EP0796356B1 - Procede d'application de revetements de phosphate sur des surfaces metalliques - Google Patents

Procede d'application de revetements de phosphate sur des surfaces metalliques Download PDF

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Publication number
EP0796356B1
EP0796356B1 EP95941068A EP95941068A EP0796356B1 EP 0796356 B1 EP0796356 B1 EP 0796356B1 EP 95941068 A EP95941068 A EP 95941068A EP 95941068 A EP95941068 A EP 95941068A EP 0796356 B1 EP0796356 B1 EP 0796356B1
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EP
European Patent Office
Prior art keywords
zinc
phosphate
phosphating
alloys
phosphating solution
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Expired - Lifetime
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EP95941068A
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German (de)
English (en)
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EP0796356A1 (fr
Inventor
Thomas Wendel
Hardy Wietzoreck
Klaus Bittner
Peter Schiefer
Marcus Schinzel
Helmut HÜLSMANN
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Chemetall GmbH
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Metallgesellschaft AG
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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
    • C23C22/18—Orthophosphates containing manganese cations
    • 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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • 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
    • C23C22/36—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 containing also phosphates
    • 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
    • C23C22/36—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 containing also phosphates
    • C23C22/364—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 containing also phosphates containing also manganese cations
    • 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
    • C23C22/36—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 containing also phosphates
    • C23C22/364—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 containing also phosphates containing also manganese cations
    • C23C22/365—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 containing also phosphates containing also manganese cations containing also zinc and nickel cations

