EP0713539B1 - Verfahren zur phosphatierenden behandlung von einseitig verzinktem stahlband - Google Patents

Verfahren zur phosphatierenden behandlung von einseitig verzinktem stahlband Download PDF

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Publication number
EP0713539B1
EP0713539B1 EP94924298A EP94924298A EP0713539B1 EP 0713539 B1 EP0713539 B1 EP 0713539B1 EP 94924298 A EP94924298 A EP 94924298A EP 94924298 A EP94924298 A EP 94924298A EP 0713539 B1 EP0713539 B1 EP 0713539B1
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EP
European Patent Office
Prior art keywords
plated
zinc
steel strip
sheet
acid
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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EP94924298A
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German (de)
English (en)
French (fr)
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EP0713539A1 (de
Inventor
Klaus Bittner
Walter K.M. Jansen
Klaus-Peter Mohr
Thomas Wendel
Hardy Wietzoreck
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Chemetall GmbH
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Metallgesellschaft AG
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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
    • C23C22/18—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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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
    • C23C22/34—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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C22/46—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 oxalates
    • C23C22/47—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 oxalates containing also phosphates

Definitions

  • the invention relates to a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet with Using phosphating solutions containing zinc, nitrate and contain nitrite.
  • the phosphating of metals pursues the goal of the metal surface
  • the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / l (DE-C-22 32 067, EP-B-39 093). Under these conditions, phosphate layers with a high content of phosphophyllite (Zn 2 Fe (PO 4 ) 2 • 4 H 2 O) are produced on steel, which is considerably more corrosion-resistant than the hopite (Zn 3 (PO 4 ) 2 • 4 H 2 O).
  • the protection quality in connection with paints can be further increased (EP-A-228 151, EP-B-414 296, EP-B-414 301, EP-A- 544 650, DE-A-39 18 136).
  • Low zinc process with the addition of z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions are widely used as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies.
  • Processes have been developed specifically for the phosphating of electrolytically galvanized or hot-dip galvanized steel strip, which allow the formation of a phosphate layer within short treatment times.
  • it is known from DE-A-32 45 411 to provide, in particular, electrolytically galvanized steel strips with a phosphate layer with a layer weight of less than 2 g / m 2 , solutions being used which are about 1 to 2.5 g / l Contain zinc ions, have a free acid content of 0.8 to 3 points and a total acid / free acid acid ratio of 5 to 10.
  • the duration of treatment should not be significantly longer than 5 seconds.
  • Another method for the phosphating of electrolytically and / or hot-dip galvanized steel strip provides for phosphating solutions which contain 0.02 to 0.75 g / l of zinc, 0 , 2 to 2.0 g / l manganese, 0.1 to 2.0 g / l nickel, 10 to 20 g / l phosphate and 0.5 to 30 g / l nitrate ions.
  • the free acid content in the range from 1.6 to 3.0 points, the total acid content in the range from 12 to 40 points and the weight ratio of nickel ions to nitrate ions in the range from 1:10 to 1:60 and the weight ratio from manganese ions to nitrate ions are in the range from 1: 1 to 1:40 (DE-A-39 27 131).
  • the object of the invention is to provide a method for phosphating treatment of one-sided galvanized or galvanized steel strip or sheet To provide sludge formation to a large extent suppresses the formation of a phosphate layer the steel side prevents the emergence and quality the phosphate layer on the galvanized or alloy galvanized steel side not affected and yet simple in terms of procedure and is economical.
  • the limits of the specified ranges for Complexing agents are important in that they are too high Complexing agent concentrations Phosphate layer formation by complexing the affect layer-forming cations.
  • complexing agent is one Phosphate sludge formation in the phosphating solution and a beginning phosphate layer formation on the Unavoidable steel side.
