EP0478648B1 - Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen - Google Patents

Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen Download PDF

Info

Publication number
EP0478648B1
EP0478648B1 EP90909688A EP90909688A EP0478648B1 EP 0478648 B1 EP0478648 B1 EP 0478648B1 EP 90909688 A EP90909688 A EP 90909688A EP 90909688 A EP90909688 A EP 90909688A EP 0478648 B1 EP0478648 B1 EP 0478648B1
Authority
EP
European Patent Office
Prior art keywords
ions
zinc
magnesium
nickel
steel
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
EP90909688A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0478648A1 (de
Inventor
Jörg Riesop
Karl-Heinz Gottwald
Wolf-Achim Roland
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0478648A1 publication Critical patent/EP0478648A1/de
Application granted granted Critical
Publication of EP0478648B1 publication Critical patent/EP0478648B1/de
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
    • C23C22/34—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
    • C23C22/368—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 magnesium 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
    • 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
    • C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations

Definitions

  • the present invention relates to a method for phosphating metal surfaces, in particular a method for producing zinc phosphate coatings containing manganese and magnesium on steel, zinc, aluminum and / or their alloys. These zinc phosphate layers containing manganese and magnesium are applied by spraying, splash-dipping and dipping with aqueous solutions.
  • Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components.
  • the pH of such solutions is usually in the range between 2.8 and 3.4.
  • the process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
  • manganese-modified zinc phosphate coatings are known as a basis of liability for modern coatings.
  • the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been proven to improve corrosion protection, especially when using surface-coated thin sheets.
  • the incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased stability to alkali.
  • the working range of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and electrolytically or hot-dip galvanized steel, whereby the generally achieved quality standard is guaranteed.
  • EP-A-0 261 704 discloses a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, by spraying or splash-dipping to form uniform phosphate layers with a high degree of coverage a phosphating solution is being worked which, in addition to zinc, phosphate and fluoride, can also contain other cations from the group nickel, manganese, magnesium and calcium.
  • a high nickel zinc phosphating process is known from WO 85/03089.
  • extraordinarily high nickel concentrations are used for phosphating.
  • part of the nickel can in principle be replaced by a series of monovalent or divalent cations. These are selected, for example, from cobalt, manganese and magnesium.
  • the nickel content of the solution to be used must be at least 1.0 g / l.
  • the ratio to be used between low zinc and high nickel content is an essential part of technical teaching.
  • the object of the present invention was to provide a phosphating process which is nickel-free or has a lower nickel content compared to the prior art, since nickel is an extremely expensive bath component and is also ecologically unsafe. Since the discharge of nickel-containing wastewater is subject to a charge, the task continued to be to achieve the layer-refining effect of nickel by means of ions that are less harmful to the environment.
  • An advantage of the present invention is that extremely low area-related masses of the phosphate layers could be obtained without loss of corrosion protection behavior. This applies in particular to steel surfaces.
  • fluoride ions are not absolutely necessary when phosphating steel or zinc surfaces.
  • the use of fluoride ions leads to a uniform one Degree of coverage of the phosphate layers on the aluminum.
  • Pure aluminum, AlMg and AlMgSi kneading materials may be mentioned as examples of aluminum surfaces and their alloys. A detailed description of the aluminum materials can be found, for example, in the aluminum pocket book, 14th edition, Aluminum-Verlag, Düsseldorf, 1988.
  • the term steel is understood to mean unalloyed to low-alloy steel, as it e.g. in the form of sheets for body construction.
  • galvanized steel includes e.g. Galvanizing on the electrolytic and on the hot-dip route and refers to zinc and zinc alloys, e.g. Z, ZE, ZNE, ZF, ZA, AZ.
  • the phosphating in the sense of the present invention takes place in spraying, splash immersion and immersion.
  • the metal surfaces to be phosphated must be free from disturbing deposits of oils, lubricants, oxides and the like.
  • the surfaces are cleaned in a suitable manner and, if necessary, with activating agents known per se, e.g. activated aqueous titanium suspensions.
  • the activating agent can usually be introduced in the cleaning bath or as a separate process step.
  • the substances generally used in phosphating technology can be used as accelerators.
  • aqueous phosphating solution which contains chlorate, nitrate, nitrite, peroxide and / or organic oxidizing agents, in particular organic nitro compounds, as accelerators.
  • phosphating solutions known in phosphating technology can be used to modify the procedure and of the layer properties included.
  • examples include: surfactants, polyhydroxycarboxylic acids, polyphosphates, ammonium, alkali, copper, cobalt ions and indifferent anions such as chloride and / or sulfate.
