EP0085626A1 - 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
EP0085626A1
EP0085626A1 EP83400204A EP83400204A EP0085626A1 EP 0085626 A1 EP0085626 A1 EP 0085626A1 EP 83400204 A EP83400204 A EP 83400204A EP 83400204 A EP83400204 A EP 83400204A EP 0085626 A1 EP0085626 A1 EP 0085626A1
Authority
EP
European Patent Office
Prior art keywords
composition
trivalent titanium
titanium
trivalent
concentrate
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.)
Granted
Application number
EP83400204A
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English (en)
French (fr)
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EP0085626B1 (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
Original Assignee
Compagnie Francaise de Produits Industriels SA
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.)
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Publication date
Application filed by Compagnie Francaise de Produits Industriels SA filed Critical Compagnie Francaise de Produits Industriels SA
Priority to AT83400204T priority Critical patent/ATE23574T1/de
Publication of EP0085626A1 publication Critical patent/EP0085626A1/de
Application granted granted Critical
Publication of EP0085626B1 publication Critical patent/EP0085626B1/de
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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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment

Definitions

  • the subject of the invention is a composition and 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.
  • It also relates to a process for preparing the composition and a concentrate which can be used for this preparation.
  • 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.
  • the object of the invention is therefore, above all, to provide a composition and a process for the treatment of phosphated metal surfaces which, while giving these surfaces protection equivalent to that achieved by the chromating solutions of the prior art, do not has the disadvantages of these.
  • the treatment composition according to the invention is characterized in that it comprises an effective proportion of trivalent titanium compound and that it is present with an acidic pH, it being understood that, by the expression "effective proportion” means the proportion of compound sufficient for the corresponding composition to give the treated metal surface protection equivalent to that obtained with known chromating solutions.
  • composition according to the invention contains trivalent titanium at a concentration of 0.01 to 2 g / 1, preferably from 0.2 to 0.6 g / 1 and has a pH of 2 to 7.
  • the composition is in the form of 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. air until the time of use being diluted at that time with the amount of preferably distilled or deionized water, chosen to achieve the effective concentration of trivalent titanium in the final composition.
  • the treatment method according to the invention is characterized in that, in a method of phosphating metal surfaces and before any application of a layer of paint, the phosphated metal surface is treated by bringing said surface into contact with a composition according to the invention, the duration of contacting must be sufficient to give the treated surface the desired corrosion resistance.
  • the processing takes place by immersion, static or dynamic, of the metal surface to be treated in the composition according to the invention, the duration of the immersion being from 10 to 60 seconds and the temperature of the composition below 90 ° C., preferably between 18 and 60 ° C.
  • composition in accordance with the invention will generally be prepared at time of use and regenerated if necessary during operation by reduction of the tetravalent titanium formed into trivalent titanium.
  • the process for preparing the composition in accordance with the invention is therefore characterized in that the trivalent titanium is prepared in situ and before the application of the composition to the phosphated metal surfaces, by bringing the titanium into contact tetravalent with a reduction means, the composition being then, during the process of treatment of the phosphated surfaces, regenerated into trivalent titanium by contacting such a fraction derived from the composition with the 'aforementioned reducing means such that the concentration of the composition of trivalent titanium compound is maintained at the effective proportion, in particular from 0.2 to 0.6 g of trivalent titanium per liter, mentioned above.
  • the above-mentioned process for preparing the composition according to the invention is characterized in that the concentrate according to the invention is used and that the concentration of trivalent titanium in the composition is maintained thus obtained at the effective value by regeneration during operation in contact with a means for 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.
  • metal surface which may be that of a metal substrate based on iron, steel, zinc, galvanized iron or steel, aluminum, d alloys of these metals, 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 carried out hot and for several minutes by immersion or by sprinkling.
  • the metal surface is treated with the composition according to the invention.
  • 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 pen composition. for a duration 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 according to the invention is prepared at the start in the form of a concentrate;
  • this concentrate can contain approximately 10 to 50 g of trivalent titanium per liter.
  • composition according to the invention must be regenerated in order to maintain its concentration of trivalent titanium at an effective value, 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; we follow the effects of the oxidation of bath and / or regeneration by simple volumetric redox dosing and the regeneration is started or stopped when the proportion of the trivalent titanium composition exceeds the limits indicated above.
  • an inert electrode is used, the method being that used in redox batteries.
  • One of the objects of the invention therefore consists of an industrial product comprising, on the one hand, the composition according to the invention in the form of a concentrate in which the titanium is preferably in the trivalent state and, on the other hand, a means of reduction capable of regenerating, by reduction of the tetravalent titanium into trivalent titanium, the composition prepared from the concentrate and, if necessary, bringing in a first phase the concentration of the composition in trivalent titanium to the desired value in the case where the starting concentrate is based on tetravalent titanium or contains too low a proportion of trivalent titanium.
  • test pieces made up of 8/10 mm thick "cold-rolled steel of current quality" panels, measuring 150 mm x 70 mm, are carefully degreased using trichlorethylene and then acetone and are then subjected to a dip phosphating treatment.
  • a commercial phosphating composition is used, in particular that known under the brand " D uridine 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 / m 2 .
  • 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 salt spray, 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 pieces consisting of 8/10 mm thick "standard cold rolled steel" panels 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 under 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 thus prepared are dried in an oven at 150 ° C for 5 minutes, then the water-soluble paint of Example 1 is applied to them by soaking, 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 eyes of five-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 .

