EP0675972A4 - - Google Patents

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Publication number
EP0675972A4
EP0675972A4 EP94904428A EP94904428A EP0675972A4 EP 0675972 A4 EP0675972 A4 EP 0675972A4 EP 94904428 A EP94904428 A EP 94904428A EP 94904428 A EP94904428 A EP 94904428A EP 0675972 A4 EP0675972 A4 EP 0675972A4
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EP
European Patent Office
Prior art keywords
ions
range
phosphate coating
forming
dissolved
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
EP94904428A
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English (en)
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EP0675972B1 (en
EP0675972A1 (en
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Publication of EP0675972A1 publication Critical patent/EP0675972A1/en
Publication of EP0675972A4 publication Critical patent/EP0675972A4/en
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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
    • C23C22/12—Orthophosphates containing zinc 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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • 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
    • C23C22/186—Orthophosphates containing manganese cations containing also copper 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
    • C23C22/362—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 zinc 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
    • C23C22/368—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 magnesium cations

Definitions

  • This invention relates to a composition and process for forming a phosphate conversion coating on active metal surfaces in order to increase the corrosion resist- ance of the surfaces, either as treated or after subsequent conventional overcoating of the conversion coating layer formed by an organic based protective coating such as a paint or lacquer.
  • a composition according to this invention is well adapted to treat ⁇ ing any of a variety of base metals, including at least steel and galvanized steel and aluminum and aluminum based alloys.
  • Nickel has been implicated as a carcinogen in some studies, so that avoidance of its use in metal finishing is desirable for health reasons. Nickel is also considered a serious pollutant, and at the levels of 0.5 - 1.5 grams per liter (hereinafter often ab- breviated "g/L") at which it is conventionally used, nickel contributes significantly to the cost of the zinc phosphate conversion coating compositions. It is an object of this invention to minimize or eliminate the use of nickel, without worsening the quality of conversion coating obtained with conventional compositions containing zinc, nickel, and manganese.
  • a working composition according to this invention is an aqueous liquid compo- 5 sition that comprises, preferably consists essentially of, still more preferably consists of, water and:
  • (C) from 1 to 200, or with increasing preference in the order given, from 20 to 100, 24 to 74, or 24 to 60 milligrams per liter ("mg/L") of dissolved Cu +2 ions;
  • Points of free acid and total acid are defined for use herein as the number of milliliters (hereinafter “ml") of 0.1 N ⁇ aOH solution required to titrate a 10 ml sample of the composition, to a phenolphthalein end point (pH 9.0) for total acid and a bromthymol blue end point (pH 3.8) for free acid, except that if the composition has a pH greater than 3.8 initially, the points of free acid are defined as the negative of the number of ml of 0.1 N strong acid solution required to titrate a 10 ml sample of the composition to a pH of 3.8.
  • a process according to this invention comprises at a minimum a step of con ⁇ tacting a metal surface to be treated with a composition according to the invention for a sufficient time to form on the metal surface a detectable conversion coating.
  • Con- ventional metal surface cleaning and/or activation steps before contact between the metal to be treated and compositions according to the invention may be used if de ⁇ sired, and are generally preferred, as part of a process according to this invention.
  • a process according to the invention also may, and usually preferably does, include con ⁇ ventional steps subsequent to the contact between the metal surface to be treated and the compositions according to the invention.
  • the phosphate ions required for the compositions according to this invention are preferably PO 4 "3 ions or other ions derivable from less complete ionization of ortho- phosphoric acid (H 3 PO 4 ). Any free unionized phosphoric acid that may be present is considered part of the content of phosphate ions, to the extent of its stoichiometric cor ⁇ respondence to PO 4 '3 ions. Other free phosphoric acids such as metaphosphoric acid and condensed phosphoric acids such as pyrophosphoric acid and all anions derivable from them may also be used to supply the necessary phosphate ions.
  • the phosphate ions are derived from orthophosphoric acid and/or its neutral or acid salts of the metal cations also specified above as part of the compositions according to this invention.
  • the zinc cations required as part of the compositions are preferably derived from neutral or acid zinc salts of orthophosphoric acid, which may be formed in situ by dissolving zinc or zinc oxide or hydroxide in a solution containing the acid.
  • cupric cations required as part of the compositions according to this inven ⁇ tion may be derived from salts such as cupric sulfate and/or nitrate, or may be ob ⁇ tained by dissolving cupric oxide in part of the phosphoric acid used.