  • the above object is achieved according to claim 1 by a process for the preparation of manganese and magnesium-containing zinc phosphate coatings on steel, zinc, aluminum and / or their alloys by spraying, spray-immersing and / or containing with an aqueous solution 0.4 to 0.6 g / l zinc (II) ions, 0.9 to 1.1 g / l manganese (II) ions, 1.4 to 1.6 g / l magnesium (II) ions, 12.0 to 16.0 g / l phosphate ions, 0.4 to 0.6 g / l fluoride ions, 1.0 to 5.0 g / l nitrate ions and optionally 0.2 to 0.8 g / l Nickel (II) ions and as accelerators: 0.02 to 0.2 g / l nitrite ions and / or 0.4 to 1 g / l chlorate ions and / or 0.2 to 1.0 g / l of an organic
  • a low-zinc process in which nickel is replaced by magnesium is thus described in a first embodiment.
  • the present invention is therefore a zinc phosphating process, which in particular Low zinc range can be used.
  • phosphate layers are generated which contain manganese as well as zinc and magnesium.
  • the addition of Ni ions can be advantageous.
  • surfaces containing zinc (Z, ZE) and in the alloys ZNE, ZF, ZA and AZ the presence of nickel results in improved phosphating results, while a positive effect was not observed on steel surfaces.
  • the solutions to be used can contain small amounts of nickel (II) ions. In this sense, preference is therefore given to solutions which contain 0.2 to 0.8 g / l, in particular 0.25 to 0.5 g / l, of nickel (II) ions.
  • 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
  • the sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
  • the phosphating is carried out at a temperature in the range from 40 to 70 ° C.
  • the surfaces of steel are preferably phosphated in the course of 1 to 5 minutes to form a layer.
  • the surface layers produced with the aid of the method according to the invention can be used well in all fields in which phosphate coatings are used.
  • a particularly advantageous application is the preparation of the metal surfaces for painting, in particular electrocoating.
  • Typical layer analysis (determination quantitatively by atomic absorption spectroscopy, AAS) of the method on: a) Steel Application type element Diving Syringes B2 B1 (nickel free) A2 A1 (nickel free) iron 6.0% 5.4% 2.3% 1.9% manganese 4.3% 4.9% 5.9% 6.1% nickel 0.8% 0.0% 0.8% 0.0% magnesium 0.7% 0.9% 1.1% 1.0% zinc 24.6% 29.5% 30.7% 31.9% Average mass per unit area according to DIN 50942: 1.0 gm ⁇ 2 1.7 gm ⁇ 2 b) Electrolytically galvanized steel Application type element Diving Syringes B2 B1 (nickel free) A2 A1 (nickel free) manganese 4.6% 5.7% 5.3% 5.7% nickel 0.8% 0.0% 0.7% 0.0% magnesium 1.2% 1.2% 1.2% 1.2% 1.2% 1.2% 1.4% zinc 34.4% 34.4% 34.1% 33.8% 33.8% Average mass per unit area according to DIN 50942: 2.5 gm ⁇ 2 2.2 gm ⁇ 2
  • Procedure B2 (diving) 5 rounds (35 days) 10 rounds (70 days) CRS 1) Z 2) ZE 3) CRS Z.
  • ZE Area according to DIN 53209 mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO Cut according to DIN 53167 in mm 0.2 1.2 1.4 0.3 1.7 1.9 Rockfall according to VW norm K 2 K 1 K 2 K 3 K 2 K 2 Procedure C (spray-immersion) 5 rounds (35 days) 10 rounds (70 days) CRS 1) Z 2) ZE 3) CRS Z.
  • blistering that occurs in paints is defined by specifying the degree of blistering.
  • the degree of bubbles according to this standard is a measure of the formation of bubbles on a coating according to the frequency of the bubbles per unit area and the size of the bubbles.
  • the degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area as well as a code letter and a code number for the size of the bubbles.
  • the code letter and the code mO means no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
  • the size of the bubbles is given the code letter g and the code number in the range from 0 to 5.
  • Code letter and code number GO has the meaning - no bubbles - while g5 is shown in accordance with the size of the bubbles in accordance with the degree of bubbles in DIN 53 209.
  • the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
  • the salt spray test according to this standard is used to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating preferably infiltrates from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic surface.
  • the salt spray test is used so that such errors can be recognized and the infiltration can be determined.
  • the VW standard P 1210 is an alternating test that consists of a combination of different standardized test methods. So in Over the course of 60 days in the present case, a test cycle that consists of 4 h salt spray test according to DIN 50 021, 4 h rest at room temperature and 16 h condensation constant climate according to DIN 50 017.
  • the test bone is bombarded with a defined amount of steel shot with a certain grain size distribution.
  • a key figure is assigned to the degree of corrosion.
  • the key figure 1 denotes an invisible corrosion, while with a key figure 10 practically the entire surface is corroded.
  • One round (7 days) of the VDA alternating climate test consists of 24 h salt spray test according to DIN 50021, 96 h condensation water change climate according to DIN 50017 48 h rest at room temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Dental Preparations (AREA)
  • Glass Compositions (AREA)
  • Materials For Medical Uses (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP90909688A 1989-06-21 1990-06-12 Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen Expired - Lifetime EP0478648B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3920296 1989-06-21
DE3920296A DE3920296A1 (de) 1989-06-21 1989-06-21 Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen
PCT/EP1990/000919 WO1990015889A1 (de) 1989-06-21 1990-06-12 Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen

