EP0796356A1 - Procede d'application de revetements de phosphate sur des surfaces metalliques - Google Patents

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

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Publication number
EP0796356A1
EP0796356A1 EP95941068A EP95941068A EP0796356A1 EP 0796356 A1 EP0796356 A1 EP 0796356A1 EP 95941068 A EP95941068 A EP 95941068A EP 95941068 A EP95941068 A EP 95941068A EP 0796356 A1 EP0796356 A1 EP 0796356A1
Authority
EP
European Patent Office
Prior art keywords
zinc
phosphate
phosphating
solution
alloys
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
EP95941068A
Other languages
German (de)
English (en)
Other versions
EP0796356B1 (fr
Inventor
Thomas Wendel
Hardy Wietzoreck
Klaus Bittner
Peter Schiefer
Marcus Schinzel
Helmut HÜLSMANN
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.)
Chemetall GmbH
Original Assignee
Metallgesellschaft AG
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.)
Filing date
Publication date
Application filed by Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0796356A1 publication Critical patent/EP0796356A1/fr
Application granted granted Critical
Publication of EP0796356B1 publication Critical patent/EP0796356B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 them with a phosphate solution containing divalent cations and phosphate and then drying the liquid film.
  • the process of producing phosphate coatings using aqueous zinc phosphate solutions is widely used in the metalworking industry.
  • the phosphate layers created with this process on the treated metal surfaces are used in particular to facilitate sliding, to prepare for non-cutting cold forming, as well as to protect against corrosion and as a paint primer.
  • Such phosphating solutions usually have a pH between about 1.8 and 3.8 and contain zinc and phosphate ions as process-determining components.
  • zinc in addition to the cation zinc, other cations, for example ammonium, calcium, cobalt, iron, potassium, copper, sodium, magnesium, manganese, may also be present.
  • oxidizing agents such as bromate, chlorate, nitrate, nitrite, organic nitro compounds, perborate, persulfate or hydrogen peroxide are generally added to the phosphating solutions.
  • additives such as Fluoride, silicon fluoride, boron fluoride, citrate and tartrate. Due to the large number of individual components and their possible combinations, there are a multitude of different compositions of the phosphating solutions.
  • the so-called low-zinc processes represent a special embodiment of the phosphating processes.
  • the phosphating solutions used here contain zinc in concentrations of only about 0.4 to 1.7 g / l and, particularly on steel, produce phosphate layers with a high proportion of phosphophyllite, which is better Provides paint adhesion and a higher resistance to paint infiltration when exposed to corrosion than is customary in the production of phosphate layers based on Hopeit from phosphating solutions with a higher zinc content.
  • phosphating processes which experts call the trication process.
  • These are low-zinc phosphating processes, in which the use of nickel in e.g. Quantities of 0.3 - 2.0 g / 1 and manganese in quantities of e.g. 0.5 - 1.5 g / 1 phosphate coatings are obtained, which are characterized by an increased alkali resistance and are therefore of importance for cathodic electrocoating, in particular for car bodies.
  • a common feature of the aforementioned phosphating processes is that the phosphating solution is brought into contact with the workpiece surfaces to be treated in immersion, flooding or spraying. After the chemical reaction has taken place and the solid, Critalline phosphate layer requires a rinsing treatment to remove any phosphating chemicals remaining on the surface, which is usually carried out in several stages. This results in rinsing solutions that cannot be disposed of in this form, but must be sent to a wastewater treatment plant.
  • One such method which is intended for preparing metal surfaces for subsequent coating with organic coatings, is to wet the metal surface with a phosphating liquid which has a pH of 1.5 to 3, is chromium-free and contains, in addition to metal phosphate, soluble molybdate, tungstate, vanadate, niobate and / or tantalate ions (EP-B-15 020).
  • the cationic component of the metal phosphate in the solution can be formed by calcium, magnesium, barium, aluminum, zinc, cadmium, iron, nickel, cobalt and / or manganese.
  • a disadvantage of the last-mentioned process is that due to the necessary additions of molydate, tungstate, vanadate, niobate and tantalate ions, the process is more cost-intensive than the conventional phosphating processes, another that the phosphate coatings obtained do not meet all requirements today e.g. B. with regard to alkali resistance and thus resistance in a subsequent cathodic electrocoating and the desired corrosion resistance, in particular 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 alloys, which does not have the known, in particular the aforementioned disadvantages, is nevertheless inexpensive and simple to carry out and leads to high-quality phosphate coatings.
  • the object is achieved by the method of the type mentioned according to the invention is designed such that the
  • Alloys necessarily contain 0.5 to 5 g / 1 zinc and in the case the phosphating of surfaces made of zinc or zinc alloys can contain zinc ions.
  • the aforementioned formulation with regard to the zinc content is intended to express that in the case of the treatment of surfaces made of iron, aluminum or their alloys, a zinc content in the concentrations mentioned is essential.
  • the phosphating solution can also contain zinc, but a zinc content is not required.
  • Elements of the 5th and 6th subgroup of the Periodic Table of the Elements are vanadium, niobium, tantalum, chromium, molybdenum and tungsten.
  • the S value is expediently set with nickel oxide, manganese oxide or possibly zinc oxide or with ammonia solution.
  • An expedient embodiment of the invention provides that, in the case of the treatment of zinc or zinc alloys, the surfaces are wetted with a phosphating solution which is zinc-free. In this particular case, the amount of zinc required to form the coating comes from the surface of the treated material.
