EP0085626B1 - Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen - Google Patents

Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen Download PDF

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Publication number
EP0085626B1
EP0085626B1 EP83400204A EP83400204A EP0085626B1 EP 0085626 B1 EP0085626 B1 EP 0085626B1 EP 83400204 A EP83400204 A EP 83400204A EP 83400204 A EP83400204 A EP 83400204A EP 0085626 B1 EP0085626 B1 EP 0085626B1
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EP
European Patent Office
Prior art keywords
composition
titanium
trivalent titanium
process according
trivalent
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.)
Expired
Application number
EP83400204A
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English (en)
French (fr)
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EP0085626A1 (de
Inventor
Joseph Schapira
Victor Ken
Jean-Loup Dauptain
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.)
Compagnie Francaise de Produits Industriels SA
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Compagnie Francaise de Produits Industriels SA
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Priority to AT83400204T priority Critical patent/ATE23574T1/de
Publication of EP0085626A1 publication Critical patent/EP0085626A1/de
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the subject of the invention is a method for the treatment, more precisely the "post-treatment" of phosphated metal surfaces, in particular when these surfaces must be subsequently coated with a layer of paint.
  • the phosphating, including iron and zinc phosphating, of the metal surfaces in question i.e. surfaces of iron, steel, zinc, iron and galvanized steel substrates, d 'aluminum and alloys of the above metals, cadmium and others, aims to protect these surfaces against corrosion; these surfaces are then optionally covered with a layer of paint which may be based more particularly on lacquers, varnishes and enamels applied for example by immersion, electrophoresis, spraying and the like.
  • These treatments which have the aim of further increasing the effectiveness of the protection against corrosion of previously phosphated metal surfaces, generally employ trivalent and / or hexavalent chromium ions in the form of chromium-based compositions or solutions of chromation. chromate applied in final or passivating rinse.
  • the object of the invention is therefore, above all, to provide a process for the treatment of phosphated metal surfaces with the aid of a composition which, while giving these surfaces protection equivalent to that produced by the chromium plating solutions. 'prior art, no longer has the disadvantages of these.
  • the treatment method according to the invention in which after phosphating of metal surfaces and before possible application of a layer of paint, the phosphated metal surface is treated by bringing said surface into contact with a composition comprising titanium, is characterized in that the composition comprises trivalent titanium at a concentration of 0.01 to 2 g / 1 and has a pH of 2 to 7, the temperature of the composition being less than 90 ° C, preferably included between 18 and 60 ° C.
  • composition used in accordance with the method according to the invention contains trivalent titanium at a concentration of 0.2 to 0.6 g / I.
  • the composition used in accordance with the process according to the invention is obtained by dilution with water from a concentrate which may contain, by way of indication, approximately 10 to 50 g of trivalent titanium per liter, this concentrate which is preferably kept away from oxygen in the air until the time of use, being diluted at that time with the quantity of water, preferably distilled or deionized, chosen to result in the concentration of trivalent titanium which corresponds to that of the composition used.
  • the relatively low stability especially in dilute solution and in contact with the oxygen of the air of the compounds containing trivalent titanium, which rapidly oxidizes to tetravalent titanium, means that the composition used in the process in accordance with invention will generally be prepared at the time of use and regenerated if necessary during operation by reduction of tetravalent titanium formed of trivalent titanium.
  • the process according to the invention is therefore characterized by the fact that the trivalent titanium to be comprised by the composition used is prepared in situ and before the application of the composition to the phosphated metal surfaces, by setting in contact with tetravalent titanium with a reduction means, the composition then being, during the process of treatment of phosphate surfaces, regenerated into. trivalent titanium by bringing into contact in particular a fraction derived from the composition with the abovementioned reduction means in such a way that the concentration of the composition in trivalent titanium compound is maintained in the proportion in particular from 0.2 to 0.6 g of trivalent titanium per liter, mentioned above.
  • the process according to the invention is characterized in that the composition used is prepared from a concentrate and that the concentration of trivalent titanium of the composition thus obtained is maintained at the value effective by regeneration during operation in contact with a means of reducing tetravalent titanium to trivalent titanium.
  • the above regeneration can take place continuously.
  • Proposing therefore, to treat, in order to improve its resistance to corrosion, a phosphated metal surface which may possibly receive one or more layers of paint subsequently, this is done as follows or in an equivalent manner.
  • said metallic surface which may be that of a metallic substrate based on iron, steel, zinc, galvanized iron or steel, aluminum, alloys of these metals, of cadmium and others, to a phosphating treatment comprising, after degreasing with the aid in particular of alkaline detergents, the action of a conventional acid phosphating composition with iron or zinc generally implemented hot and for several minutes by immersion or by sprinkling.
  • the metal surface is treated in accordance with the method according to the invention using a composition which contains a trivalent titanium compound at a concentration of 0, 01 to 2 g, preferably 0.2 to 0.6 g of trivalent titanium per liter and has an acid pH of 2 to 7, preferably 2 to 5.
