EP0675972B1 - Substantially nickel-free phosphate conversion coating composition and process - Google Patents

Substantially nickel-free phosphate conversion coating composition and process Download PDF

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Publication number
EP0675972B1
EP0675972B1 EP94904428A EP94904428A EP0675972B1 EP 0675972 B1 EP0675972 B1 EP 0675972B1 EP 94904428 A EP94904428 A EP 94904428A EP 94904428 A EP94904428 A EP 94904428A EP 0675972 B1 EP0675972 B1 EP 0675972B1
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EP
European Patent Office
Prior art keywords
range
composition
ions
concentration
lies
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EP94904428A
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German (de)
English (en)
French (fr)
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EP0675972A1 (en
EP0675972A4 (zh
Inventor
Robert W. Miller
Michael Petschel
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Henkel Corp
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Henkel Corp
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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 resistance 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 treating any of a variety of base metals, including at least steel and galvanized steel and aluminum and aluminum based alloys.
  • phosphate conversion coating compositions and processes are already described in the art. Those believed to be generally considered of highest quality at present include zinc, nickel, and at least one other divalent metal such as manganese in the composition.
  • 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 abbreviated "g/L") at which it is conventionally used, nickel contributes significantly to the cost of the zinc phosphate conversation 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.
  • g/L grams per liter
  • Fosfa-Col &c.'s French Patent No. 2,203,893 in the context of "normal-zinc" processes operating at Zn-concentrations of e.g. 2.94 g/L Zn, discloses Ni-free solutions which contain minimal concentrations of copper, which however must abide by the requirement that the ratio in gram-atoms of zinc to copper must lie in the range of from 100 to 1,500, exemplified as 0.011 and 0.019 mg/L.
  • Henkel KGaA's EPA 0,633,950 (corresponding to International Publication WO 93/20259) which was unpublished at the priority date of the present Application but is itself of earlier date discloses a composition and process for phosphatizing using an aqueous solution comprising 0.2 to 2 g/L Zn ions, 0.5 to 25 mg/L Cu ions, 5 to 30 g/L of phosphate (P 2 O 5 ) and 0.5 to 5 g/L hydroxylamine.
  • an aqueous liquid zinc phosphatizing composition which contains no more than 0.2 g/L of Ni +2 and otherwise comprises water together with:
  • compositions preferably contain from 5-20, still more preferably from 13-18 g/L of dissolved phosphate ions.
  • compositions preferably contain, with increasing preference in the order given, from 0.57 to 1.24, from 0.60 to 0.95, or from 0.71 to 0.87, g/L of dissolved Zn +2 ions.
  • compositions preferably contain from 26 to 60 milligrams per liter ("mg/L") of dissolved CU +2 ions.
  • an effective amount of a conventional hydroxylamine accelerator is from 0.1 to 10 g/L of hydroxylamine or a stoichiometrically-equivalent amount of at least one component capable of furnishing hydroxylamine in water solution.
  • compositions preferably contain, with increasing preference in the order given, from 7 to 25, from 13 to 24, from 16 to 22, or from 18 to 21 "points" of total acid.
  • a process according to this invention comprises at a minimum a step of contacting 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.
  • Conventional 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 desired, 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 conventional steps subsequent to the contact between the metal surface to be treated and the compositions according to the invention. These subsequent steps, e.g., may include rinsing with water, any conventional reactive post treatments, e.g., with compositions according to the teachings of U.S. Patent 4,963,596 or with chromate containing solutions, and painting or otherwise protecting the surface with an outer coating of an organic based solid material.
  • 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 correspondence to PO 4 -3 ions. Other free phosphoric acids such a 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 the invention may be derived from salts such as cupric sulfate and/or nitrate, or may be obtained by dissolving cupric oxide in part of the phosphoric acid used.
  • the accelerator component required in compositions according to the invention preferably is or includes from 0.5 to 6 g/L, or more preferably from 0.5 to 2.0, g/L, measured as its stoichiometric equivalent as hydroxylamine, of at least one 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.
  • 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 fluosilicate 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 fluosilicate 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 0.2 g/L of Ni +2 , and with increasing preference in the order given they contain no more than 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of Ni +2 . Similarly, with increasing preference in the order given and with independent preference for each noted component, the compositions contain no more than 0.5, 0.2, 0.10, 0.07, 0.03, 0.01, 0.005, or 0.001 g/L of any cation with a valence of three or higher, chloride ions including complex chloride ions, and chlorate ions.
  • 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 coating 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 illustrate the use of HAS accelerator. Specific compositions are shown in Table 1 below. These compositions were prepared according to the following general procedure:
  • 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 Compositions 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 commercial post treatment composition containing hexavalent and trivalent chromium; and (7) Rinse with deionized water for 30 sec at 20-25°C.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Glass Compositions (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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 EP0675972A4 (zh) 1995-11-02
EP0675972B1 true 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
CA2591141C (en) * 2004-12-28 2012-02-28 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

Family Cites Families (12)

* 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
DE1287413B (de) * 1965-11-06 1969-01-16 Metallgesellschaft Ag Verfahren zur Vorbereitung von Stahl fuer die elektrophoretische Beschichtung mit Lacken
US3597283A (en) * 1969-10-08 1971-08-03 Lubrizol Corp Phosphating solutions for use on ferrous metal and zinc surfaces
IT975560B (it) * 1972-10-20 1974-08-10 Sec Accomandita Semplice Fosfa Procedimento di fosfatazione di su perfici metalliche destinate a ver niciatura particolarmente per elet troforesi e soluzione relativa a tale procedimento
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
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
DE4210513A1 (de) * 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
CN1026341C (zh) * 1992-04-21 1994-10-26 陈金田 常温快速磷化液
DE4214992A1 (de) * 1992-05-06 1993-11-11 Henkel Kgaa Kupfer enthaltendes, nickelfreies Phosphatierverfahren

Also Published As

Publication number Publication date
CN1090606A (zh) 1994-08-10
JPH08504890A (ja) 1996-05-28
ES2136726T3 (es) 1999-12-01
CA2150545A1 (en) 1994-07-07
BR9307702A (pt) 1999-08-31
PL309404A1 (en) 1995-10-02
DE69326021T2 (de) 1999-12-23
CZ164995A3 (en) 1996-01-17
ATE183247T1 (de) 1999-08-15
ZA939636B (en) 1994-08-15
EP0675972A1 (en) 1995-10-11
AU5848194A (en) 1994-07-19
CZ287997B6 (cs) 2001-03-14
WO1994014999A1 (en) 1994-07-07
CN1092245C (zh) 2002-10-09
EP0675972A4 (zh) 1995-11-02
DE69326021D1 (de) 1999-09-16
SG55084A1 (en) 1998-12-21

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