EP1060290B1 - Solution aqueuse et procede pour phosphater des surfaces metalliques - Google Patents

Solution aqueuse et procede pour phosphater des surfaces metalliques Download PDF

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Publication number
EP1060290B1
EP1060290B1 EP99911702A EP99911702A EP1060290B1 EP 1060290 B1 EP1060290 B1 EP 1060290B1 EP 99911702 A EP99911702 A EP 99911702A EP 99911702 A EP99911702 A EP 99911702A EP 1060290 B1 EP1060290 B1 EP 1060290B1
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EP
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Prior art keywords
solution
aqueous
phosphate
nitroguanidine
aqueous solution
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 - Lifetime
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EP99911702A
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German (de)
English (en)
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EP1060290A1 (fr
Inventor
Peter Schubach
Joachim Heitbaum
Thomas Kolberg
Margit Fleischhacker-Jeworrek
Peter Jörns
Michael Deemer
Ralf Stickler
Jürgen SPECHT
Michael Lenhard
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Chemetall GmbH
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Chemetall GmbH
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    • 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
    • C23C22/12—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
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/82—After-treatment
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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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)
  • Chemically Coating (AREA)
  • Catalysts (AREA)

Claims (20)

  1. Solution aqueuse contenant des phosphates, permettant de former une couche de phosphates sur des surfaces métalliques en fer, en acier, en zinc, en alliage de zinc, en aluminium ou en alliage d'aluminium, qui contient de 0,3 à 5 g/l d'ions Zn2+, de 0,1 à 2 g/l de nitroguanidine et de 0,05 à 0,5 g/l d'hydroxylamine, et dans laquelle le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/30 et l'indice d'acide vaut de 0,03 à 0,3, cet indice d'acide indiquant le rapport de la quantité d'acide libre, calculée en P2O5 libre, à la quantité totale de P2O5.
  2. Solution aqueuse conforme à la revendication 1, contenant de 0,1 à 1,5 g/l de nitroguanidine.
  3. Solution aqueuse conforme à l'une des revendications 1 à 2, contenant de 0,1 à 0,4 g/l d'hydroxylamine.
  4. Solution aqueuse conforme à l'une des revendications 1 à 3, contenant de 0,3 à 3 g/l d'ions Zn2+.
  5. Solution aqueuse conformé à l'une des revendications 1 à 4, contenant de 0,5 à 20 g/l d'ions NO3 -.
  6. Solution aqueuse conforme à l'une des revendications 1 à 5, contenant de 0,01 à 3 g/l d'ions Mn2+ et/ou de 0,01 à 3 g/l d'ions Ni2+ et/ou de 1 à 100 mg/l d'ions Cu2+ et/ou de 0,01 à 3 g/l d'ions Co2+.
  7. Solution aqueuse conforme à l'une des revendications 1 à 5, contenant de 0,01 à 3 g/l d'ions F- et/ou de 0,05 à 3,5 g/l d'au moins un fluorure complexe.
  8. Solution aqueuse conforme à l'une des revendications 1 à 7, contenant, en tant que fluorure complexe, des ions (SiF6)2- ou (BF4)-.
  9. Procédé de phosphatation de surfaces métalliques, dans lequel on nettoie une surface métallique, puis on la traite avec une solution aqueuse contenant des phosphates, conforme à l'une des revendications 1 à 8, pendant un laps de temps de 5 secondes à 10 minutes et à une température de 15 à 70 °C, et enfin, on la lave avec de l'eau.
  10. Procédé conforme à la revendication 9, dans lequel le traitement de la surface métallique avec la solution de phosphatation s'effectue par pulvérisation, immersion, pulvérisation-immersion, ou application au rouleau.
  11. Procédé conforme à l'une des revendications 9 à 10, dans lequel, dans la solution de phosphatation employée en pulvérisation, le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/30, et la pulvérisation dure de 5 à 300 secondes.
  12. Procédé conforme à l'une des revendications 9 à 10, dans lequel, dans la solution de phosphatation employée en bain d'immersion, le rapport pondéral Zn2+/P2O5 vaut de 1/5 à 1/18, et l'immersion dure de 5 secondes à 10 minutes.
  13. Procédé conforme à l'une des revendications 9 à 12, dans lequel, après avoir nettoyé la surface métallique, on la traite avec un agent d'activation qui contient un phosphate comprenant du titane.
  14. Procédé conforme à l'une des revendications 9 à 13, dans lequel, après l'opération de lavage qui suit la phosphatation, on traite la surface métallique avec un agent de passivation.
  15. Procédé conforme à la revendication 9, dans lequel la nitroguanidine est incorporée dans la solution aqueuse sous forme d'une suspension aqueuse stable.
  16. Procédé conforme à la revendication 15, dans lequel la suspension aqueuse stable contient, en guise d'agent stabilisant, un silicate à structure en feuillets.
  17. Procédé conforme à la revendication 16, dans lequel on emploie, comme agent stabilisant, le silicate à structure en feuillets [Mg6(Si7,4Al0,6)O20(OH)4]Na0,6 . xH2O ou [(Mg5,4Li0,6)Si8O20(OH,F)4]Na0,6 . xH2O à raison de 10 à 30 grammes par litre de suspension de nitroguanidine.
  18. Procédé conforme à la revendication 15, dans lequel la suspension aqueuse stable contient un agent stabilisant constitué d'un polysaccharide et d'un polyéthylèneglycol, présents en un rapport pondéral de 1/1 à 1/3 du polysaccharide au polyéthylèneglycol, cet agent stabilisant étant employé à raison de 5 à 20 grammes par litre de suspension de nitroguanidine.
  19. Emploi d'une solution aqueuse contenant des phosphates, conforme à l'une des revendications 1 à 8, et d'un procédé de phosphatation conforme à l'une des revendications 9 à 18, pour le traitement de pièces ouvrées avant revêtement.
  20. Emploi conforme à la revendication 20, pour le traitement de pièces avant revêtement électrophorétique.
EP99911702A 1998-02-27 1999-02-24 Solution aqueuse et procede pour phosphater des surfaces metalliques Expired - Lifetime EP1060290B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19808440 1998-02-27
DE19808440A DE19808440C2 (de) 1998-02-27 1998-02-27 Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens
PCT/EP1999/001186 WO1999043868A1 (fr) 1998-02-27 1999-02-24 Solution aqueuse et procede pour phosphater des surfaces metalliques