  • the proportions of 0.2 to 0.6 g of trivalent titanium per liter correspond to a value of 4.17 10-3 to 1.25 - 10-2 gram atoms of trivalent titanium per liter.
  • the pH can be adjusted using soda, ammonia, hydrofluoric acid, nitric acid and other acids or bases.
  • the composition is used at a temperature below 90 ° C. and in particular chosen from the range from 18 to 60 ° C.
  • the treatment preferably takes place by immersing the metal surface in the composition for a period generally between 10 and 60 seconds.
  • composition can also be applied by spraying; this technique is less advantageous because of the sensitivity of trivalent titanium with respect to oxidation.
  • the treatment is followed by rinsing with water and drying, in particular hot, of the metal surface before possible application of a paint which can be chosen from lacquers, varnishes, enamels and the like, applied by any process. suitable.
  • the quality of the anti-corrosion protection conferred can be tested by the salt spray test which will be more particularly discussed in relation to the examples. This test is described in the American standards ASTM B 117 and ASTM D 1654-61. The assessment of the corrosion resistance conferred is made using a scale ranging from 0 (zero resistance) to 10 (very good corrosion resistance).
  • the trivalent titanium compound can be chosen from the group comprising chloride, bromide, fluoride, oxalate and trivalent titanium sulfate which have been found to be particularly active.
  • composition used in accordance with the invention must be regenerated to maintain its concentration of trivalent titanium at an effective value, this which can be achieved by contacting a reduction means, in particular a reducing agent.
  • the treatment enclosure containing the composition can be made to include a bypass pipe in which the reducing agent is placed.
  • the composition can be taken from the bottom of the enclosure, passed through the bypass pipe containing the reducing agent and reintroduced onto the surface of the bath constituting the composition.
  • the immersion treatment is of the dynamic type with translation of the parts comprising the phosphated surfaces to be treated, it will be advantageously arranged so that the direction of the current created within the composition, as a result of the sampling in the bypass line, is contrary to the translational movement of the parts.
  • the reduction means can be either a metallic or chemical reducing agent placed in a column, or an electrolysis cell, the column or cell being traversed by the composition to be regenerated continuously or discontinuously so that the titanium concentration trivalent is maintained at the effective value; the effects of the oxidation of the bath and / or of the regeneration are followed by simple volumetric redox dosing and the regeneration is started or stopped when the proportion of the composition in trivalent titanium goes beyond the limits indicated above.
  • an inert electrode is used, the method being that used in redox batteries.
  • test pieces made up of panels of "cold-rolled steel of current quality, thickness 8/10 mm and -measuring 150 mm x 70 mm, are carefully degreased using trichlorethylene then acetone; they are then subjected to a dip phosphating treatment.
  • a commercial phosphating composition is used, in particular that known under the brand "Duridine 49" ® and the concentration of which is 3% by weight.
  • This composition contains phosphating agents and surfactants.
  • the duration of the quenching of the test pieces in the phosphating composition is 10 minutes.
  • the coating obtained is an iron phosphate coating whose layer weight varies between 0.2 and 0.3 g / m2 .
  • test pieces are divided into three sets of five.
  • test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to this satin fog, the results obtained are examined. using ASTM D 1654-61. These results are shown in Table I below; they represent the means of the results of the three series of tests carried out with the three sets of fifteen test pieces.
  • test specimens consisting of panels of "cold-rolled steel of standard quality, 8/10 mm thick, measuring 150 mm x 70 mm. These test pieces are carefully degreased using trichlorethylene and then acetone before undergoing a phosphating conversion treatment by soaking.
  • This treatment is carried out with the same phosphating composition as in Example 1 and in the conditions described in this example.
  • Curve C shown in FIG. 2 illustrates the variation in the content of the bath in grams of Ti (III) per liter of composition (ordinate axis) as a function of the time T expressed in minutes during which recycling is maintained (abscissa axis) in the conditions which have just been specified.
  • test pieces are dried in an oven at 150 ° C. for 5 minutes, then the water-soluble paint of example 1 is applied to them by dipping while respecting the conditions described in this example.
  • test pieces are then subjected to a 5% salt spray corrosion test at a temperature of 35 ° C. under the conditions specified in standard ASTM B 117. After 96 hours of exposure to said salt spray, the results obtained are examined in accordance with to ASTM D 1654-61. These results are shown in Table II below; they represent the averages of the results of the tests carried out on three sets of twenty-five test pieces.
  • a zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .
  • the three sets of five test pieces are then treated respectively as the three sets of five test pieces of Example 1.
  • Example 2 After drying and application of the water-soluble paint under the conditions of Example 1, the three series of test pieces are treated as described in standard ASTM B 117. After 384 hours of exposure to salt spray, the results are examined. obtained using ASTM 1654-61. These results are shown in Table III below; they represent the means of the results of three tests, that is to say tests carried out with three sets of three series of five test pieces.
  • a zinc phosphate coating is obtained, the layer weight of which varies between 2 and 3 g / m 2 .

