EP0287133B1 - Verfahren zur Phosphatierung vor der Elektrotauchlackierung - Google Patents

Verfahren zur Phosphatierung vor der Elektrotauchlackierung Download PDF

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Publication number
EP0287133B1
EP0287133B1 EP88200219A EP88200219A EP0287133B1 EP 0287133 B1 EP0287133 B1 EP 0287133B1 EP 88200219 A EP88200219 A EP 88200219A EP 88200219 A EP88200219 A EP 88200219A EP 0287133 B1 EP0287133 B1 EP 0287133B1
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EP
European Patent Office
Prior art keywords
workpieces
phosphating solution
contacted
process according
phosphating
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
Application number
EP88200219A
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German (de)
English (en)
French (fr)
Other versions
EP0287133A1 (de
Inventor
Gerhard Müller
Werner Dr. Rausch
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.)
GEA Group AG
Original Assignee
Metallgesellschaft AG
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Filing date
Publication date
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Publication of EP0287133A1 publication Critical patent/EP0287133A1/de
Application granted granted Critical
Publication of EP0287133B1 publication Critical patent/EP0287133B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C23C22/05—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
    • C23C22/07—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

Definitions

  • the invention relates to a method for phosphating workpieces made of steel or partially galvanized steel, in which the cleaned and rinsed workpieces are first activated with an aqueous, weakly alkaline solution containing titanium phosphate and then with an aqueous acidic, NO3, fur and zinc phosphate-containing phosphating solution by immersion treated and its application to the pretreatment for cathodic electrocoating.
  • the object of the invention is to provide a method for the phosphating of steel or partially galvanized steel which provides uniformly covering phosphate layers and is particularly well suited as a pretreatment for electrocoating.
  • the method of the type mentioned according to the invention is designed in such a way that the workpieces are brought into contact with a phosphating solution at a temperature of 40 to 60 ° C. for the pretreatment for the electrocoating 1.8 to 5 g / l Zn 0.1 to 7 g / l Fe (II) 8 to 25 g / l P2O5 5 to 30 g / l NO3 contains and in which the ratio of free acid to total acid is set to 0.04 to 0.07.
  • the method according to the invention is used to treat steel, e.g. of cold-rolled strip and sheet made of soft, unalloyed steels as well as of high-strength cold-rolled thin sheets made of phosphorous steels, micro-alloyed steels and dual-phase steels.
  • the galvanizing layers on galvanized steel include e.g. those produced on the hot-dip path, based on Zn, Zn + Fe, Zn + Al, Zn + Al + Si, and those obtained on the electrolytic path based on Zn, Zn + Ni, Zn + Fe.
  • the method according to the invention can be applied to workpieces of various types and shapes, ie flat parts, deep-drawn parts, welding, folding, flanging and adhesive constructions.
  • workpieces of various types and shapes ie flat parts, deep-drawn parts, welding, folding, flanging and adhesive constructions.
  • adequate ventilation and outflow of the liquid must be ensured.
  • Typical workpieces of complex shape and with a wide variety of materials are automobile bodies.
  • the workpieces are first cleaned in the usual way, for example with alkaline degreasing agents, and then rinsed in water. This is followed by treatment in an aqueous, slightly alkaline solution in which activating titanium phosphate is finely dispersed.
  • Phosphating takes place in the temperature range from 40 to 60 ° C. Below this temperature, the phosphating process becomes too slow to form opaque phosphate layers in reasonable times. Above 60 ° C, energy losses rise sharply and there is an increasing risk of disruptive drying and incrustation.
  • the phosphating process according to the invention belongs to the group of processes on the "iron side” and is therefore characterized by comparatively low sludge formation.
  • the iron (II) concentration can be below 0.1 g / l. After a few throughputs, however, it quickly reaches the area according to the invention as a result of the pickling removal taking place on the steel.