  • nitrite concentration setting phosphating on the galvanized or alloy galvanized steel side and the complexation of the detached iron can be adversely affected. So can e.g. B. at too high a nitrite concentration starting layer formation on the steel side not be avoided.
  • Such a beginning The subsequent phosphating can form layers affect in the automotive plant, but leads in any case to undesirable sludge formation.
  • a special one a suitable countermeasure is to Nitrite concentration of the phosphating solution using nitrite-degrading substances, such as urea and / or To keep amidosulfonic acid within the stated limits. This can be done through continuous or discontinuous addition happen.
  • a special one elegant method provides for the nitrite concentration by keeping within the necessary limits that one in the phosphating solution Urea concentration of 1 to 3 g / l and / or one Amidosulfonic acid concentration from 0.5 to 2 g / l sets. This becomes a steady state created by the urea or Amidosulfonic acid content is reduced as much nitrite as created by auto-catalysis.
  • Steel strips or sheets to be used can be on the galvanized or alloy galvanized side layers made of electrolytic zinc (ZE), hot zinc (Z), or Alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / aluminum (ZA or AZ). To the latter are usually also alloys e.g. B. 55 wt .-% Al and 45 wt .-% Zn counted.
  • the quality of the phosphate layer produced can be improved if according to another Embodiment of the invention the galvanized or alloy galvanized steel strip or sheet with one Phosphating solution is brought into contact with the further divalent cations, especially manganese and or nickel ions.
  • the concentrations in the Phosphating solution to 1 to 3 g / l, in particular 1.5 to 2.5 g / l manganese ions, and / or 0.1 to 2.5 g / l, in particular 0.5 to 1.5 g / l of nickel ions.
  • Phosphating solution is in the treatment of it hot-dip galvanized or hot dip galvanized steel strip or sheet indispensable to work with phosphating solutions, which contain complex and / or simple fluoride.
  • inventions are also used in the treatment of electrolytically galvanized steel strip or sheet Phosphating solutions used that complex and / or simple fluoride, preferably in Amounts from 0.1 to 3 g / l (calculated as F).
  • complex fluoride is fluoroborate, fluorosilicate. Fluorotitanate and / or fluorozirconate preferred.
  • Phosphating treatment of the strip or sheet can by conventional methods, i.e. in diving or syringes. It is particularly advantageous however, to apply the solution by spraying.
  • the phosphating solution is usually supplemented by a supplementary concentrate, with the control e.g. B. is done automatically via a conductivity measurement.
  • a suitable supplement concentrate contains e.g. B. 10 to 30 wt .-% P 2 O 5 , 3 to 20 wt .-% NO 3 and 0 to 2 wt .-% zinc.
  • the zinc content in the supplemental concentrate depends essentially on the reactivity of the zinc or alloy zinc layer on the steel strip or sheet. If this layer has a higher reactivity and thus larger amounts of zinc get into the bath due to the pickling of the phosphating solution, a supplementary solution with lower zinc concentrations within the range of 0 to 2% by weight is possible.
  • the supplemental concentrate can also be zinc-free.
  • the supplemental solution can also already contain the complexing agent for iron and, if necessary, the NO 2 -degrading substance; however, for reasons of better adjustability of the required concentrations, it will generally be preferable to supplement these two substances separately.
  • phosphate layers are produced, the layer weight of which is approximately 1 to 2 g / m 2 .
  • phosphating was carried out with a solution which had the following components: zinc 1.8 g / l P 2 O 5 14.5 g / l nickel 1.3 g / l manganese 2.0 g / l Tartaric acid 1 g / l urea 1 g / l NO 3 7 g / l NO 2 0.040 g / l.
  • the S value of the phosphating solution was 0.17% Temperature of the phosphating solution was 50 to 55 ° C set. The application was done by spraying for a period of 8 seconds.
  • the phosphating treatment was carried out over a period of 16 hours with a bath size of 25 m 3 . Then a wet sludge amount of 2 ml / 1 phosphating solution was determined. This corresponds to approx. 0.6 ml of sludge per m 2 of penetrated steel surface.
  • a perfect phosphate layer had formed on the zinc side, the layer weight of which was 1.6 g / m 2 .
  • the steel side was in perfect condition, ie showed practically no layer formation.