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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)

Claims (9)

1. Verfahren zur Behandlung von phosphatierten Metalloberflächen, in welchem vor einem eventuellen Auftragen einer Farbschicht die phosphatierte Metalloberfläche durch Inkontaktbringen der genannten Oberfläche mit einer Titan enthaltenden Zusammensetzung behandelt wird, dadurch gekennzeichnet, daß die Zusammensetzung dreiwertiges Titan in einer Konzentration von 0,01 bis 2 g/l enthält und einen pH-Wert von 2 bis 7 aufweist, wobei die Temperatur der Zusammensetzung unter 90 °C liegt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Inkontaktbringen durch Eintauchen erfolgt und 10 bis 60 Sekunden dauert.
3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die eingesetzte Zusammensetzung dreiwertiges Titan in einer Konzentration von 0,2 bis 0,6 g/l enthält.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Temperatur der eingesetzten Zusammensetzung zwischen 18 und 60 °C beträgt.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die eingesetzte Zusammensetzung durch Verdünnen eines 10 bis 50g dreiwertiges Titan je Liter enthaltenden Konzentrates mit Wasser hergestellt wird.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die eingesetzte Zusammensetzung durch Verdünnen eines wenigstens ein obergflächenaktives Mittel und wenigstens ein Stabilisierungsmittel enthaltenden Konzentrates mit Wasser hergestellt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die eingesetzte Zusammensetzung durch Verdünnen eines Konzentrates, das
- von 0,001 bis 0,02 g/I oberflächenaktive Mittel, ausgewählt unter Natriumalkylsulfonaten und ethoxylierten Kohlenwasserstoffen,
- von 1 bis 500 mg/I Stabilisierungsmittel, ausgewählt unter Pyrogallol und Hydrochinon, enthält, mit Wasser hergestellt wird.
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das dreiwertige Titan, das durch die eingesetzte Zusammensetzung aufgebracht werden soll, in situ und vor dem Aufbringen der Zusammensetzung auf die phosphatierten Metalloberflächen durch Inberührungbringen von 4- wertigem Titan mit einem Reduktionsmittel bereitet wird, wobei die Zusammensetzung in der Folge, während der Behandlung der phosphatierten Oberflächen, bezüglich des Gehaltes an dreiwertigem Titan regeneriert wird, indem eine von der Zusammensetzung abgeleitete Fraktion mit dem vorstehend genannten Reduktionsmittel derart in Kontakt gebracht wird, daß die Konzentration der Zusammensetzung an Verbindungen des dreiwertigen Titans in einem Bereich von 0,2 bis 0,6 g dreiwertiges Titan je Liter gehalten wird.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das Reduktionsmittel von vierwertigem Titan zu dreiwertigem Titan ein in einer Kolonne angeordnetes metallisches oder chemisches Reduktionsmittel oder eine Elektrolysezelle ist.
EP83400204A 1982-01-29 1983-01-28 Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen Expired EP0085626B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83400204T ATE23574T1 (de) 1982-01-29 1983-01-28 Zusammensetzung und verfahren zur behandlung von phosphatierten metalloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8201476A FR2520758A1 (fr) 1982-01-29 1982-01-29 Composition et procede pour le traitement de surfaces metalliques phosphatees
FR8201476 1982-01-29

