WO1994014999A1 - 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
WO1994014999A1
WO1994014999A1 PCT/US1993/012044 US9312044W WO9414999A1 WO 1994014999 A1 WO1994014999 A1 WO 1994014999A1 US 9312044 W US9312044 W US 9312044W WO 9414999 A1 WO9414999 A1 WO 9414999A1
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WO
WIPO (PCT)
Prior art keywords
ions
range
phosphate coating
forming
dissolved
Prior art date
Application number
PCT/US1993/012044
Other languages
English (en)
French (fr)
Inventor
Robert W. Miller
Michael Petschel
Original Assignee
Henkel Corporation
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 Henkel Corporation filed Critical Henkel Corporation
Priority to ES94904428T priority Critical patent/ES2136726T3/es
Priority to EP94904428A priority patent/EP0675972B1/en
Priority to JP6515227A priority patent/JPH08504890A/ja
Priority to DE69326021T priority patent/DE69326021T2/de
Priority to PL93309404A priority patent/PL309404A1/xx
Priority to AU58481/94A priority patent/AU5848194A/en
Priority to BR9307702-5A priority patent/BR9307702A/pt
Publication of WO1994014999A1 publication Critical patent/WO1994014999A1/en

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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.

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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)
PCT/US1993/012044 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process WO1994014999A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
ES94904428T ES2136726T3 (es) 1992-12-22 1993-12-15 Composicion y procedimiento de revestimiento de conversion de fosfato practicamente exento de niquel.
EP94904428A EP0675972B1 (en) 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process
JP6515227A JPH08504890A (ja) 1992-12-22 1993-12-15 実質的にニッケルを含まないリン酸塩化被膜を形成するための組成物および方法
DE69326021T DE69326021T2 (de) 1992-12-22 1993-12-15 Im wesentlichen nickelfreier phosphatkonversionsüberzug-zusammensetzung und verfahren
PL93309404A PL309404A1 (en) 1992-12-22 1993-12-15 Stable nickel-free phosphate coating composition and method of obtaining same
AU58481/94A AU5848194A (en) 1992-12-22 1993-12-15 Substantially nickel-free phosphate conversion coating composition and process
BR9307702-5A BR9307702A (pt) 1992-12-22 1993-12-15 Composição lìquida aquosa, e, processo para a produção de um revestimento de fosfato e um revestimento protetor sobre a superfìcie de um substrato metálico

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99546592A 1992-12-22 1992-12-22
US07/995,465 1992-12-22

Publications (1)

Publication Number Publication Date
WO1994014999A1 true WO1994014999A1 (en) 1994-07-07

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ID=25541841

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/012044 WO1994014999A1 (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)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711849A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Aktiengesellschaft Verfahren zum Aufbringen von Phosphatüberzügen
WO1997014821A1 (de) * 1995-10-18 1997-04-24 Henkel Kommanditgesellschaft Auf Aktien Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen
WO1997016581A2 (de) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Nitratarme, manganfreie zinkphosphatierung
WO1997030190A1 (de) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Zinkphosphatierung mit geringen gehalten an kupfer und mangan
AU697424B2 (en) * 1995-03-29 1998-10-08 Henkel Kommanditgesellschaft Auf Aktien A phosphating process with a metal-containing after-rinse
WO1999014397A1 (de) * 1997-09-17 1999-03-25 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur phosphatierung von stahlband
EP1828436A1 (en) * 2004-12-28 2007-09-05 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating process that reduces laser scale resulting in improved paint adhesion

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Publication number Priority date Publication date Assignee Title
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
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

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EP0459541A1 (de) * 1990-04-27 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Verfahren zur Phosphatierung von Metalloberflächen

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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
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
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EP0459541A1 (de) * 1990-04-27 1991-12-04 METALLGESELLSCHAFT Aktiengesellschaft Verfahren zur Phosphatierung von Metalloberflächen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711849A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Aktiengesellschaft Verfahren zum Aufbringen von Phosphatüberzügen
AU697424B2 (en) * 1995-03-29 1998-10-08 Henkel Kommanditgesellschaft Auf Aktien A phosphating process with a metal-containing after-rinse
WO1997014821A1 (de) * 1995-10-18 1997-04-24 Henkel Kommanditgesellschaft Auf Aktien Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen
WO1997016581A2 (de) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Nitratarme, manganfreie zinkphosphatierung
WO1997016581A3 (de) * 1995-10-27 1997-06-19 Henkel Kgaa Nitratarme, manganfreie zinkphosphatierung
WO1997030190A1 (de) * 1996-02-19 1997-08-21 Henkel Kommanditgesellschaft Auf Aktien Zinkphosphatierung mit geringen gehalten an kupfer und mangan
AU708141B2 (en) * 1996-02-19 1999-07-29 Henkel Kommanditgesellschaft Auf Aktien Zinc phosphatizing using low concentrations of copper and manganese
WO1999014397A1 (de) * 1997-09-17 1999-03-25 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur phosphatierung von stahlband
EP1828436A1 (en) * 2004-12-28 2007-09-05 Henkel Kommanditgesellschaft Auf Aktien Iron phosphating process that reduces laser scale resulting in improved paint adhesion
EP1828436A4 (en) * 2004-12-28 2011-01-26 Henkel Ag & Co Kgaa LASERZUNDER VERRINGERND AND THEREFORE IN IMPROVED PUNCHING RESULTING IRON PHOSPHATING PROCESS

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CN1090606A (zh) 1994-08-10
JPH08504890A (ja) 1996-05-28
ES2136726T3 (es) 1999-12-01
EP0675972B1 (en) 1999-08-11
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
CN1092245C (zh) 2002-10-09
EP0675972A4 (zh) 1995-11-02
DE69326021D1 (de) 1999-09-16
SG55084A1 (en) 1998-12-21

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