  • the ratio of free acid to total acid is of great importance for the implementation of the method according to the invention. Below 0.04, valuable components of the phosphating solution are lost due to increasing sludge formation. Above 0.07, the rate of phosphating drops sharply.
  • the setting of the optimal ratio is carried out by adjusting the concentration of the bath components, if necessary with the use of further cations, e.g. of Na, K, NH4, or other anions, e.g. of Cl, SO4.
  • the workpieces are brought into contact with a phosphating solution which contains a maximum of 3 g / l Zn and preferably 0.5 to 5 g / l Fe (II).
  • Additional layers can be modified to modify the layer formation divalent cations, for example from the group Ca, Co, Cu, Mg, Mn, Ni, are added to the phosphating solution.
  • the workpieces are preferably brought into contact with a phosphating solution which additionally contains manganese in an amount of up to 3 g / l or magnesium in an amount of up to 3 g / l.
  • a phosphating solution which additionally contains manganese in an amount of up to 3 g / l or magnesium in an amount of up to 3 g / l.
  • cobalt is added, up to 0.3 g / l and nickel up to 0.15 g / l are preferred.
  • streaky phosphate layers can be formed on steel.
  • Another expedient embodiment of the invention consists in bringing the workpieces into contact with a phosphating solution which contains up to 3 g / l, preferably at least 0.3 g / l, of hydroxylamine.
  • concentration of Ni can be increased to 0.5 g / l if at least 0.3 g / l of hydroxylamine are present at the same time.
  • Hydroxylamine has an accelerating effect on the phosphating process.
  • the workpieces are brought into contact with a phosphating solution containing up to 3 g / l SiF6 and / or up to 3 g / l BF4 and / or up to 1.5 g / l F contains.
  • Additions of preferably up to 3 g / l tartaric acid and / or citric acid serve to reduce the weight per unit area of the phosphate layers and to further accelerate the layer formation.
  • phosphating solutions which contain up to 0.5 g / l, preferably 0.05 to 0.35 g / l, of m-nitrobenzenesulfonate.
  • m-Nitrobenzenesulfonate causes a strong acceleration of the phosphating with a simultaneous significant reduction in the thickness of the phosphate.
  • the contact of the phosphating solution with oxygen-containing gas and the addition of chlorate and / or peroxide compounds can be used for this oxidation.
  • the phosphating process according to the invention can also do so be modified that the immersion in the phosphating solution is preceded by a spraying with the phosphating solution and / or is connected.
  • the diving times are usually in the range from 2 to 5 minutes, while the pre-spraying and / or post-spraying takes from a few seconds to about 0.5 minutes.
  • the phosphating process according to the invention is carried out in such a way that phosphate layers with a basis weight of 1 to 5 g / m2 are produced. In this way, optimal corrosion protection is combined with good bending adhesion of the paint coatings.
  • the layers formed by the process according to the invention are suitable as a primer for anodic and cathodic electrocoating materials. Particularly favorable results are achieved if the process is used for pretreatment for cathodic electrocoating and lacquer film thicknesses in the range from approximately 15 to 40 ⁇ m are to be achieved.
  • the electrocoat layers can serve as a base coat for further layers of paint or as single-layer paints.
  • Sheets of body steel and galvanized steel were degreased with an alkaline cleaner, rinsed in water, with an aqueous suspension of about 50 mg / l titanium phosphate in an aqueous solution of 1 g / l disodium phosphate and 0.25 g / l tetrasodium pyrophosphate by immersion at 40 ° C for 1 min and then in the phosphating solutions 1 to 6 listed in the table phosphated at 55 ° C in diving.
  • a minimum phosphating time of 2 to 3 minutes was found on steel and less than 1 minute on galvanized steel.
  • the treatment time in the phosphating bath is defined as the minimum phosphating time, which is necessary for the formation of a visually uniformly covering phosphate layer.
  • the layer weight for steel was between 3.6 and 4.3 g / m2, for zinc between 2.2 and 3.0 g / m2.
  • Free acid (total acid) is defined as the amount of ml n / 10 NaOH required to neutralize 10 ml bath sample against dimethyl yellow (phenolphthalein). The ratio of free acid to total acid was (0.054 to 0.063): 1.
  • rinsing was carried out with water, passivated with a rinse solution containing chromium, rinsed with demineralized water and then electrodeposited cathodically.