  • the accelerator component required in compositions according to the invention preferably includes at least one of the following: (i) from 0.01 to 0.2 g/1 of nitrite ions, (ii) from 0.5 to 5 g/1 of H 2 O 2 , (iii) from 0.05 to 2 g/1 of m-nitrobenzenesulfonate ions, (iv) from 0.05 to 2 g/1 of m-nitrobenzoate ions, (v) from 0.05 to 2 g/1 of p-nitro- phenol, and (vi) from 0.1 to 10, more preferably from 0.5 to 6, or still more preferably from 0.5 to 2.0, g L, measured as it stoichiometric equivalent as hydroxylamine, of a component capable of furnishing hydroxylamine in water solution.
  • the accelerator is hydroxylamine sulfate (hereinafter often abbreviated "HAS") or a similar safe and readily available source of dissolved hydroxylamine.
  • HAS hydroxylamine sulfate
  • the second most preferable accelerator is nitrite ions.
  • the acidity of the compositions according to the invention is preferably derived from phosphoric, sulfuric, and/or nitric acids.
  • the free fluoride may be derived from complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
  • complex fluoride ions such as fluoborate (BF 4 2 ), fluohafnate (HfF 6 "2 ), fluosilicate (SiF 6 '2 ), fluotitanate (TiF 6 "2 ), fluozirconate (ZrF 6 “2 ), and mixtures thereof; more preferably, from fluoborate and fluo- silicate and mixtures thereof.
  • simple fluorides such as alkali metal fluorides are also entirely satisfactory sources of free fluoride.
  • compositions according to the invention contain no more than 0.5, 0.2, 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of each of Ni +2 , any cation with a valence of three or higher, chloride ions including complex chloride ions, and chlorate ions.
  • chloride ions are present in sufficient quantity to be readily determined analytically, it is preferred that the ratio of the concentration in g/L of complex fluoride ions to the concentration in g/L of chloride ions have a value of at least 8:1, or more preferably a value of at least 14:1.
  • contact between the metal surface to be treated and a composition according to the invention may be accomplished by spraying, dipping, or any other convenient method or combination of methods.
  • the temperature during contact between the metal treated and the composition according to the invention preferably is, with increasing preference in the order given, in the range from 21 to 85, 25 to 55, or 31 to 44, ° C.
  • the total time of contact between the composition according to the invention and the metal surface to be conversion coated preferably is, with increasing preference in the order given, in the range from 5 sec to 15 minutes (hereinafter often abbreviated "min"), 15 seconds (hereinafter often abbreviated "sec”) to 10 min, 30 sec to 5 min, or 90 to 120 sec.
  • the add-on mass of the phosphate coating formed preferably is, with increasing preference in the order given, in the range from 1.1 to 5.4, 1.6 to 4.3, or 2.2 to 3.8, grams per square meter (hereinafter "g/m 2 ) of surface treated.
  • the weight percent of copper in the coat ⁇ ing formed preferably is, with increasing preference in the order given, from 0.50 to 10, 1.0 to 8.0, 2.0 to 6.0, 3.0 to 4.1.
  • compositions except for one comparison example, illustrate the use of
  • HAS accelerator HAS accelerator. Specific compositions are shown in Table 1 below. These composi- tions, except for comparison example 13 which was prepared from a commercially compounded concentrate, were prepared according to the following general procedure: An amount of water equal to about three-quarters of the volume eventually desired for the composition was initially used, and an amount of zinc dihydrogen phosphate suffi ⁇ cient to provide the desired zinc ion concentration in the final desired volume was dis ⁇ solved in this water. An amount of 75 % aqueous solution of orthophosphoric acid that was sufficient, together with the previously added zinc dihydrogen phosphate, to provide the desired final concentration of phosphate ions in the desired final volume was then added.
  • Test panels of cold rolled steel, galvanized steel, and/or conventional aluminum alloys used in automobile and appliance manufacture were used and subjected to the following general sequence of process steps: (1) Conventional alkaline cleaner for 120 sec at 43° C; (2) Water rinse at 38° C for 60 sec; (3) Conventional colloidal titanium phosphate activator for 30 sec at 38° C; (4) Contact with one of Composi ⁇ tions 1 - 12 from Table 1 below for 120 sec at 35° C or at 43° C; (5) Cold water rinse at 20 - 25 ° C for 60 sec; (6) Post treatment for 30 sec with a conventional commer ⁇ cial post treatment composition containing hexavalent and trivalent chromium; and (7) Rinse with deionized water for 30 sec at 20 - 25 ° C.
  • compositions were prepared in the same general manner as for Group I, except that sodium nitrite instead of HAS was used as the accelerator and cupric ni ⁇ trate with an average of 2.5 molecules of water of hydration per cupric ion was used as the copper source.
  • Compositions are as follows:
  • Example 14 was used for spray phosphating at 33° C in a process sequence other ⁇ wise like those of Group I above.
  • Example 14 was used for immersion phosphating at 57° C in a process sequence otherwise like those of Group I above.
EP94904428A 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process Expired - Lifetime EP0675972B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US99546592A 1992-12-22 1992-12-22
PCT/US1993/012044 WO1994014999A1 (en) 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process
US995465 1997-10-06

