate 5 g Zinc oxide 1 g White spirit 5% aromat. 5 g Boric acid 1 g REMCOPAL 334 1 g Hydroxy ethyl cellulose 0.5 g REMCOPAL 349 1.6g
  • the measured values are plotted on the graph of FIG. 1 which represents the evolution of the viscosity in cps as a function of time in days.
  • FIG. 1 shows that the viscosity of the two baths evolves differently: while the bath according to example 2 gradually degrades as a result of gelling from two days, to reach a maximum viscosity at the end of 'About ten days, the bath according to Example 1, according to the invention, retains its fluidity.
  • the dry coating thus obtained has a thickness of approximately 3.5 to 4 »m.
  • the sheets thus treated are subjected to adhesion and corrosion resistance tests, as set out below.
  • the adhesion is all the better as the detachment of the coating is superficial.
  • the strip of adhesive tape has a light gray appearance denoted "5".
  • the rating 5 corresponds to a coating from which no trace has been removed.
  • the test is carried out on the flat non-deformed surface.
  • the adhesion tests were carried out with baths aged 1, 2, 3, 4, 7 and 10 days corresponding to those used for measuring the viscosity of the bath.
  • the quantity of red rust produced is measured as a function of the duration of exposure to salt spray according to standard NF T 41002.
  • the degree of corrosion was measured (expressed as a percentage of corroded surface relative to the total surface) after an exposure of 168 hours, then 400 hours to salt spray with the baths of the previous comparative tests aged 1, 2, 3, 4, 7 and 10 days.
  • Example 2 A bath identical to that of Example 1 is prepared, using zinc dust as the zinc source, for example the Ultra Fine Special quality sold by OLD MOUNTAIN (particle diameter 2-3 "m) and replacing weight by weight, dimethylformamide by dimethyl acetamide:
  • the resistance to salt spray is greater than 600 hours.
  • the resistance to salt spray is greater than 800 hours.
  • a solution A is prepared consisting of 150 g of zinc dust (Ultra Fine Special quality sold by the company VIEILLE MONTAGNE), 30 g of nonyl phenol with 10 moles of ethylene oxide (CEMULSOL NP 10 sold by RHONE-POULENC), 60 g of cyclohexanone and 2 g of hydroxymethyl cellulose.
  • Solution B consists of 27.6 g of chromic acid, 17.4 g of magnesium chromate and 298 g of water.
  • Solution C is identical to that described in Example 1.
  • the three mixed solutions provide 1170 g of ready-to-use bath.
  • the resistance to salt spray is greater than 600 hours.
  • a bath identical to that of Example 1 is prepared in which part of the lamellar zinc (namely 30 g) is replaced by lamellar aluminum (30 g).
  • the lamellar aluminum used is that marketed under the brand Chromal II by the company ECKARTWERKE and the particle size of which is comparable to that of zinc (approximately 18 m in its longest length).
  • a coating on screws is made in two applications as described above with intermediate firing at 180 ° C.
  • the resistance to salt spray is greater than 500 hours.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (6)