  • the wetting of the respective metal surfaces can e.g. by immersion and subsequent draining, by pouring over and spinning off, by brushing, by spraying with compressed air, air-les and electrostatically.
  • a particularly elegant method of applying the phosphating solution is carried out by rolling with structured or smooth rollers in the same direction or in the opposite direction.
  • the drying following the wetting of the metal surface can in principle already take place at room temperature. However, it is advantageous to work at higher temperatures because this considerably reduces the time for the formation of the phosphate layer. Drying is preferably carried out at temperatures between 50 and 200'C, but an object temperature of 90 "C should not be exceeded.
  • a preferred development of the invention is that
  • Aluminum or its alloys contains 0.8 to 4 g / 1 zinc.
  • the aforementioned embodiment of the invention leads to particularly high quality phosphate coatings.
  • Hydrogen fluoride or their aqueous solution introduced. These additives in particular bring about the formation of a uniform and closed coating which practically does not tend to stick.
  • 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 : 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 responsible for the zinc content of the phosphate coating is particularly optimal runs.
  • the embodiment of the invention with a phosphate coating weight of 0.5 to 2 g / m * enables the phosphate coating to be formed in a particularly short time and, moreover, of particularly high quality.
  • Phosphate layers produced that 0.5 to 3 wt .-% nickel
  • the metal surfaces must be sufficiently clean to ensure proper wetting with the phosphating solution. This is generally the case when e.g. B. strip material is treated immediately after the galvanizing by the method according to the invention. However, if the metal surface is oiled or dirty, degreasing or cleaning must be carried out using methods known per se and then rinsed.
  • Phosphating solution 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 Surface, ie after an exposure time of about 0.5 to 5 see.
  • the present invention provides a method capable of producing phosphate coatings in a matter of seconds. Another advantage over known processes is that an activating pretreatment before phosphating can be omitted.
  • the phosphate coatings produced are particularly of high quality with regard to the adhesion imparting of subsequently applied paints, plastics or adhesives. Their quality is similar to that of the phosphate layers produced using the so-called trication process. This is surprising insofar as the phosphate coatings obtained by the process according to the invention are generally are amorphous, whereas the layers formed by the trication method are always crystalline.
  • Another important advantage of the invention is that phosphate layers are produced which significantly improve the forming behavior of the metals treated in this way, without the weldability being significantly impaired thereby.
  • phosphate coatings produced using the method according to the invention can be used well in all fields in which phosphate coatings are used.
  • a particularly advantageous application is the preparation of the metal surfaces for the subsequent painting, in particular the electrocoating.
  • the method according to the invention is of particularly outstanding importance for its application to the phosphating of galvanized or alloy-galvanized steel strips.
  • galvanized or alloy-galvanized steel strip is understood to mean strips which are a coating of Elektroytzmk (ZE), hot-dip zinc (Z), alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / aluminum (ZA or AZ) ) exhibit. To the latter, alloys with z. B. 55 wt .-% Al and 45 wt .-% Zn counted.
  • the total number of points is determined by titrating 1 ml of the phosphating solution after dilution with water to about 50 ml using phenolphthalein as an indicator until the color changes from colorless to red.
  • the number of ml n / 10 sodium hydroxide used for this gives the total number of points.
  • the so-called S value is obtained by dividing the free acid by the total P, 0 5 .
  • the total P 2 0 5 is determined by, following 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, 0 5 .
  • Phosphating solution applied which contained the following components - dissolved in deionized water.
  • the phosphating solution had a temperature of 25 * C, a pH value of 1.7 and an S value of 0.6.
  • the content was
  • the application of the phosphating solution was carried out with the help of a roll coating machine (roll coater), as it is also used for coil coating.
  • the applied wet film of 5 ml phosphating solution per m 2 of metal surface was dried after an exposure time of 2 seconds in a continuous furnace at 200 "C. When leaving the furnace, the strip had an object temperature of 60 * C.
  • the phosphate coating applied was uniform, closed and had a dry layer weight of
  • the tape provided with a phosphate coating by the process according to the invention showed excellent behavior during deformation, both in the lacquered and in the unpainted state.
  • the adhesion and corrosion protection values of subsequently applied organic coatings also met today's requirements.
  • the strip phosphated by the process according to the invention can also pass through the process usual in the automotive plant. This means that the individual body parts can first be shaped in a customary manner and assembled by welding to form the body and then the treatment system cleaning-rinsing-activating-
  • Phosphating solution is:
  • the free acid content was 1.5 and the total acid content 27.8
  • 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:
  • 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
  • the solution had an S value of 0.56, a free acid content of 9.4 and a total acid content of 29.2 (based on 1 ml
  • the dry phosphate layer had a basis weight of 1.95 g / ⁇ r and a composition of 37% by weight p, 0 3 3.9% by weight manganese, 1.5% by weight nickel and 1.9% by weight zinc here were the properties of the phosphate layer in terms of adhesion and Corrosion protection in connection with a subsequently applied coating as expected.