Publications (3)

Publication Number Publication Date
EP0675972A1 EP0675972A1 (en) 1995-10-11
EP0675972A4 true EP0675972A4 (zh) 1995-11-02
EP0675972B1 EP0675972B1 (en) 1999-08-11

Family

ID=25541841

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94904428A Expired - Lifetime EP0675972B1 (en) 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process

Country Status (14)

Country Link
EP (1) EP0675972B1 (zh)
JP (1) JPH08504890A (zh)
CN (1) CN1092245C (zh)
AT (1) ATE183247T1 (zh)
AU (1) AU5848194A (zh)
BR (1) BR9307702A (zh)
CA (1) CA2150545A1 (zh)
CZ (1) CZ287997B6 (zh)
DE (1) DE69326021T2 (zh)
ES (1) ES2136726T3 (zh)
PL (1) PL309404A1 (zh)
SG (1) SG55084A1 (zh)
WO (1) WO1994014999A1 (zh)
ZA (1) ZA939636B (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4440300A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19538778A1 (de) * 1995-10-18 1997-04-24 Henkel Kgaa Schichtgewichtssteuerung bei Hydroxylamin-beschleunigten Phosphatiersystemen
DE19540085A1 (de) * 1995-10-27 1997-04-30 Henkel Kgaa Nitratarme, manganfreie Zinkphosphatierung
DE19606017A1 (de) * 1996-02-19 1997-08-21 Henkel Kgaa Zinkphosphatierung mit geringen Gehalten an Kupfer und Mangan
DE19740953A1 (de) * 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
DE10320313B4 (de) * 2003-05-06 2005-08-11 Chemetall Gmbh Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes
WO2006071226A1 (en) * 2004-12-28 2006-07-06 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating process that reduces laser scale resulting in improved paint adhesion
DE102006052919A1 (de) * 2006-11-08 2008-05-15 Henkel Kgaa Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen
CN103924226B (zh) * 2014-04-25 2016-06-15 山东大学 一种分级结构磷酸锌化学转化膜的制备方法
CN104032293B (zh) * 2014-06-11 2016-02-17 安徽江南机械有限责任公司 一种不含镍单组分高耐蚀性环保黑色磷化液