Publications (2)

Publication Number Publication Date
EP0478648A1 EP0478648A1 (de) 1992-04-08
EP0478648B1 true EP0478648B1 (de) 1995-01-18

Family

ID=6383236

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90909688A Expired - Lifetime EP0478648B1 (de) 1989-06-21 1990-06-12 Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen

Country Status (12)

Country Link
US (1) US5207840A (ko)
EP (1) EP0478648B1 (ko)
JP (1) JPH04506233A (ko)
KR (1) KR0171219B1 (ko)
AT (1) ATE117381T1 (ko)
BR (1) BR9007437A (ko)
CA (1) CA2062952A1 (ko)
DE (2) DE3920296A1 (ko)
ES (1) ES2067031T3 (ko)
PT (1) PT94426B (ko)
WO (1) WO1990015889A1 (ko)
ZA (1) ZA904795B (ko)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
WO1995007370A1 (de) * 1993-09-06 1995-03-16 Henkel Kommanditgesellschaft Auf Aktien Nickelfreies phosphatierverfahren
DE4440300A1 (de) * 1994-11-11 1996-05-15 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen
DE19500927A1 (de) * 1995-01-16 1996-07-18 Henkel Kgaa Lithiumhaltige Zinkphosphatierlösung
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
US5900073A (en) * 1996-12-04 1999-05-04 Henkel Corporation Sludge reducing zinc phosphating process and composition
DE19740953A1 (de) * 1997-09-17 1999-03-18 Henkel Kgaa Verfahren zur Phosphatierung von Stahlband
JP3828675B2 (ja) * 1998-04-23 2006-10-04 新日本製鐵株式会社 耐食性、加工性に優れた表面処理鋼板およびその製造方法
DE19834796A1 (de) 1998-08-01 2000-02-03 Henkel Kgaa Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung
US6607844B1 (en) * 1999-03-15 2003-08-19 Kobe Steel, Ltd. Zn-Mg electroplated metal sheet and fabrication process therefor
US6322906B1 (en) 1999-07-08 2001-11-27 Kawasaki Steel Corporation Perforative corrosion resistant galvanized steel sheet
CN1245535C (zh) * 1999-09-17 2006-03-15 杰富意钢铁株式会社 表面处理钢板及其制造方法
DE10109480A1 (de) * 2001-02-28 2002-09-05 Volkswagen Ag Verfahren zur Beschichtung einer Aluminiumoberfläche
JP4233565B2 (ja) 2002-07-10 2009-03-04 ヒェメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属表面を被覆する方法
DE10320313B4 (de) * 2003-05-06 2005-08-11 Chemetall Gmbh Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes
DE10323305B4 (de) * 2003-05-23 2006-03-30 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände
US7815751B2 (en) * 2005-09-28 2010-10-19 Coral Chemical Company Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings
DE102008004728A1 (de) 2008-01-16 2009-07-23 Henkel Ag & Co. Kgaa Phosphatiertes Stahlblech sowie Verfahren zur Herstellung eines solchen Blechs
US10442480B2 (en) * 2017-06-30 2019-10-15 Caterpillar Inc. Coating for seal assembly