Landscapes

  • 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)
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 true EP0085626A1 (de) 1983-08-10
EP0085626B1 EP0085626B1 (de) 1986-11-12

Family

ID=9270495

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83400204A Expired EP0085626B1 (de) 1982-01-29 1983-01-28 Zusammensetzung und Verfahren zur Behandlung von phosphatierten Metalloberflächen

Country Status (7)

Country Link
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)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4600447A (en) * 1984-01-07 1986-07-15 Henkel Kommanditgesellschaft Auf Aktien After-passivation of phosphated metal surfaces
US5073196A (en) * 1989-05-18 1991-12-17 Henkel Corporation Non-accelerated iron phosphating
US5391240A (en) * 1990-10-08 1995-02-21 Henkel Kommanditgesellschaft Auf Aktien Process for the passivating post-treatment of phosphatized metal surfaces

Families Citing this family (2)

* 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
US5128211A (en) * 1991-02-28 1992-07-07 Diversey Corporation Aluminum based phosphate final rinse

Citations (7)

* 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
FR2117256A5 (de) * 1970-12-02 1972-07-21 Amchem Prod
FR2232615A1 (de) * 1973-06-11 1975-01-03 Pennwalt Corp
FR2274706A1 (fr) * 1974-06-17 1976-01-09 Lubrizol Corp Traitement de surfaces metalliques avec des solutions de chrome trivalent et articles obtenus
FR2339683A1 (fr) * 1976-01-30 1977-08-26 Parker Ste Continentale Procede de post-traitement d'une surface de zinc ou d'alliages de zinc prealablement soumise a une conversion chimique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1521879B2 (de) * 1966-07-12 1975-08-28 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum Aufbringen von Phosphatüberzügen auf Eisen und Stahl
CA1091914A (en) * 1976-07-05 1980-12-23 Hideo Kogure Metal surface treatment liquid and rust preventive paint
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

Patent Citations (7)

* 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
FR2117256A5 (de) * 1970-12-02 1972-07-21 Amchem Prod
FR2232615A1 (de) * 1973-06-11 1975-01-03 Pennwalt Corp
FR2274706A1 (fr) * 1974-06-17 1976-01-09 Lubrizol Corp Traitement de surfaces metalliques avec des solutions de chrome trivalent et articles obtenus
FR2339683A1 (fr) * 1976-01-30 1977-08-26 Parker Ste Continentale Procede de post-traitement d'une surface de zinc ou d'alliages de zinc prealablement soumise a une conversion chimique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4600447A (en) * 1984-01-07 1986-07-15 Henkel Kommanditgesellschaft Auf Aktien After-passivation of phosphated metal surfaces
US5073196A (en) * 1989-05-18 1991-12-17 Henkel Corporation Non-accelerated iron phosphating
US5391240A (en) * 1990-10-08 1995-02-21 Henkel Kommanditgesellschaft Auf Aktien Process for the passivating post-treatment of phosphatized metal surfaces

Also Published As

Publication number Publication date
FR2520758B1 (de) 1984-04-27
JPS58136781A (ja) 1983-08-13
EP0085626B1 (de) 1986-11-12
CA1197674A (en) 1985-12-10
ATE23574T1 (de) 1986-11-15
FR2520758A1 (fr) 1983-08-05
US4497666A (en) 1985-02-05
DE3367630D1 (en) 1987-01-02

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