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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)

Abstract

L'invention concerne un procédé d'application de revêtements de phosphate sur des surfaces de zinc, de fer, d'aluminium ou d'alliages de ceux-ci, ledit procédé consistant à imprégner les surfaces d'une solution de phosphatation exempte d'éléments des cinquième et sixième sous-groupes de la classification périodique des éléments, et contenant 0,5 à 8 g/l de nickel, 2 à 20 g/l de manganèse, 18 à 170 g/l de phosphate (sous forme de P2O5) et présentant un indice d'acide compris entre 0,4 et 0,8. L'imprégnation, suivie immédiatement d'un séchage, est réalisée de façon à produire une couche de phosphate présentant un poids surfacique compris entre 0,3 et 3,0 g/m<2>. La solution de phosphatation comprend nécessairement 0,5 à 5,0 g/l de zinc, si la phosphatation s'effectue sur des surfaces de fer, d'aluminium ou d'alliages de ceux-ci. Au cas où la phosphatation s'effectue sur des surfaces de zinc ou d'alliages de zinc, la solution ne contient pas nécessairement de zinc, et, de préférence, est exempte de zinc. Ce procédé est appliqué de façon particulièrement avantageuse dans la phosphatation de feuillards d'acier zingués ou galvanisés avec des alliages.
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 true EP0796356A1 (fr) 1997-09-24
EP0796356B1 EP0796356B1 (fr) 1998-11-04

