EP0060716B1 - Phosphating metal surfaces - Google Patents

Phosphating metal surfaces Download PDF

Info

Publication number
EP0060716B1
EP0060716B1 EP82301330A EP82301330A EP0060716B1 EP 0060716 B1 EP0060716 B1 EP 0060716B1 EP 82301330 A EP82301330 A EP 82301330A EP 82301330 A EP82301330 A EP 82301330A EP 0060716 B1 EP0060716 B1 EP 0060716B1
Authority
EP
European Patent Office
Prior art keywords
zinc
ion
process according
iron
phosphate
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.)
Expired
Application number
EP82301330A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0060716A1 (en
Inventor
Yasutake Mino
Ryoichi Murakami
Koichi Saito
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.)
Henkel Corp
Original Assignee
Nippon Paint Co Ltd
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 Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Priority to AT82301330T priority Critical patent/ATE33684T1/de
Publication of EP0060716A1 publication Critical patent/EP0060716A1/en
Application granted granted Critical
Publication of EP0060716B1 publication Critical patent/EP0060716B1/en
Expired 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
    • C23C22/73—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 characterised by the process
    • 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
    • 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

Definitions

  • This invention relates to a process for phosphating metal surfaces, and to a composition suitable for use in that process.
  • Japanese Patent Publication (unexamined) No. 107784/1980 (Nippon Paint Co. Ltd.) concerns a method of phosphating iron-based metal surfaces which is particularly suitable for treating manufactured products having complicated surfaces, such as automobile bodies.
  • the method is in use commercially in the automotive industry for pretreating automobile bodies prior to cationic electrocoating, which is a coating process now used extensively in this industry.
  • the phosphating method is carried out by first subjecting the metal surface to a dipping treatment with an acidic aqueous solution containing 0.5 to 1.5 g/I of zinc ion, 5 to 30 g/I of phosphate ion, and 0.01 to 0.2 g/I of nitrite ion and/or 0.05 to 2 g/I of m-nitrobenzenesulfonate ion at a bath temperature of 40 to 70°C for 15 seconds or more, followed by spraying with the above solution for 2 seconds or more.
  • U.S. Patent 3,338,755 discloses a process for phosphating metal surfaces with a phosphating solution containing zinc, manganese, phosphate, nitrate, and nitrite, as essential ingredients, in stated proportions.
  • German Patent 29 31 693 discloses a phosphating process using a solution containing zinc, manganese, phosphate, nitrate, and chlorate ions in stated gram-atom relationships.
  • the present invention provides an improved phosphating method for metal surfaces, which is particularly suitable for treating metal surfaces, such as those of car bodies, which have both iron-based surfaces and zinc-based surfaces.
  • the method is especially advantageous for forming phosphate coating films suitable for electrocoating particularly cationic electrocoating.
  • the invention provides a process for phosphating an iron- or zinc-based metal surface comprising subjecting the metal surface to a dipping treatment in an acidic aqueous solution which contains:
  • the invention also provides this solution as an acidic aqueous composition for phosphating an iron- or zinc-based metal surface.
  • the acidic aqueous solution may also contain one or more of the following:
  • the metal surface can then be coated with a siccative coating, for example by a known electrocoating process, preferably by the cationic electrocoating process.
  • iron- or zinc-based metal surface means iron-based surfaces, iron alloy-based surfaces, zinc-based surfaces, and zinc alloy-based surfaces.
  • Zinc- and zinc alloy-based surfaces include, for example, zinc plated steel plate formed by hot dipping, alloyed zinc plated steel plate formed by hot dipping, zinc plated steel plate formed by electroplating and alloyed zinc plated steel plate formed by electroplating.
  • An important advantage of the present invention is that surfaces of metal components, such as car bodies, that contain both iron-based surfaces and zinc-based surfaces can be treated by the process of the invention with excellent results.
  • the process of the invention produces better conversion coatings than are obtainable with conventional dip treating processes, and the amount of etching of the metal surfaces during the present process is only 2/3 to 4/5 that of conventional processes, so that both the quantity of chemicals used in the process as well as sludge formation is only from 2/3 to 4/5 that of conventional processes.
  • the present process is equally applicable to the treatment of a single metal surface of a type described above.
  • a particularly useful method of carrying out the present process is first to degrease the metal surface to be phosphated for example by spraying and/or dipping the metal surface in a known alkaline degreasing agent at 50°­60°C for two minutes; washing the metal surface with tap water; spraying and/or dip treating the metal surface with a known surface conditioner at room temperature for 10-30 seconds; dipping the surface into the present acidic aqueous solution at 40°­70°C for at least 15 seconds; and washing the metal surface with tap water followed by deionized water.