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB526816A (en) * 1939-03-14 1940-09-26 Samuel Thomas Roberts Improvements in the conversion of zinc, zinc alloy, galvanised, cadmium and cadmium alloy surfaces for ensuring paint and enamel adhesion
US2813812A (en) * 1952-06-24 1957-11-19 Parker Rust Proof Co Method for coating iron or zinc with phosphate composition and aqueous solution therefor
FR1465983A (fr) * 1965-11-06 1967-01-13 Parker Ste Continentale Procédé de traitement de l'acier en vue de l'application de peinture par électrophorèse
DE2049350A1 (de) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
EP0123980A1 (en) * 1979-05-02 1984-11-07 Amchem Products, Inc. Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
WO1993022474A1 (de) * 1992-05-06 1993-11-11 Henkel Kommanditgesellschaft Auf Aktien Kupfer enthaltendes, nickelfreies phosphatierverfahren
EP0633950A1 (de) * 1992-03-31 1995-01-18 Henkel Kgaa Nickelfreie phosphatierverfahren.

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4013483A1 (de) * 1990-04-27 1991-10-31 Metallgesellschaft Ag Verfahren zur phosphatierung von metalloberflaechen
CN1022496C (zh) * 1991-06-29 1993-10-20 兰州中进高新技术公司 室温磷化液及其配制方法
CN1026341C (zh) * 1992-04-21 1994-10-26 陈金田 常温快速磷化液

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB526816A (en) * 1939-03-14 1940-09-26 Samuel Thomas Roberts Improvements in the conversion of zinc, zinc alloy, galvanised, cadmium and cadmium alloy surfaces for ensuring paint and enamel adhesion
US2813812A (en) * 1952-06-24 1957-11-19 Parker Rust Proof Co Method for coating iron or zinc with phosphate composition and aqueous solution therefor
FR1465983A (fr) * 1965-11-06 1967-01-13 Parker Ste Continentale Procédé de traitement de l'acier en vue de l'application de peinture par électrophorèse
DE2049350A1 (de) * 1969-10-08 1971-04-15 Lubrizol Corp Phosphatierungslosungen und ihre Verwendung zum Korrosionsschutz von Eisen metall und Zinkoberflachen
FR2203893A1 (en) * 1972-10-20 1974-05-17 Fosfa Col Sas Di A Dal Pane Et Ambient temp. phosphating - using accelerator contg. bath to produce coating espec. amenable to accepting electrophoretic paint coatings
EP0123980A1 (en) * 1979-05-02 1984-11-07 Amchem Products, Inc. Composition and process for zinc phosphate coating a metal surface and a process for painting the coated surface
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
EP0633950A1 (de) * 1992-03-31 1995-01-18 Henkel Kgaa Nickelfreie phosphatierverfahren.
WO1993022474A1 (de) * 1992-05-06 1993-11-11 Henkel Kommanditgesellschaft Auf Aktien Kupfer enthaltendes, nickelfreies phosphatierverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 80, no. 1, 14 January 1974, Columbus, Ohio, US; abstract no. 6279w, IMAO H.: "Pretreating metal before electrocoating" page 195; *

Also Published As

Publication number Publication date
EP0675972B1 (en) 1999-08-11
EP0675972A1 (en) 1995-10-11
ZA939636B (en) 1994-08-15
JPH08504890A (ja) 1996-05-28
AU5848194A (en) 1994-07-19
CN1092245C (zh) 2002-10-09
CZ287997B6 (cs) 2001-03-14
CA2150545A1 (en) 1994-07-07
DE69326021T2 (de) 1999-12-23
ATE183247T1 (de) 1999-08-15
BR9307702A (pt) 1999-08-31
CN1090606A (zh) 1994-08-10
WO1994014999A1 (en) 1994-07-07
PL309404A1 (en) 1995-10-02
DE69326021D1 (de) 1999-09-16
ES2136726T3 (es) 1999-12-01
CZ164995A3 (en) 1996-01-17
SG55084A1 (en) 1998-12-21

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