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)
EP88200219A 1987-04-11 1988-02-09 Verfahren zur Phosphatierung vor der Elektrotauchlackierung Expired - Lifetime EP0287133B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873712339 DE3712339A1 (de) 1987-04-11 1987-04-11 Verfahren zur phosphatierung vor der elektrotauchlackierung
DE3712339 1987-04-11

Publications (2)

Publication Number Publication Date
EP0287133A1 EP0287133A1 (de) 1988-10-19
EP0287133B1 true EP0287133B1 (de) 1992-03-25

Family

ID=6325439

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88200219A Expired - Lifetime EP0287133B1 (de) 1987-04-11 1988-02-09 Verfahren zur Phosphatierung vor der Elektrotauchlackierung

Country Status (8)

Country Link
EP (1) EP0287133B1 (es)
JP (1) JP2674075B2 (es)
AU (1) AU1442788A (es)
BR (1) BR8801679A (es)
CA (1) CA1332910C (es)
DE (2) DE3712339A1 (es)
ES (1) ES2030493T3 (es)
GB (1) GB2204067B (es)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2636919B2 (ja) * 1989-01-26 1997-08-06 日本パーカライジング株式会社 鉄鋼の冷間塑性加工用潤滑処理方法
JPH0819531B2 (ja) * 1989-03-02 1996-02-28 日本ペイント株式会社 金属表面のリン酸亜鉛処理方法
DE3913089A1 (de) * 1989-04-21 1990-10-25 Henkel Kgaa Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
DE3920296A1 (de) * 1989-06-21 1991-01-10 Henkel Kgaa Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen
DE3927614A1 (de) * 1989-08-22 1991-02-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
US5082511A (en) * 1989-09-07 1992-01-21 Henkel Corporation Protective coating processes for zinc coated steel
US5261973A (en) * 1991-07-29 1993-11-16 Henkel Corporation Zinc phosphate conversion coating and process
US5143562A (en) 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
DE4326388A1 (de) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
DE19541285C2 (de) * 1995-11-06 2003-04-17 Kluthe Gmbh Chem Werke Verfahren und Mittel zur Phosphatierung von Metalloberflächen
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
JPH10204649A (ja) * 1997-01-24 1998-08-04 Nippon Parkerizing Co Ltd 金属表面のりん酸塩処理水溶液及び処理方法
US6179934B1 (en) 1997-01-24 2001-01-30 Henkel Corporation Aqueous phosphating composition and process for metal surfaces
DE19718891C2 (de) * 1997-05-03 2001-03-15 Kluthe Gmbh Chem Werke Verfahren und Mittel zur Phosphatierung von Aluminiumoberflächen
JPH11264076A (ja) * 1998-01-14 1999-09-28 Nippon Paint Co Ltd 低鉛ｅｄ用の下地化成処理方法
DE19808755A1 (de) 1998-03-02 1999-09-09 Henkel Kgaa Schichtgewichtsteuerung bei Bandphosphatierung
AU1581700A (en) * 1998-07-21 2000-02-28 Brent International Plc Nickel-zinc phosphate conversion coatings
DE19905479A1 (de) * 1999-02-10 2000-08-17 Metallgesellschaft Ag Verfahren zur Phospatisierung von Zink- oder Aluminiumoberflächen
JP2001295063A (ja) * 2000-04-10 2001-10-26 Nippon Parkerizing Co Ltd 非鉄金属材料およびめっき鋼板へのりん酸塩被膜の形成方法
JP4992385B2 (ja) * 2006-10-31 2012-08-08 Ｊｆｅスチール株式会社 有機樹脂被覆リン酸塩処理亜鉛系めっき鋼板及びその製造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL271948A (es) * 1960-12-02
BE635970A (es) * 1962-11-13
DE2240049B2 (de) * 1972-08-16 1977-05-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur herstellung von phosphatueberzuegen auf eisen und stahl und konzentrate zur herstellung und ergaenzung der dabei verwendeten phosphatierungsloesung
IT975560B (it) * 1972-10-20 1974-08-10 Sec Accomandita Semplice Fosfa Procedimento di fosfatazione di su perfici metalliche destinate a ver niciatura particolarmente per elet troforesi e soluzione relativa a tale procedimento
GB1408702A (en) * 1973-02-09 1975-10-01 Pyrene Chemical Services Ltd Phosphate coating compositions and processes
JPS5165041A (en) * 1974-12-04 1976-06-05 Nippon Packaging Kk Kinzokuno rinsanenhimakukeiseihoho
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
GB2080835B (en) * 1980-07-25 1984-08-30 Pyrene Chemical Services Ltd Prevention of sludge in phosphating baths
DE3245411A1 (de) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
DE3311738A1 (de) * 1983-03-31 1984-10-04 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metalloberflaechen
DE3345498A1 (de) * 1983-12-16 1985-06-27 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur herstellung von phosphatueberzuegen
FR2569203B1 (fr) * 1984-08-16 1989-12-22 Produits Ind Cie Fse Procede de traitement par conversion chimique de substrats en zinc ou en l'un de ses alliages, concentre et bain utilises pour la mise en oeuvre de ce procede
CA1257527A (en) * 1984-12-20 1989-07-18 Thomas W. Tull Cold deformation process employing improved lubrication coating

Also Published As

Publication number Publication date
BR8801679A (pt) 1988-11-16
GB2204067B (en) 1991-11-27
ES2030493T3 (es) 1992-11-01
GB8808478D0 (en) 1988-05-11
CA1332910C (en) 1994-11-08
JP2674075B2 (ja) 1997-11-05
AU1442788A (en) 1988-10-13
DE3712339A1 (de) 1988-10-20
GB2204067A (en) 1988-11-02
DE3869455D1 (de) 1992-04-30
EP0287133A1 (de) 1988-10-19
JPS64277A (en) 1989-01-05

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