EP0478648B1 - Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium - Google Patents

Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium Download PDF

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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
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EP
European Patent Office
Prior art keywords
ions
zinc
magnesium
nickel
steel
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Expired - Lifetime
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EP90909688A
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German (de)
English (en)
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EP0478648A1 (fr
Inventor
Jörg Riesop
Karl-Heinz Gottwald
Wolf-Achim Roland
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C23C22/368—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.

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  • 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)
  • Coating By Spraying Or Casting (AREA)
  • Glass Compositions (AREA)
  • Materials For Medical Uses (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (7)

  1. Procédé de production d'enduits de phosphate de zinc, contenant du manganèse et du magnésium sur de l'acier, du zinc, de l'aluminium et/ou sur leurs alliages par projection, immersion et projection et/ou immersion avec une solution aqueuse, contenant:
    des ions zinc (II), manganèse (II) et magnésium (II) ainsi qu'éventuellement des ions nickel (II), en outre des ions phosphate, des ions fluorure et des ions nitrate ainsi que comme accélérateur des ions nitrite et/ou des ions chlorate et/ou un oxydant organique.
    caractérisé en ce que :
    on traite les surfaces métalliques avec des solutions, qui contiennent les composants suivants:
       0,4 à 0,6 g/l d'ions Zinc (II)
       0,9 à 1,1 g/l d'ions Manganèse (II)
       1,4 à 1,6 g/l d'ions Magnésium (II)
       12,0 à 16,0 g/l d'ions Phosphate,
       0,4 à 0,6 g/l d'ions fluorure,
       1,0 à 5,0 g/l d'ions nitrate et éventuellement
       0,2 à 0,8 g/l d'ions nickel (II).
    ainsi que comme accélérateurs
       0,02 à 0,2 g/l d'ions nitrite et/ou
       0,4 à 1,0 g/l d'ions chlorate et/ou
       0,2 à 1,0 g/l d'un oxydant organique.
    dans lequel la solution aqueuse comporte une teneur en acide libre de 0,6 à 1,8 point et une teneur en acide total de 15 à 30 points et Na⁺ est présent dans la quantité nécessaire pour l'ajustage de l'acide libre.
  2. Procédé selon la revendication 1, caractérisé en ce que la solution aqueuse contient 0,25 à 0,5 g/l d'ions nickel (II).
  3. Procédé selon les revendications 1 ou 2, caractérisé en ce que comme oxydant organique on utilise de l'acide 3-nitrobenzènesulfonique.
  4. Procédé selon la revendication 3, caractérisé en ce qu'on introduit le sel de sodium de l'acide 3-nitrobenzènesulfonique.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on réalise la phosphatation à une température comprise entre 40 et 70°C.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on phosphate les surfaces d'acier, d'acier galvanisé, d'aluminium ou les surfaces valorisées d'alliage suivant le temps de 1 à 5 mm pour la formation d'une couche.
  7. Procédé selon une ou plusieurs des revendications 1 à 6 en tant que préparation des surfaces pour le laquage, en particulier pour le laquage par trempage électrophorétique.
EP90909688A 1989-06-21 1990-06-12 Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium Expired - Lifetime EP0478648B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3920296A DE3920296A1 (de) 1989-06-21 1989-06-21 Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen
DE3920296 1989-06-21
PCT/EP1990/000919 WO1990015889A1 (fr) 1989-06-21 1990-06-12 Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium

Publications (2)

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

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EP90909688A Expired - Lifetime EP0478648B1 (fr) 1989-06-21 1990-06-12 Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium

Country Status (12)

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

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DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
CN1041001C (zh) * 1993-09-06 1998-12-02 汉克尔股份两合公司 无镍的磷酸盐化处理金属表面的方法
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
EP1067212A1 (fr) * 1999-07-08 2001-01-10 Kawasaki Steel Corporation Tôle d'acier galvanisée perforante résistant à la corrosion
KR100419322B1 (ko) * 1999-09-17 2004-02-21 제이에프이 스틸 가부시키가이샤 표면처리강판 및 그 제조방법
DE10109480A1 (de) * 2001-02-28 2002-09-05 Volkswagen Ag Verfahren zur Beschichtung einer Aluminiumoberfläche
DE50310042D1 (de) * 2002-07-10 2008-08-07 Chemetall Gmbh Verfahren zur beschichtung von metallischen oberflächen
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

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

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