EP0713539A1 - Procede de phosphatage d'un feuillard d'acier galvanise une face - Google Patents

Procede de phosphatage d'un feuillard d'acier galvanise une face

Info

Publication number
EP0713539A1
EP0713539A1 EP94924298A EP94924298A EP0713539A1 EP 0713539 A1 EP0713539 A1 EP 0713539A1 EP 94924298 A EP94924298 A EP 94924298A EP 94924298 A EP94924298 A EP 94924298A EP 0713539 A1 EP0713539 A1 EP 0713539A1
Authority
EP
European Patent Office
Prior art keywords
galvanized
steel strip
sheet
alloy
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.)
Granted
Application number
EP94924298A
Other languages
German (de)
English (en)
Other versions
EP0713539B1 (fr
Inventor
Klaus Bittner
Walter K.M. Jansen
Klaus-Peter Mohr
Thomas Wendel
Hardy Wietzoreck
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.)
Chemetall GmbH
Original Assignee
Metallgesellschaft AG
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 Metallgesellschaft AG filed Critical Metallgesellschaft AG
Publication of EP0713539A1 publication Critical patent/EP0713539A1/fr
Application granted granted Critical
Publication of EP0713539B1 publication Critical patent/EP0713539B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 the phosphating treatment of one-sided galvanized or alloy-galvanized steel strip or sheet with the aid of phosphating solutions which contain zinc, nitrate and nitrite.
  • phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves improve the corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a significant increase in the adhesion and resistance to infiltration when exposed to corrosion.
  • phosphate layers serve as insulation against the passage of electrical currents and, in conjunction with lubricants, to facilitate sliding processes.
  • 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 / 1 (DE-C-22 32 067, EP-B-39 093).
  • the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / 1 (DE-C-22 32 067, EP-B-39 093).
  • phosphate layers with a high content of phosphophyllite (Zn-Fe (P0 4 ) 2 • 4 H 2 0) are produced on steel, which is considerably more corrosion-resistant than the hopite (Zn- (PO.) ⁇ • deposited from zinc-rich phosphating solutions. 4 H 2 0).
  • nickel and / or manganese ions in the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / 1 (DE-C-22 32 067, EP-B-39 09
  • Low-zinc phosphating solutions can further increase the protection quality in connection with paints (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 / 1 manganese ions and z. B. 0.3 to 2.0 g / 1 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.
  • Allow phosphate layer within short treatment times For example, it is from the
  • DE-A-32 45 411 known, in particular electrolytically galvanized steel strips with a phosphate layer
  • Phosphating of electrolytically and / or hot-dip galvanized steel strip provides for phosphating solutions to be applied over a period of 2 to 30 seconds in the temperature range from 40 to 70 ° C., which contain 0.02 to 0.75 g / 1 zinc, 0.2 to
  • Range from 1.6 to 3.0 points, the content of Total acid 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 of manganese ions to nitrate ions 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 the phosphating treatment of one-sided galvanized or alloy-galvanized steel strip or sheet, which largely suppresses sludge formation, prevents the formation of a phosphate layer on the steel side, and the formation and quality of the phosphate layer on the galvanized or alloy-galvanized steel side is not impaired and is nevertheless simple and economical to carry out the process.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the galvanized or alloy-galvanized steel strip or sheet is baked for 4 to 20 seconds with a solution of a temperature of 45 to 80 ° C. Brings contact that
  • the limits of the specified ranges for complexing agents are important insofar as too high complexing agent concentrations impair the formation of the phosphate layer by complexing the layer-forming cations. If the amount of complexing agent added is too low, phosphate sludge formation in the phosphating solution and starting phosphate layer formation on the steel side cannot be avoided. With a higher or lower setting of the nitrite concentration, the phosphating on the galvanized or alloy-galvanized steel side and the complexation of the detached iron can be adversely affected. So z. B. with an excessive nitrite concentration, an incipient layer formation on the steel side cannot be avoided. Such beginning layer formation can impair the subsequent phosphating in the automotive plant, but in any case leads to undesirable sludge formation.
  • a particularly suitable countermeasure is to keep the nitrite concentration of the phosphating solution within the limits mentioned by means of nitrite-degrading substances such as urea and / or amidosulfonic acid. This can be done by continuous or discontinuous addition.
  • a particularly elegant method provides for the nitrite concentration to be kept within the required limits by having a urea concentration of 1 to 3 g / l and / or in the phosphating solution Amidosulfonic acid concentration of 0.5 to 2 g / 1. This creates a steady state in that as much nitrite is broken down by the urea or amidosulfonic acid content as is produced by autocatalysis.
  • the steel strips or sheets to be used within the method according to the invention can have layers of electrolytic zinc (ZE), hot zinc (Z), or alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / Have aluminum (ZA or AZ).
  • ZE electrolytic zinc
  • ZNE zinc / nickel
  • ZF zinc / iron
  • ZA or AZ zinc / Have aluminum
  • the latter are usually alloys with z. B. 55 wt .-% Al and 45 wt .-% Zn counted.
  • This embodiment of the invention has the advantage that the sludge formation is particularly low and that good phosphate layers are also formed on the galvanized or alloy-galvanized side.
  • the galvanized or alloy galvanized Steel strip or sheet is brought into contact with a solution which, as a complexing agent, contains chelating agents such as tartaric acid, citric acid,
  • Ethylenediaminetetraacetic acid, nitrilotriacetic acid and / or oxalic acid contains.
  • the contents of the phosphating solutions in the aforementioned complexing agents should preferably be used
  • the quality of the phosphate layer produced can be improved if, in accordance with a further embodiment of the invention, the galvanized or alloy-galvanized steel strip or sheet is brought into contact with a phosphating solution which contains further divalent cations, in particular manganese and or nickel ions.
  • a phosphating solution which contains further divalent cations, in particular manganese and or nickel ions.
  • phosphating solutions which contain complex and / or simple fluoride preferably in amounts of 0.1 to 3 g / l (calculated as F ), contain.
  • Fluoroborate, fluorosilicate is a complex fluoride. Fluorotitanate and / or fluorozirconate preferred.
  • the phosphating treatment of the strip or sheet can be carried out by conventional methods, that is to say in immersion or spraying. However, it is particularly advantageous 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 ° 5 ' 3 to 20 wt - -% N0 3 and ° 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 attack 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 supplementary concentrate also contains 0.2 to 2% by weight of nickel and / or 1 to 4% by weight of manganese.
  • the supplementary solution can also already contain the complexing agent for iron and, if necessary, the N0 2 -degrading substance; however, for reasons of better adjustability of the required concentrations, it will generally be preferable to supplement these two substances separately.
  • Nickel 1.3 g / i
  • the phosphating treatment was carried out over a period of time