  • the present acidic aqueous solution has a zinc ion concentration within the range of 0.5 to 1.5 g/l.
  • the amount of zinc ion is less than about 0.5 g/l, an even phosphate film is not formed on an iron-based surface, and a partially blue-coloured film is formed.
  • the amount of zinc ion exceeds about 1.5 g/I, then though an even phosphate film is formed, the film that forms on an iron-based surface tends to be in the form of leaf-like crystals, such as those formed in the spray process, which are unsuitable as a substrate for cationic electrocoating.
  • the amount of manganese ion is less than about 0.6 g/I, the manganese content in the film formed on the zinc-based surface is insufficient, resulting in inadequate adhesivity of the coating film to the phosphate substrate after cationic electrocoating.
  • the amount of manganese ion exceeds about 3 g/I, no further improvement in the phosphate coating is realized, and hence it is uneconomical to use amounts in excess of about 3 g/I.
  • a source of zinc ions for use in the practice of the invention, one or more of the following can be employed: zinc oxide, zinc carbonate, and zinc nitrate.
  • a source of phosphate ions one or more of the following can be used: sodium phosphate, zinc phosphate, and manganese phosphate.
  • manganese carbonate manganese nitrate
  • manganese chloride manganese phosphate
  • nitrite ions As an example of a source of nitrite ions, one or more of the following can be employed: sodium nitrite and ammonium nitrite.
  • sources of chlorate ions chloric acid, sodium chlorate or ammonium chlorate can be used.
  • one or both of the following can be employed: sodium m-nitrobenzenesulfonate, and hydrogen peroxide.
  • the addition of the nickel ion results in further improvement in the performance of the phosphate conversion coating, so that the adhesion and the corrosion-resistance of the film produced by cationic electrocoating are also further improved.
  • nickel carbonate, nickel nitrate, nickel chloride or nickel phosphate can be used for nickel ions; and sodium nitrate, ammonium nitrate, zinc nitrate, manganese nitrate or nickel nitrate for nitrate ions.
  • the present process is usually carried out at a temperature in the range of 40° to 70°C, preferably 45° to 60°C.
  • a temperature in the range of 40° to 70°C, preferably 45° to 60°C.
  • the conversion coating deteriorates, and long periods of treatment time are required to obtain a satisfactory coating.
  • the temperature is higher than about 70°C, the conversion coating accelerators begin to decompose at an unacceptable rate, changing the composition of the bath and resulting in an unacceptable conversion coating. Also, precipitates, begin to form in the bath.
  • the duration that the metal surface contacts the solution in the dip treatment is usually at least 15 seconds, and preferably is from 30 to 120 seconds. When treatment times shorter than about 15 seconds are employed, an adequate phosphate film is not formed.
  • the components can advantageously be subjected first to dipping treatments for 15 seconds or more, preferably 30 to 90 seconds, and then to spray treatment with the solution for 2 seconds or more, preferably for 5 to 45 seconds.
  • the spray treatment is preferably carried out for as long a period within the above range as the speed of the production line will permit.
  • the dipping treatment according to the present invention includes the combination of dipping followed by spraying.
  • Examples I to VII are Examples of the process and compositions of the invention.
  • Examples VIII to XIII are Examples given for comparison purposes.
  • Cross-cuts were made on an electrocoated plate; 5% brine was sprayed thereon for 500 hours (zinc plated steel plate) or 1000 hours (cold rolled steel plate).
  • grids 100 squares were made at 1 mm intervals or at 2 mm intervals using a sharp cutter; an adhesive tape was attached to each surface; and the number of squares of coating film that remained on the plate after the removal of the adhesive tape were counted.
  • a coated plate was set at a 15 degree angle to the horizontal plane, and an arrow with a cone shaped head with a 90 degree vertical angle, made of alloyed steel (material quality, JIS-G-4404, hardness Hv 700 or higher), weighing 1.00 g and 14.0 mm in total length was dropped repeatedly from a distance of 150 cm, until 25 scratches were made on the coated surface. Subsequently, the coated plate was subjected to 4 cycles of testing, each cycle consisting of first the brine spray test (JIS-Z-2871, 24 hours), second, a moisture test (temperature of 40°C, relative humidity 85%, 120 hours), and third, standing at room temperature (24 hours). After testing, the average value (mm) of the largest diameter of rust spots and blisters was obtained, with the results shown in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Chemically Coating (AREA)
  • Glass Compositions (AREA)
  • Secondary Cells (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP82301330A 1981-03-16 1982-03-16 Phosphating metal surfaces Expired EP0060716B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82301330T ATE33684T1 (de) 1981-03-16 1982-03-16 Phosphatierung von metalloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP38411/81 1981-03-16
JP56038411A JPS57152472A (en) 1981-03-16 1981-03-16 Phosphating method for metallic surface for cation type electrodeposition painting