  1. Verfahren, geeignet um einem Metallsubstrat eine Schutzbeschichtung gegen Korrosion zu vermitteln, auf Basis von hexavalentem Chrom, welche eine Hilfe einer zusätzlichen Schutzschicht nicht benötigt, und welches umfaßt:
    - einen Vorbereitungsschritt des Metallsubstrats durch Entfetten, gegebenenfalls gefolgt von mechanischem oder chemischem Beizen,
    - einen Behandlungsschritt durch Eintauchen, Besprengen oder mit Rollen mittels eines Bades, welches geeignet ist dem Metallsubstrat die gewünschte Schutzbeschichtung zu vermitteln, wobei das Bad mindestens ein teilchenförmiges Metall, Chromsäure und/oder eines seiner Derivate als Oxidationsmittel, mindestens ein wasserlösliches Lösungsmittel mit hohem Siedepunkt und Wasser umfaßt,
    - sowie einen Erwärmungsschritt bei erhöhter Temperatur,
    wobei das Verfahren dadurch gekennzeichnet ist, daß das wasserlösliche Lösungsmittel mit hohem Siedepunkt ausgewählt wird aus denen des aprotischen polaren Typs und denen des Ketontyps, wobei verstanden wird, daß
    - das Lösungsmittel vom aprotischen polaren Typ der Formel (II) entspricht,
    Figure imgb0013
     worin die Reste R₁, R₂ und R₃ lineare oder verzweigte C₁ bis C₁₈ Alkylgruppen darstellen, die gleich oder unterschiedlich sein und untereinander einen Ring bilden können, wobei der Rest R₁ auch Wasserstoff sein kann, und
    - das Lösungsmittel vom Ketontyp der Formel (I) entspricht,
    Figure imgb0014
     worin die Reste R₁ und R₂ lineare oder verzweigte C₁ bis C₁₈ Alkylgruppen darstellen, die gleich oder unterschiedlich sein und untereinander einen Ring bilden können, oder ein Polyketonderivat oder ein Lacton umfaßt, wobei das Lösungsmittel vom Ketontyp, das Polyketonderivat und das Lacton ausgewählt werden unter denjenigen, bei denen die Wasserlöslichkeit mindestens gleich 5 % (Gew./Gew.) beträgt, der Flammpunkt mehr als oder gleich 50°C beträgt, und der Siedepunkt mindestens gleich 100 °C beträgt.
  2. Bad auf Basis von hexavalentem Chrom, welches geeignet ist einem Metallsubstrat eine Schutzbeschichtung gegen Korrosion zu vermitteln, mindestens umfassend ein teilchenförmiges Metall, Chromsäure und/oder eines seiner Derivate als Oxidationsmittel, mindestens ein wasserlösliches Lösungsmittel mit hohem Siedepunkt und Wasser, wobei das Bad zur Verwendung im Rahmen des Verfahrens nach Anspruch 1 bestimmt ist, dadurch gekennzeichnet, daß das wasserlösliche Lösungsmittel mit hohem Siedepunkt ausgewählt wird aus denen des aprotischen polaren Typs und denen des Ketontyps, wobei verstanden wird, daß
    - das Lösungsmittel vom aprotischen polaren Typ der Formel (II) entspricht,
    Figure imgb0015
     worin die Reste R₁, R₂ und R₃ lineare oder verzweigte C₁ bis C₁₈ Alkylgruppen darstellen, die gleich oder unterschiedlich sein und untereinander einen Ring bilden können, wobei der Rest R₁ auch Wasserstoff sein kann, und
    - das Lösungsmittel vom Ketontyp der Formel (I) entspricht,
    Figure imgb0016
     worin die Reste R₁ und R₂ lineare oder verzweigte C₁ bis C₁₈ Alkylgruppen darstellen, die gleich oder unterschiedlich sein und untereinander einen Ring bilden können, oder ein Polyketonderivat oder ein Lacton umfaßt, wobei das Lösungsmittel vom Ketontyp, das Polyketonderivat oder das Lacton ausgewählt werden unter denjenigen, bei denen die Wasserlöslichkeit mindestens gleich 5 % (Gew./Gew.) beträgt, der Flammpunkt mehr als oder gleich 50°C beträgt, und der Siedepunkt mindestens gleich 100 °C beträgt.
  3. Handelsform für die Bestandteile des Bads nach Anspruch 2, dadurch gekennzeichnet, daß sie zwei Einheiten umfaßt, wovon die erste Chromsäure und/oder eines seiner Derivate in Pulverform oder konzentrierter Lösung umfaßt, während die zweite das teilchenförmige Metall als gegebenenfalls konzentrierte Dispersion oder Aufschlämmung, das wasserlösliche organische Lösungsmittel und gegebenenfalls ein oder mehrere oberflächenaktive Mittel und einen oder mehrere rheologische Zusatzstoffe umfaßt, wobei die erste und zweite Einheit an einer ersten bzw. zweiten Stelle eines Kits angeordnet sind.
  4. Handelsform nach Anspruch 3, dadurch gekennzeichnet, daß sie eine dritte Einheit umfaßt, welche einen Teil oder die Gesamtheit der oberflächenaktiven Mittel und rheologischen Zusatzstoffe umfaßt und in einer dritten Stelle des Kits angeordnet ist.
  5. Bad nach Anspruch 2, dadurch gekennzeichnet, daß das wasserlösliche Lösungsmittel vom Ketontyp oder vom polaren aprotischen Typ in einer Menge vorhanden ist, so daß das Verhältnis Lösungsmittel/Chromat-Ion zwischen 0,5 und 20 liegt.
  6. Bad nach einem der Ansprüche 2 und 5, dadurch gekennzeichnet, daß das wasserlösliche Lösungsmittel ausgewählt ist aus der Gruppe umfassend Cyclohexanan, Hexan-2,5-dion, Gammabutyrolacton, Dimethylformamid, Dimethylacetamid, N-Methylpyrrolidon.
EP90403105A 1989-11-06 1990-11-02 Verfahren und Bad zum Auftragen einer Schutzbeschichtung auf der Basis von sechswertigem Chrom auf Metalloberflächen und Handelsform der Badbestandteilen Expired - Lifetime EP0436408B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8914526 1989-11-06
FR8914526A FR2654117B1 (fr) 1989-11-06 1989-11-06 Procede propre a conferer a un substrat metallique un revetement protecteur a base de chrome hexavalent, bain mis en óoeuvre dans ce procede et forme commerciale des constituants du bain.