Definitions

  • the invention relates to a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their alloys by wetting with a divalent cation and Phosphate-containing phosphating solution and subsequent Drying up the liquid film.
  • Such phosphating solutions usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components. Besides the cation zinc can other cations, e.g. Ammonium, calcium, cobalt, iron, potassium, Copper, sodium, magnesium, manganese, be present.
  • the phosphating solutions in general oxidizing agents, such as bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate or Hydrogen peroxide added.
  • additives such as Fluoride, silicon fluoride, boron fluoride, citrate and tartrate. Due to the large number of individual components and their possible combinations results in a variety of different compositions of the Phosphating solutions.
  • a special design of the phosphating process is the so-called low-zinc processes.
  • the used here Phosphating solutions contain zinc in concentrations of only about 0.4 to 1.7 g / l and produce phosphate layers especially on steel with a high proportion of phosphophyllite, which has better paint adhesion and a higher resistance to paint infiltration Corrosion stress offers than it does in the generation of Phosphate layers based on Hopeit from phosphating solutions with higher Zinc content is common.
  • a comparatively new development are phosphating processes, which are referred to in the professional world as the trication method.
  • low-zinc phosphating processes in which Use of nickel in e.g. Quantities of 0.3 - 2.0 g / l and manganese in Amounts of e.g. 0.5-1.5 g / l phosphate coatings are obtained which are characterized by increased alkali resistance and therefore for the cathodic electrocoating, in particular of Car bodies are important.
  • Another trication method provides for the concentrations of nickel to a value between about 80 and 94 mol%, of manganese between about 0.5 and 10 mol% and zinc between about 5.5 and 19.5 mol% (based to the sum of the cations).
  • the content of Total acidity 10 to 40 points, the free acidity 0.5 to 2 points and the ratio of total acid to free acid is 10 to 60 (US-A-4596607).
  • the aforementioned phosphating process has in common that the Phosphating solution in dipping, flooding or spraying with the Phosphating solution in dipping, flooding or spraying with the treating workpiece surfaces is brought into contact.
  • Critalline phosphate layer is required for the removal of on the Surface remaining phosphating chemicals of a rinsing treatment, which is usually carried out in several stages.
  • rinsing solutions that are not disposed of in this form can, but must be sent to a wastewater treatment plant.
  • a disadvantage of such a procedure is, however, that due to the requirement that the Components of the phosphating solution the freedom for adaptation the composition of the phosphating solution to the Practice needs are severely limited.
  • Coating solutions can be applied while diving or Spray and then squeeze off the excess solution or by roller application, in which only the required Amount of liquid is applied to the metal surface, respectively.
  • the treatment solution can be applied while diving or Spray and then squeeze off the excess solution or by roller application, in which only the required Amount of liquid is applied to the metal surface, respectively.
  • which depends on the application of the treatment liquid subsequent drying can in principle be carried out at room temperature respectively. In general, however, it is common to have higher temperatures apply, preferably temperatures between 50 and 100 ° C. to get voted.
  • the process consists of using a metal surface To wet phosphating liquid that has a pH of 1.5 to 3, is chromium-free and, in addition to metal phosphate, soluble molybdate, Contains tungstate, vanadate, niobate and / or tantalate ions (EP-B-15 020).
  • the cationic component of the solution metal phosphate by calcium, magnesium, barium, Aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese be formed.
  • a disadvantage of the latter method is that due to the required additives molydate, tungstate, vanadate, niobate and Tantalizations cost more than the process conventional phosphating process, another is that the obtained Phosphate coatings do not meet all requirements today, e.g. B. with regard to alkali resistance and thus resistance to a subsequent cathodic electrocoating and the desired corrosion resistance, especially in connection with a subsequent painting, are sufficient.
  • the object of the invention is to provide a method for applying Phosphate coatings on surfaces of zinc, iron, aluminum or their To provide alloys that are known, in particular does not have the aforementioned disadvantages, yet inexpensive and is simple to implement and of high quality Phosphate coatings leads.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the surfaces are coated with a phosphating solution which is free from elements of the 5th and 6th subgroups of the Periodic Table of the Elements, 0.5 to 8 g / l nickel 2 to 20 g / l manganese 18 to 170 g / l Phosphate (calculated as P 2 O 5 ) contains and has an S value of 0.4 to 0.8, wetted in such a way that a phosphate layer weight of 0.3 to 3.0 g / m 2 results after drying, the phosphating solution in the case of phosphating surfaces from iron, aluminum or their alloys necessarily contains 0.5 to 5 g / l zinc and can contain zinc ions in the case of phosphating surfaces made of zinc or zinc alloys.
  • the S value is expediently set using nickel oxide, manganese oxide or possibly zinc oxide or with ammonia solution.
  • An expedient embodiment of the invention provides, in the case of Treatment of zinc or zinc alloys with a surface To wet the phosphating solution, which is zinc-free. In this In a special case comes the necessary for the formation of the coating Amount of zinc from the surface of the treated material.
  • the wetting of the respective metal surfaces can e.g. by Diving and then draining, by pouring over and Spin off, by brushing, by spraying with compressed air, air-les as well as electrostatically.
  • Diving and then draining by pouring over and Spin off
  • brushing by spraying with compressed air, air-les as well as electrostatically.
  • a particularly elegant one The method of application of the phosphating solution is carried out by Rolling with structured or smooth rolls in synchronism or in the opposite direction.
  • drying can take place at room temperature. However, it is advantageous to work at higher temperatures because thereby the time for the formation of the phosphate layer considerably is shortened. Drying is preferably carried out at temperatures between 50 and 200 ° C, but with an object temperature of 90 ° C should not be exceeded.
  • a preferred development of the invention consists in wetting the surfaces with a phosphating solution 0.8 to 6 g / l Nickel, 3 to 16 g / l Manganese, 30 to 140 g / l Phosphate (calculated as P 2 O 5 ) and in the case of phosphating surfaces made of iron or aluminum or their alloys contains 0.8 to 4 g / l zinc.