Publications (2)

Publication Number Publication Date
EP0060716A1 EP0060716A1 (en) 1982-09-22
EP0060716B1 true EP0060716B1 (en) 1988-04-20

Family

ID=12524551

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82301330A Expired EP0060716B1 (en) 1981-03-16 1982-03-16 Phosphating metal surfaces

Country Status (10)

Country Link
EP (1) EP0060716B1 (ja)
JP (1) JPS57152472A (ja)
AT (1) ATE33684T1 (ja)
AU (1) AU554406B2 (ja)
BR (1) BR8201400A (ja)
CA (1) CA1200739A (ja)
CS (1) CS179582A2 (ja)
DE (1) DE3278367D1 (ja)
ES (1) ES510472A0 (ja)
MX (2) MX172180B (ja)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2138844A (en) * 1983-04-26 1984-10-31 Pyrene Chemical Services Ltd Formation of phosphate coatings on zinc and iron surfaces
EP0135622A1 (en) * 1983-08-22 1985-04-03 Nippon Paint Co., Ltd. Phosphating metal surfaces
GB2148951A (en) * 1983-11-02 1985-06-05 Pyrene Chemical Services Ltd Phosphating processes and compositions
EP0172806A1 (en) * 1984-01-06 1986-03-05 Ford Motor Company Alkaline resistance phosphate conversion coatings
EP0213567A1 (de) * 1985-08-26 1987-03-11 HENKEL CORPORATION (a Delaware corp.) Verfahren zum Aufbringen von Phosphatüberzügen
EP0219779A2 (de) * 1985-10-18 1987-04-29 Gerhard Collardin GmbH Verfahren zur Phosphatierung elektrolytisch verzinkter Metallwaren
US4941930A (en) * 1986-09-26 1990-07-17 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
EP0385806A1 (en) * 1989-03-02 1990-09-05 Nippon Paint Co., Ltd. Phosphate coatings for metal surfaces
WO1990012901A1 (de) * 1989-04-21 1990-11-01 Henkel Kommanditgesellschaft Auf Aktien Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
WO1991002829A2 (de) * 1989-08-17 1991-03-07 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
AU624433B2 (en) * 1986-09-26 1992-06-11 Ppg Industries Ohio, Inc. Concentrated coating compositions
US5211769A (en) * 1989-12-19 1993-05-18 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
US5244512A (en) * 1991-05-18 1993-09-14 Nippon Paint Co., Ltd. Method for treating metal surface with zinc phosphate
US5268041A (en) * 1990-04-27 1993-12-07 Metallgesellschaft Ag Process for phosphating metal surfaces
EP1012355A1 (en) * 1996-12-04 2000-06-28 Henkel Corporation Sludge reducing zinc phosphating process and composition
US6447662B1 (en) 1998-08-01 2002-09-10 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing, rerinsing and cathodic electro-dipcoating
US6620263B1 (en) 1999-11-04 2003-09-16 Henkel Kommanditgesellschaft Auf Aktien Zinc phosphating process and composition with reduced pollution potential

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5935681A (ja) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd カチオン型電着塗装用金属表面のリン酸塩処理方法
SG52645A1 (en) 1985-08-27 1998-09-28 Henkel Corp A process for phosphate-coating metal surfaces
US4793867A (en) * 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
JPS63227786A (ja) * 1987-03-16 1988-09-22 Nippon Parkerizing Co Ltd 鋼板の電着塗装前処理用りん酸塩処理方法
JPH07100870B2 (ja) * 1990-04-24 1995-11-01 日本ペイント株式会社 金属表面のリン酸亜鉛皮膜処理方法
US5328526A (en) * 1992-04-03 1994-07-12 Nippon Paint Co., Ltd. Method for zinc-phosphating metal surface
CN1041001C (zh) * 1993-09-06 1998-12-02 汉克尔股份两合公司 无镍的磷酸盐化处理金属表面的方法
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
US7531056B2 (en) * 2003-11-28 2009-05-12 Bridgestone Corporation Run-flat tire support and manufacturing method for the same
JP6075167B2 (ja) * 2012-04-18 2017-02-08 Ｊｆｅスチール株式会社 自動車の足回り部材の溶接部塗装後耐食性改善方法および自動車の足回り部材ならびに自動車の足回り部材の製造方法
CN104603490B (zh) 2012-08-23 2017-06-09 皮尔伯格泵技术有限责任公司 机械式内燃机驱动流体泵
EP2888496B1 (en) 2012-08-23 2016-06-22 Pierburg Pump Technology GmbH Mechanical combustion-engine-driven fluid pump