Publications (2)

Publication Number Publication Date
EP0085626A1 EP0085626A1 (de) 1983-08-10
EP0085626B1 true EP0085626B1 (de) 1986-11-12

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EP83400204A Expired EP0085626B1 (de) 1982-01-29 1983-01-28 Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen

Country Status (7)

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US (1) US4497666A (de)
EP (1) EP0085626B1 (de)
JP (1) JPS58136781A (de)
AT (1) ATE23574T1 (de)
CA (1) CA1197674A (de)
DE (1) DE3367630D1 (de)
FR (1) FR2520758A1 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2448684A (en) * 1983-03-02 1984-09-06 Parker Chemical Company Metal treatment before phosphate coating
DE3400339A1 (de) * 1984-01-07 1985-08-29 Gerhard Collardin GmbH, 5000 Köln Verfahren zur nachpassivierung von phosphatierten metalloberflaechen unter verwendung von nickel- und/oder kupfer-kationen enthaltenden loesungen
US5073196A (en) * 1989-05-18 1991-12-17 Henkel Corporation Non-accelerated iron phosphating
DE4031817A1 (de) * 1990-10-08 1992-04-09 Henkel Kgaa Verfahren zur passivierenden nachbehandlung von phosphatierten metalloberflaechen
US5128211A (en) * 1991-02-28 1992-07-07 Diversey Corporation Aluminum based phosphate final rinse

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE154542C (de) *
US2970935A (en) * 1959-03-02 1961-02-07 Parker Rust Proof Co Method of rinsing metallic surfaces with solutions containing hexavalent chromium
FR1388662A (fr) * 1962-10-15 1965-02-12 Parker Ste Continentale Procédé et solution pour le traitement des surfaces métalliques pourvues d'un revêtement chimique
DE1521879B2 (de) * 1966-07-12 1975-08-28 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen und Stahl
US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
US3895970A (en) * 1973-06-11 1975-07-22 Pennwalt Corp Sealing rinse for phosphate coatings of metal
GB1461244A (en) * 1974-06-17 1977-01-13 Lubrizol Corp Treatment of metal surfaces with trivalent chromium solutions
JPS5292836A (en) * 1976-01-30 1977-08-04 Nippon Packaging Kk Zinc or its alloys subjected to chemical conversion
GB1586975A (en) * 1976-07-05 1981-03-25 Kansai Paint Co Ltd Surface treatment of metals
US4165242A (en) * 1977-11-21 1979-08-21 R. O. Hull & Company, Inc. Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating
US4233088A (en) * 1979-03-29 1980-11-11 International Lead Zinc Research Organization, Inc. Phosphatization of steel surfaces and metal-coated surfaces
US4281037A (en) * 1980-08-08 1981-07-28 Dap, Inc. Cleaning and priming composition containing titanium acetylacetonate and method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Gmelins Handbuch der anorganischen Chemie, vol. 41 (1951), pages 373, 413 *
Römpps Chemie-Lexikon (1977), pages 3608, 3609, 3612 *

Also Published As

Publication number Publication date
JPS58136781A (ja) 1983-08-13
DE3367630D1 (en) 1987-01-02
EP0085626A1 (de) 1983-08-10
CA1197674A (en) 1985-12-10
ATE23574T1 (de) 1986-11-15
FR2520758B1 (de) 1984-04-27
FR2520758A1 (fr) 1983-08-05
US4497666A (en) 1985-02-05

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