  • a phosphating solution 0.8 to 6 g / l Nickel, 3 to 16 g / l Manganese, 30 to 140 g / l Phosphate (calculated as P 2 O 5 ) and in the case of phosphating surfaces made of iron or aluminum or their alloys contains 0.8 to 4 g / l zinc.
  • Further advantageous embodiments of the invention consist of wetting the surfaces with a phosphating solution which has an S value of 0.5 to 0.7 or wetting the surfaces with the phosphating solution in such a way that after drying a phosphate layer weight of 0, 5 to 2 g / m 2 results.
  • the setting of the preferred S value of 0.5 to 0.7 is particularly important in the treatment of zinc surfaces with zinc-free phosphating solutions, since the pickling attack of the phosphating solution on the zinc surface, which is responsible for the zinc content of the phosphate coating, then proceeds particularly optimally.
  • the embodiment of the invention with the setting of a phosphate coating weight of 0.5 to 2 g / m 2 enables the phosphate coating to be formed in a particularly short time and also of particularly high quality.
  • phosphate layers are produced which contain 0.5 to 3% by weight of nickel 1.5 to 8% by weight manganese 1.0 to 35% by weight zinc 25 to 40% by weight Phosphate (calculated as P 2 O 5 ) contain.
  • the metal surfaces must be sufficiently clean be. This is generally the case when e.g. B. tape material immediately after the galvanizing by the method according to the invention is treated. However, if the metal surface is oiled or is dirty, degreasing or cleaning with the help of itself to connect known methods and then to rinse.
  • the phosphating solution to be used in the process according to the invention is expediently used at a temperature in the range from 20 to 80 ° C.
  • the amount of the solution is usually between 2 and 10 ml per m 2 of metal surface. The drying takes place - if it happens under the influence of heat - practically immediately after wetting the surface, ie after an exposure time of about 0.5 to 5 seconds.
  • the present invention provides a method that is able to produce phosphate coatings in a matter of seconds. Another advantage over known methods is that there is no need for an activating pre-treatment before phosphating can.
  • the phosphate coatings produced are particularly high Quality with regard to the provision of detention afterwards applied paints, plastics or adhesives. They are the same their quality is that produced with the help of the so-called trication method Phosphate layers. This is surprising in that the one after Phosphate coatings obtained according to the process of the invention as a rule are amorphous, whereas those formed by the trication method Layers are always crystalline.
  • Another significant advantage of the invention is that Phosphate layers are generated that change the forming behavior of the so treated metals significantly improved without the Weldability is significantly affected.
  • the phosphate coatings produced by the process according to the invention are good in all areas where phosphate coatings are applied applicable.
  • a particularly advantageous application is in Preparation of the metal surfaces for the subsequent painting, especially electrocoating.
  • the invention is particularly important Process for its application to the phosphating of galvanized or galvanized steel strips.
  • Galvanized or alloy galvanized steel strips become strips understood that an edition of Elektroytzink (ZE), Feuerzink (Z), Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or Zinc / aluminum (ZA or AZ).
  • ZE Elektroytzink
  • ZNE zinc / nickel
  • ZF zinc / iron
  • ZA or AZ Zinc / aluminum
  • the latter are usually also alloys with e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.
  • the total score (GS) is determined by using 1 ml of the Phosphating solution after dilution with water to about 50 ml Use of phenolphthalein as an indicator until the color changes from titrated colorless to red. The number of used for this ml n / 10 sodium hydroxide solution give the total number of points.
  • the so-called S value is obtained by dividing the free acid by the total P 2 O 5 .
  • the total P 2 O 5 is determined by, after the determination of the free acid, the titration solution after adding 20 ml of 30% strength neutral potassium oxalate solution against phenolphthalein as an indicator until the color changes to red with n / 10 NaOH is titrated.
  • the consumption of ml n / 10 NaOH between the envelope with dimethyl yellow and the envelope with phenolphthalein gives the total P 2 O 5 .
  • the phosphating solution had a temperature of 25 ° C, one pH value of 1.7 and an S value of 0.6.
  • the content was Free acid 5.9 ml, total acid 17.1 ml.
  • the phosphating solution was applied with the help of a roll coating machine (roll coater), as is also used for coil coating.
  • the wet film of 5 ml of phosphating solution per m 2 of metal surface applied was dried in a continuous oven at 200 ° C. after an exposure time of 2 seconds. When leaving the furnace, the belt had an object temperature of 60 ° C.
  • the strip phosphated by the process according to the invention can also pass through the process usual in the automotive plant.
  • the phosphating takes place here during a treatment time of 3.5 min and a temperature of the phosphating solution of 52 ° C.
  • the composition of the phosphating solution is: 14 g / l Phosphate (calculated as P 2 O 5 ) 1.4 g / l zinc 1.0 g / l manganese 1.0 g / l nickel 70 mg / l Sodium nitrite 185 mg / l free fluoride.
  • the free acid content was 1.5 and the total acid content 27.8 Points were measured using a 10 ml bath sample. Of the S value was set to 0.08.
  • the phosphate coating produced in this way has a weight per unit area of 2.56 g / m 2 and contained 31% by weight of P 2 O 5 , 35% by weight of zinc, 6.4% by weight of manganese, 1.7% by weight. -% nickel.
  • the bodies are first provided with a cathodic electrodeposition paint and then with the customary automotive paint structure.
  • Test sheets with which the aforementioned process was simulated were subjected to the following tests: Stone chip test plus VDA alternating test, outdoor weathering, cross-cut plus 240 h condensation water constant climate test.
  • phosphating solution with a temperature of 27 ° C, which had the following composition, was applied to an electrolytically galvanized strip surface: phosphate 134 g / l (calculated as P 2 O 5 ) manganese 14.8 g / l nickel 5.42 g / l.
  • the solution had an S value of 0.62, a free acid content of 10.3 and a total acid content of 29.7 (based on a bath sample of 1 ml).
  • the wet film of the solution on the belt surface was 3 ml / m 2 .
  • the solution had an S value of 0.56, containing free acid of 9.4 and a total acid content of 29.2 (based on 1 ml Bath sample).
  • the dry phosphate layer had a basis weight of 1.95 g / m 2 and a composition of 37% by weight of P 2 O 5 , 3.9% by weight of manganese, 1.5% by weight of nickel and 1.9% by weight .-% zinc.
  • the properties of the phosphate layer with regard to adhesion and corrosion protection in connection with a subsequently applied coating were in line with expectations.