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EP0436408A1 EP0436408A1 (de) 1991-07-10
EP0436408B1 true EP0436408B1 (de) 1995-08-23

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US (1) US5259884A (de)
EP (1) EP0436408B1 (de)
JP (1) JPH07116614B2 (de)
AT (1) ATE126834T1 (de)
CA (1) CA2029381A1 (de)
DE (1) DE69021856T2 (de)
ES (1) ES2077047T3 (de)
FR (1) FR2654117B1 (de)

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CN102911534B (zh) * 2012-10-18 2015-06-17 王宏 水基无铬锌铝涂液及其制备方法和使用方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2762732A (en) * 1951-11-19 1956-09-11 Parker Rust Proof Co Solution for and method of cleaning and coating metallic surfaces
GB1184562A (en) * 1966-04-05 1970-03-18 Ass Chem Co Anti-Corrosive Coating Compositions
GB1273413A (en) * 1968-05-17 1972-05-10 Diamond Shamrock Corp Improvements in or relating to coated metals
US3755003A (en) * 1970-07-24 1973-08-28 Diamond Shamrock Corp Method of preparing and using concrete reinforcing elements
US3907608A (en) * 1971-08-19 1975-09-23 Diamond Shamrock Corp Coated metal and method
BE787704A (fr) * 1971-08-19 1973-02-19 Diamond Shamrock Corp Compostion de revetement, metal revetu et revetement comprenant l'application par voie electrique de couches de finition.
US3779815A (en) * 1972-01-03 1973-12-18 Diamond Shamrock Corp Applying chromic acid-amino acid, or lactam, or amide coating compositions to metals
BR7302780D0 (pt) * 1972-04-21 1974-08-15 Diamond Shamrock Corp uma composicao liquida de revestimento para aplicacao a uconcentrado de composicao, e processo para a preparacao dem substrato de metal
US3954510A (en) * 1972-10-18 1976-05-04 Diamond Shamrock Corporation Metal treating compositions of controlled pH
SE387133B (sv) * 1972-10-18 1976-08-30 Diamond Shamrock Corp Sett att framstella en grundfergsoverdragningskomposition
FR2311074A1 (fr) * 1975-05-15 1976-12-10 Diamond Shamrock Corp Composition de pre-melange pour composition de revetement de substrats metalliques
GB8424159D0 (en) * 1984-09-25 1984-10-31 Pyrene Chemical Services Ltd Cromate coatings for metals
FR2600072B1 (fr) * 1986-06-13 1988-10-21 Dacral Sa Composition de revetement anticorrosion a stabilite amelioree, et substrat revetu

Also Published As

Publication number Publication date
DE69021856D1 (de) 1995-09-28
FR2654117A1 (fr) 1991-05-10
JPH07116614B2 (ja) 1995-12-13
ATE126834T1 (de) 1995-09-15
CA2029381A1 (en) 1991-05-07
FR2654117B1 (fr) 1994-02-04
JPH03294485A (ja) 1991-12-25
US5259884A (en) 1993-11-09
ES2077047T3 (es) 1995-11-16
EP0436408A1 (de) 1991-07-10
DE69021856T2 (de) 1996-01-11

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