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0018841A1 (en) * 1979-05-02 1980-11-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition and process for zinc-phosphate coating a metal surface, coated metal surface and a process for painting the coated surface

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS506418B1 (ja) * 1971-07-06 1975-03-13
JPS5811513B2 (ja) * 1979-02-13 1983-03-03 日本ペイント株式会社 金属表面の保護方法
GB2072225B (en) * 1980-03-21 1983-11-02 Pyrene Chemical Services Ltd Process and composition for coating metal surfaces

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0018841A1 (en) * 1979-05-02 1980-11-12 Amchem Products, Inc. a Corporation organised under the Laws of the State of Delaware United States of America Composition and process for zinc-phosphate coating a metal surface, coated metal surface and a process for painting the coated surface

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2138844A (en) * 1983-04-26 1984-10-31 Pyrene Chemical Services Ltd Formation of phosphate coatings on zinc and iron surfaces
EP0135622A1 (en) * 1983-08-22 1985-04-03 Nippon Paint Co., Ltd. Phosphating metal surfaces
GB2148951A (en) * 1983-11-02 1985-06-05 Pyrene Chemical Services Ltd Phosphating processes and compositions
EP0172806A1 (en) * 1984-01-06 1986-03-05 Ford Motor Company Alkaline resistance phosphate conversion coatings
EP0172806A4 (en) * 1984-01-06 1986-05-16 Ford Motor Co ALKALINE RESISTANCE PHOSPHATE CONVERSION COATING.
AU594685B2 (en) * 1985-08-26 1990-03-15 Parker Chemical Company Method of forming phosphate coatings on zinc
EP0213567A1 (de) * 1985-08-26 1987-03-11 HENKEL CORPORATION (a Delaware corp.) Verfahren zum Aufbringen von Phosphatüberzügen
EP0219779A2 (de) * 1985-10-18 1987-04-29 Gerhard Collardin GmbH Verfahren zur Phosphatierung elektrolytisch verzinkter Metallwaren
US4762572A (en) * 1985-10-18 1988-08-09 Gerhard Collardin Gmbh Process for phosphating electrolytically zinc-coated metals
EP0219779A3 (en) * 1985-10-18 1988-12-21 Gerhard Collardin Gmbh Phosphatizing process for electrolytically galvanized metal objects
AU624433B2 (en) * 1986-09-26 1992-06-11 Ppg Industries Ohio, Inc. Concentrated coating compositions
US4941930A (en) * 1986-09-26 1990-07-17 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US5238506A (en) * 1986-09-26 1993-08-24 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel-manganese phosphate coating
EP0385806A1 (en) * 1989-03-02 1990-09-05 Nippon Paint Co., Ltd. Phosphate coatings for metal surfaces
WO1990012901A1 (de) * 1989-04-21 1990-11-01 Henkel Kommanditgesellschaft Auf Aktien Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
WO1991002829A3 (de) * 1989-08-17 1991-04-04 Henkel Kgaa Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
WO1991002829A2 (de) * 1989-08-17 1991-03-07 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
US5211769A (en) * 1989-12-19 1993-05-18 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate
US5399208A (en) * 1989-12-19 1995-03-21 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate
US5268041A (en) * 1990-04-27 1993-12-07 Metallgesellschaft Ag Process for phosphating metal surfaces
US5244512A (en) * 1991-05-18 1993-09-14 Nippon Paint Co., Ltd. Method for treating metal surface with zinc phosphate
EP1012355A1 (en) * 1996-12-04 2000-06-28 Henkel Corporation Sludge reducing zinc phosphating process and composition
US6447662B1 (en) 1998-08-01 2002-09-10 Henkel Kommanditgesellschaft Auf Aktien Process for phosphatizing, rerinsing and cathodic electro-dipcoating
US6620263B1 (en) 1999-11-04 2003-09-16 Henkel Kommanditgesellschaft Auf Aktien Zinc phosphating process and composition with reduced pollution potential

Also Published As

Publication number Publication date
EP0060716A1 (en) 1982-09-22
ATE33684T1 (de) 1988-05-15
JPS57152472A (en) 1982-09-20
MX172180B (es) 1993-12-07
AU8150782A (en) 1982-09-23
ES8302127A1 (es) 1983-02-01
CS179582A2 (en) 1984-06-18
CA1200739A (en) 1986-02-18
DE3278367D1 (en) 1988-05-26
ES510472A0 (es) 1983-02-01
MX156539A (es) 1988-09-08
BR8201400A (pt) 1983-02-01
JPH0137478B2 (ja) 1989-08-07
AU554406B2 (en) 1986-08-21

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