Family

ID=6535385

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Country Link
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)
WO (1) WO1996017977A1 (fr)
ZA (1) ZA9510440B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001066826A1 (fr) * 2000-03-07 2001-09-13 Chemetall Gmbh Procede de phosphatation utilisation des pieces en metal ainsi phosphatees

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19749508A1 (de) * 1997-11-08 1999-05-12 Henkel Kgaa Korrosionsschutz von verzinkten und legierungsverzinkten Stahlbändern
CN1111569C (zh) * 1998-04-13 2003-06-18 赵全玺 无机磷酸盐涂料
US6235111B1 (en) * 1998-11-25 2001-05-22 Ez Environmental Solutions, Corporation Closed-loop phosphatizing system and method
CA2358625A1 (fr) 2000-10-10 2002-04-10 Henkel Corporation Revetement de conversion au phosphate
US20040188323A1 (en) * 2003-03-24 2004-09-30 Tzatzov Konstantin K. Active coating system for reducing or eliminating coke build-up during petrochemical processes
CN100338260C (zh) * 2004-05-14 2007-09-19 深圳市成功科技有限公司 铝合金暖气片复合镀镍方法
US20060002832A1 (en) * 2004-05-19 2006-01-05 Ez Environmental Solutions Corporation, A California Corporation Selectable closed-loop phosphatizing wash & rinse system and method
US7514153B1 (en) 2005-03-03 2009-04-07 The United States Of America As Represented By The Secretary Of The Navy Method for deposition of steel protective coating
CN100366796C (zh) * 2005-04-22 2008-02-06 吉林大学 一种在水溶液中制备无机磷酸盐薄膜的方法
US8137805B2 (en) * 2007-06-21 2012-03-20 Caterpillar Inc. Manganese based coating for wear and corrosion resistance
US8137761B2 (en) * 2008-06-13 2012-03-20 Caterpillar Inc. Method of coating and induction heating a component
CN101660164B (zh) * 2008-08-26 2011-12-28 宝山钢铁股份有限公司 一种润滑性电镀锌钢板及其生产方法
CA2778888C (fr) * 2009-10-26 2013-12-10 Nippon Steel Corporation Tole d'acier allie, galvanise par immersion a chaud, presentant d'excellentes formabilite et resistance au decollement post-adherence, et procede de fabrication associe
KR101405781B1 (ko) 2009-10-26 2014-06-10 신닛테츠스미킨 카부시키카이샤 합금화 용융 아연 도금 강판과 그 제조 방법
JP5189691B1 (ja) 2011-06-17 2013-04-24 株式会社神戸製鋼所 圧粉磁心用鉄基軟磁性粉末およびその製造方法、ならびに圧粉磁心
DE102017117080A1 (de) * 2017-07-28 2019-01-31 Thyssenkrupp Ag Stahlblech mit einer Konversionsschicht, Verfahren zur Herstellung eines konversionsbeschichteten Stahlblechs und Behandlungsmittel zur Applizierung einer Konversionsschicht auf einem Stahlblech
CN112410768B (zh) * 2020-10-30 2023-06-23 马鞍山钢铁股份有限公司 一种镀锌钢板表面处理剂、表面处理剂的制备方法及自润滑镀锌钢板、钢板的制备方法
CN112522689B (zh) * 2020-10-30 2023-06-23 马鞍山钢铁股份有限公司 一种合金化镀锌钢板表面处理剂、制备方法及合金化镀锌钢板、热成形零部件
CN113529062A (zh) * 2021-07-13 2021-10-22 山东大学 一种锌合金表面磷酸锌化学转化膜及其制备方法和应用
CN115068699A (zh) * 2022-06-30 2022-09-20 卓阮医疗科技（苏州）有限公司 一种可吸收固定钉、其制备方法及其在固定口腔引导骨再生屏障膜中的应用