Publications (2)

Publication Number Publication Date
EP1060290A1 EP1060290A1 (fr) 2000-12-20
EP1060290B1 true EP1060290B1 (fr) 2002-09-18

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EP99911702A Expired - Lifetime EP1060290B1 (fr) 1998-02-27 1999-02-24 Solution aqueuse et procede pour phosphater des surfaces metalliques

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US (1) US6497771B1 (fr)
EP (1) EP1060290B1 (fr)
JP (1) JP2002505378A (fr)
KR (1) KR20010041417A (fr)
CN (1) CN1292041A (fr)
AT (1) ATE224466T1 (fr)
AU (1) AU740987B2 (fr)
BR (1) BR9909236A (fr)
CA (1) CA2325012A1 (fr)
DE (2) DE19808440C2 (fr)
PL (1) PL342623A1 (fr)
SI (1) SI20378A (fr)
SK (1) SK12352000A3 (fr)
TR (1) TR200002495T2 (fr)
WO (1) WO1999043868A1 (fr)

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DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
ATE399218T1 (de) 2002-07-10 2008-07-15 Chemetall Gmbh Verfahren zur beschichtung von metallischen oberflächen
US20040118483A1 (en) * 2002-12-24 2004-06-24 Michael Deemer Process and solution for providing a thin corrosion inhibiting coating on a metallic surface
US20040261752A1 (en) * 2003-06-26 2004-12-30 Wolfgang Rein Phosphatized and bushingless piston and connecting rod assembly having an internal gallery and profiled piston pin
US6923153B2 (en) 2003-06-26 2005-08-02 Mahle Technology, Inc. Piston and connecting rod assembly having phosphatized bushingless connecting rod and profiled piston pin
US7581315B2 (en) 2004-11-16 2009-09-01 Mahle Technology, Inc. Connecting rod assembly for an internal combustion engine and method of manufacturing same
US7516546B2 (en) * 2004-11-16 2009-04-14 Mahle Technology, Inc. Method of manufacturing a connecting rod assembly for an internal combustion engine
US8613137B2 (en) 2004-11-16 2013-12-24 Mahle International Gmbh Connecting rod lubrication recess
CN102953055B (zh) * 2012-11-07 2014-05-14 长沙沃尔金属表面技术有限公司 一种黑色磷化液及其使用方法
KR101968836B1 (ko) * 2017-09-26 2019-04-12 현대제철 주식회사 전기아연도금강판 및 이의 제조방법
JP7443253B2 (ja) * 2018-02-19 2024-03-05 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング 複合金属構造体の選択的リン酸塩処理方法

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US2768104A (en) * 1952-03-25 1956-10-23 Heintz Mfg Co Method for coating iron
GB2148950B (en) * 1983-10-26 1987-02-04 Pyrene Chemical Services Ltd Phosphating composition and processes
CA1257527A (fr) * 1984-12-20 1989-07-18 Thomas W. Tull Procede de deformation a froid avec enduction lubrifiante amelioree
DE3800835A1 (de) * 1988-01-14 1989-07-27 Henkel Kgaa Verfahren zur phosphatierung von metalloberflaechen
US5137589A (en) * 1990-02-09 1992-08-11 Texo Corporation Method and composition for depositing heavy iron phosphate coatings
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
DE4210513A1 (de) * 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
EP0717787B1 (fr) * 1993-09-06 1998-01-14 Henkel Kommanditgesellschaft auf Aktien Procede de phosphatage sans nickel
DE4417965A1 (de) * 1994-05-21 1995-11-23 Henkel Kgaa Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
DE19634685A1 (de) * 1996-08-28 1998-03-05 Metallgesellschaft Ag Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen

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BR9909236A (pt) 2000-11-14
EP1060290A1 (fr) 2000-12-20
KR20010041417A (ko) 2001-05-15
TR200002495T2 (tr) 2000-12-21
DE19808440C2 (de) 2000-08-24
DE19808440A1 (de) 1999-09-09
AU740987B2 (en) 2001-11-22
DE59902751D1 (de) 2002-10-24
ATE224466T1 (de) 2002-10-15
CA2325012A1 (fr) 1999-09-02
SK12352000A3 (sk) 2001-05-10
PL342623A1 (en) 2001-06-18
CN1292041A (zh) 2001-04-18
SI20378A (sl) 2001-04-30
AU3029899A (en) 1999-09-15
US6497771B1 (en) 2002-12-24
JP2002505378A (ja) 2002-02-19
WO1999043868A1 (fr) 1999-09-02

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