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics
US3726720A (en) * 1971-05-24 1973-04-10 Lubrizol Corp Metal conditioning compositions
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
DE3631759A1 (de) * 1986-09-18 1988-03-31 Metallgesellschaft Ag Verfahren zum erzeugen von phosphatueberzuegen auf metalloberflaechen
US4717431A (en) * 1987-02-25 1988-01-05 Amchem Products, Inc. Nickel-free metal phosphating composition and method for use
DE3711931A1 (de) * 1987-04-09 1988-10-20 Metallgesellschaft Ag Verfahren zur bestimmung von zink in phosphatierbaedern
DE3712339A1 (de) * 1987-04-11 1988-10-20 Metallgesellschaft Ag Verfahren zur phosphatierung vor der elektrotauchlackierung

Also Published As

Publication number Publication date
JPH04506233A (ja) 1992-10-29
WO1990015889A1 (de) 1990-12-27
DE59008322D1 (de) 1995-03-02
US5207840A (en) 1993-05-04
KR0171219B1 (ko) 1999-02-18
EP0478648A1 (de) 1992-04-08
ATE117381T1 (de) 1995-02-15
BR9007437A (pt) 1992-04-14
DE3920296A1 (de) 1991-01-10
PT94426B (pt) 1997-02-28
CA2062952A1 (en) 1990-12-22
PT94426A (pt) 1991-02-08
ZA904795B (en) 1991-02-27
KR920702731A (ko) 1992-10-06
ES2067031T3 (es) 1995-03-16

Similar Documents

Publication Publication Date Title
EP0478648B1 (de) Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatüberzügen
EP0633950B1 (de) Nickelfreie phosphatierverfahren
DE2155670B2 (de) Zinkphosphatierungsloesung fuer aluminium, zink oder eisen
EP0370535B1 (de) Verfahren zum Aufbringen von Phosphatüberzügen
EP0796356A1 (de) Verfahren zum aufbringen von phosphatüberzügen auf metalloberflächen
EP0359296B1 (de) Phosphatierverfahren
EP0155547B1 (de) Verfahren zur Zink-Calcium-Phosphatierung von Metalloberflächen bei niedriger Behandlungstemperatur
EP0361375A1 (de) Verfahren zum Aufbringen von Phosphatüberzügen
EP0134895B1 (de) Verfahren und Mittel zum beschleunigten und schichtverfeinernden Aufbringen von Phosphatüberzügen auf Metalloberflächen
DE4326388A1 (de) Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
EP0486576B1 (de) Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
EP0469011B1 (de) Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
EP0264811B1 (de) Verfahren zum Erzeugen von Phosphatüberzügen
WO1998013534A2 (de) Verfahren zur phosphatierung von stahlband
EP0662164B1 (de) Verfahren zum phosphatieren von verzinkten stahloberflächen
EP0215041B1 (de) Verfahren zum phosphatieren von metalloberflächen
WO1999014397A1 (de) Verfahren zur phosphatierung von stahlband
WO1993022474A1 (de) Kupfer enthaltendes, nickelfreies phosphatierverfahren
EP0866888B1 (de) Verfahren zur phosphatierung von metalloberflächen
EP0355525B1 (de) Verfahren zur Erzeugung von Überzügen auf Zink
WO1990015167A1 (de) Verfahren zur erzeugung von manganhaltigen phosphatüberzügen auf metalloberflächen
DE19905479A1 (de) Verfahren zur Phospatisierung von Zink- oder Aluminiumoberflächen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19911213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL SE

17Q First examination report despatched

Effective date: 19940308

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL SE

REF Corresponds to:

Ref document number: 117381

Country of ref document: AT

Date of ref document: 19950215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59008322

Country of ref document: DE

Date of ref document: 19950302

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2067031

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950420

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980603

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980609

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19980615

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980622

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19980629

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980813

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990414

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990612

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990612

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19990621

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990630

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19990630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990612

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20000101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000613

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 20000613

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 90909688.5

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20020204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050612