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1192515A (fr) * 1957-12-31 1959-10-27 Procédé pour préparer les pièces en fer ou en acier en vue de leur formage à froid
NL293566A (fr) * 1962-06-04
JPS506418B1 (fr) * 1971-07-06 1975-03-13
GB1415999A (en) * 1973-05-29 1975-12-03 Pyrene Chemical Services Ltd Process for forming phosphate coatings
DE2327304C3 (de) * 1973-05-29 1982-01-21 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum Aufbringen von Phosphatüberzügen auf Metalle
DE2905535A1 (de) * 1979-02-14 1980-09-04 Metallgesellschaft Ag Verfahren zur oberflaechenbehandlung von metallen
DE2907094A1 (de) * 1979-02-23 1980-09-04 Metallgesellschaft Ag Phosphatierungsloesungen
DE3016576A1 (de) * 1980-04-30 1981-11-05 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung
DE3048629C2 (de) * 1980-12-23 1982-11-04 Siemens AG, 1000 Berlin und 8000 München Verfahren und Anordnung zur Reduzierung des Speicherplatzbedarfes von Zeichen oder grafische Muster beschreibenden binären Zeichenfolgen in Zeichengeneratoren
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
DE3236247A1 (de) * 1982-09-30 1984-04-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur oberflaechenbehandlung von aluminium
DE3247729A1 (de) * 1982-12-23 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur behandlung von metalloberflaechen, insbesondere solchen von aluminium, aluminiumlegierungen und stahl, sowie hierfuer geeignete waessrige badloesungen
ATE39134T1 (de) * 1983-08-22 1988-12-15 Nippon Paint Co Ltd Phosphatierung von metalloberflaechen.
US4596607A (en) * 1985-07-01 1986-06-24 Ford Motor Company Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application
FR2601698B3 (fr) * 1986-07-17 1988-10-21 Solypro Nouvelle Exploit Bain et procede de phosphatation
US5232523A (en) * 1989-03-02 1993-08-03 Nippon Paint Co., Ltd. Phosphate coatings for metal surfaces
DE3927131A1 (de) * 1989-08-17 1991-02-21 Henkel Kgaa Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
US5082511A (en) * 1989-09-07 1992-01-21 Henkel Corporation Protective coating processes for zinc coated steel
DE4029956A1 (de) * 1990-09-21 1992-03-26 Metallgesellschaft Ag Phosphatierverfahren
GB9207725D0 (en) * 1992-04-08 1992-05-27 Brent Chemicals Int Phosphating solution for metal substrates
DE19606018A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt
WO2000072114A2 (fr) * 1999-05-21 2000-11-30 Scholarone, Inc. Systeme et procede pour la publication de manuscrits

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9617977A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001066826A1 (fr) * 2000-03-07 2001-09-13 Chemetall Gmbh Procede de phosphatation utilisation des pieces en metal ainsi phosphatees
US7208053B2 (en) 2000-03-07 2007-04-24 Chemetall Gmbh Method for applying a phosphate covering and use of metal parts thus phospated

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ZA9510440B (en) 1997-06-09
JPH10510322A (ja) 1998-10-06
ATE173034T1 (de) 1998-11-15
CA2207932A1 (fr) 1996-06-13
ES2124032T3 (es) 1999-01-16
CA2207932C (fr) 2007-05-08
DE59504172D1 (de) 1998-12-10
WO1996017977A1 (fr) 1996-06-13
KR970707322A (ko) 1997-12-01
AU700492B2 (en) 1999-01-07
EP0796356B1 (fr) 1998-11-04
US5904786A (en) 1999-05-18
CN1169165A (zh) 1997-12-31
AU4259996A (en) 1996-06-26
DE4443882A1 (de) 1996-06-13
MX9704126A (es) 1998-02-28
CN1066207C (zh) 2001-05-23

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