Landscapes

  • 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)
  • Electroplating Methods And Accessories (AREA)
  • Coating With Molten Metal (AREA)
EP94924298A 1993-08-06 1994-07-29 Procede de phosphatage d'un feuillard d'acier galvanise sur une face Expired - Lifetime EP0713539B1 (fr)

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 (fr) 1993-08-06 1994-07-29 Procede de phosphatage d'un feuillard d'acier galvanise une face

Publications (2)

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

Family

ID=6494574

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94924298A Expired - Lifetime EP0713539B1 (fr) 1993-08-06 1994-07-29 Procede de phosphatage d'un feuillard d'acier galvanise sur une face

Country Status (9)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0804632A4 (fr) * 1993-12-15 1997-11-05

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DE19756735A1 (de) * 1997-12-19 1999-06-24 Henkel Kgaa Phosphatierung von einseitig verzinktem Stahlband
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DE102006051384A1 (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
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
CN112888809A (zh) * 2018-10-08 2021-06-01 凯密特尔有限责任公司 金属表面的无镍磷化方法和用于这种方法的组合物
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
CN121161201B (zh) * 2025-11-14 2026-02-03 陕西友发钢管有限公司 热浸镀锌钢管高上锌量控制方法及系统

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* Cited by examiner, † Cited by third party
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* Cited by examiner, † Cited by third party
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EP0804632A4 (fr) * 1993-12-15 1997-11-05

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ATE170931T1 (de) 1998-09-15
JP3372954B2 (ja) 2003-02-04
DE4326388A1 (de) 1995-02-09
ZA945881B (en) 1996-02-05
US5795408A (en) 1998-08-18
WO1995004842A1 (fr) 1995-02-16
DE59406893D1 (de) 1998-10-15
EP0713539B1 (fr) 1998-09-09
CN1131444A (zh) 1996-09-18
ES2122318T3 (es) 1998-12-16
JPH09501202A (ja) 1997-02-04

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