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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)
  • Materials For Medical Uses (AREA)

Claims (7)

  1. Procédé d'application de revêtements de phosphate sur des surfaces de zinc, fer, aluminium ou leurs alliages par mouillage avec une solution de phosphatage contenant des cations bivalents et du phosphate, suivi d'une dessication du film liquide, caractérisé en ce qu'on mouille les surfaces avec une solution de phosphatage, exempte d'éléments des 5ème et 6ème sous-groupes de la table périodique des éléments de Mendeleïev, contenant 0,5 à 8 g/l de nickel 2 à 20 g/l de manganèse 18 à 170 g/l de phosphate (calculé sous la forme P2O5)
    et présentant une valeur S de 0,4 à 0,8, de telle façon qu'il résulte après dessication un poids du film de phosphate de 0,3 à 3,0 g/m2, la solution de phosphatage contenant nécessairement 0,5 à 5 g/l de zinc dans le cas du phosphatage de surfaces en fer, aluminium ou leurs alliages et pouvant contenir du zinc dans le cas du phosphatage de surfaces en zinc ou alliages de zinc.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise dans le cas du phosphatage de surfaces en zinc ou alliages de zinc une solution de phosphatage exempte de zinc.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on mouille les surfaces avec une solution de phosphatage, contenant 0,8 à 6 g/l de nickel 3 à 16 g/l de manganèse 30 à 140 g/l de phosphate (calculé sous la forme P2O5)
    et contenant également 0,8 à 4 g/l de zinc dans le cas du phosphatage de surfaces en fer, aluminium ou leurs alliages.
  4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce qu'on mouille les surfaces avec une solution de phosphatage, contenant en supplément 2 à 10 g/l de SiO2 et 0,05 à 0,5 g/l de fluorure (calculé sous la forme F).
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on mouille les surfaces avec une solution de phosphatage, présentant une valeur S de 0,5 à 0,7.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on mouille les surfaces avec une solution de phosphatage de sorte qu'il résulte après dessiccation un poids du film de phosphate de 0,5 à 2 g/m2.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que les surfaces à phosphater sont composées en feuillard d'acier zingué ou galvanisé par dépôt d'alliage.
EP95941068A 1994-12-09 1995-12-05 Procede d'application de revetements de phosphate sur des surfaces metalliques Expired - Lifetime EP0796356B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4443882A DE4443882A1 (de) 1994-12-09 1994-12-09 Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
DE4443882 1994-12-09
PCT/EP1995/004774 WO1996017977A1 (fr) 1994-12-09 1995-12-05 Procede d'application de revetements de phosphate sur des surfaces metalliques

Publications (2)

Publication Number Publication Date
EP0796356A1 EP0796356A1 (fr) 1997-09-24
EP0796356B1 true EP0796356B1 (fr) 1998-11-04

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EP95941068A Expired - Lifetime EP0796356B1 (fr) 1994-12-09 1995-12-05 Procede d'application de revetements de phosphate sur des surfaces metalliques

Country Status (13)

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US (1) US5904786A (fr)
EP (1) EP0796356B1 (fr)
JP (1) JPH10510322A (fr)
KR (1) KR970707322A (fr)
CN (1) CN1066207C (fr)
AT (1) ATE173034T1 (fr)
AU (1) AU700492B2 (fr)
CA (1) CA2207932C (fr)
DE (2) DE4443882A1 (fr)
ES (1) ES2124032T3 (fr)
MX (1) MX9704126A (fr)
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AU700492B2 (en) 1999-01-07
ZA9510440B (en) 1997-06-09
AU4259996A (en) 1996-06-26
CN1066207C (zh) 2001-05-23
CA2207932A1 (fr) 1996-06-13
ATE173034T1 (de) 1998-11-15
EP0796356A1 (fr) 1997-09-24
ES2124032T3 (es) 1999-01-16
CN1169165A (zh) 1997-12-31
CA2207932C (fr) 2007-05-08
MX9704126A (es) 1998-02-28
DE4443882A1 (de) 1996-06-13
JPH10510322A (ja) 1998-10-06
DE59504172D1 (de) 1998-12-10
KR970707322A (ko) 1997-12-01
US5904786A (en) 1999-05-18
WO1996017977A1 (fr) 1996-06-13

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