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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)
  • Coating With Molten Metal (AREA)
  • Electroplating Methods And Accessories (AREA)
EP94924298A 1993-08-06 1994-07-29 Verfahren zur phosphatierenden behandlung von einseitig verzinktem stahlband Expired - Lifetime EP0713539B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4326388A DE4326388A1 (de) 1993-08-06 1993-08-06 Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
DE4326388 1993-08-06
PCT/EP1994/002510 WO1995004842A1 (de) 1993-08-06 1994-07-29 Verfahren zur phosphatierenden behandlung von einseitig verzinktem stahlband

Publications (2)

Publication Number Publication Date
EP0713539A1 EP0713539A1 (de) 1996-05-29
EP0713539B1 true EP0713539B1 (de) 1998-09-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP94924298A Expired - Lifetime EP0713539B1 (de) 1993-08-06 1994-07-29 Verfahren zur phosphatierenden behandlung von einseitig verzinktem stahlband

Country Status (9)

Country Link
US (1) US5795408A (es)
EP (1) EP0713539B1 (es)
JP (1) JP3372954B2 (es)
CN (1) CN1131444A (es)
AT (1) ATE170931T1 (es)
DE (2) DE4326388A1 (es)
ES (1) ES2122318T3 (es)
WO (1) WO1995004842A1 (es)
ZA (1) ZA945881B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
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EP1916317A1 (de) 2006-10-27 2008-04-30 Seppeler Holding und Verwaltungs GmbH & Co. KG Verfahren zur Vorbewitterung von Metallteilen mit einer vorwiegend aus Zink bestehenden Oberfläche

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DE19756735A1 (de) * 1997-12-19 1999-06-24 Henkel Kgaa Phosphatierung von einseitig verzinktem Stahlband
US20040221924A1 (en) * 1999-09-30 2004-11-11 Klaus-Dieter Nittel Method for applying manganese phosphate layers
WO2002046494A1 (fr) * 2000-12-04 2002-06-13 Jfe Steel Corporation Tôle d'acier zinguée et son procédé de production
CN102304709B (zh) * 2011-04-25 2013-10-30 大连三达奥克化学股份有限公司 用于汽车专用工具的黑色磷化剂及制备方法
CN102677034A (zh) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 一种中温低渣锌系磷化液
CN103184444B (zh) * 2013-03-29 2016-08-03 柳州煜华科技有限公司 一种适用于金属紧固件的磷化液
RU2560891C1 (ru) * 2014-05-05 2015-08-20 Федеральное государственное унитарное предприятие федеральный научно-производственный центр "Производственное объединение "Старт" им. М.В. Проценко" (ФГУП ФНПЦ "ПО "Старт" им. М.В. Проценко") Способ фосфатирования железокобальтового сплава
CN105369238B (zh) * 2015-11-23 2017-11-14 安徽千和新材料科技发展有限公司 汽车用镀锌钢板电泳前常温无渣磷化液及其制备方法
US10465292B2 (en) * 2016-10-07 2019-11-05 Goodrich Corporation Anti-corrosion and/or passivation composition for metal-containing substrates and methods for making, enhancing, and applying the same
WO2020074529A1 (en) * 2018-10-08 2020-04-16 Chemetall Gmbh Method for ni-free phosphatizing of metal surfaces and composition for use in such a method
US11566330B2 (en) * 2019-04-16 2023-01-31 Ppg Industries Ohio, Inc. Systems and methods for maintaining pretreatment baths
CN113755777B (zh) * 2021-09-23 2023-01-24 马鞍山钢铁股份有限公司 一种环保型表面处理的镀锌钢板及其制备方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1916317A1 (de) 2006-10-27 2008-04-30 Seppeler Holding und Verwaltungs GmbH & Co. KG Verfahren zur Vorbewitterung von Metallteilen mit einer vorwiegend aus Zink bestehenden Oberfläche

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Publication number Publication date
EP0713539A1 (de) 1996-05-29
DE59406893D1 (de) 1998-10-15
CN1131444A (zh) 1996-09-18
DE4326388A1 (de) 1995-02-09
JP3372954B2 (ja) 2003-02-04
ZA945881B (en) 1996-02-05
WO1995004842A1 (de) 1995-02-16
ES2122318T3 (es) 1998-12-16
ATE170931T1 (de) 1998-09-15
JPH09501202A (ja) 1997-02-04
US5795408A (en) 1998-08-18

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