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EP0478648A1 - 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.

Info

Publication number
EP0478648A1
EP0478648A1 EP90909688A EP90909688A EP0478648A1 EP 0478648 A1 EP0478648 A1 EP 0478648A1 EP 90909688 A EP90909688 A EP 90909688A EP 90909688 A EP90909688 A EP 90909688A EP 0478648 A1 EP0478648 A1 EP 0478648A1
Authority
EP
European Patent Office
Prior art keywords
ions
zinc
magnesium
steel
nickel
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
EP90909688A
Other languages
German (de)
English (en)
Other versions
EP0478648B1 (fr
Inventor
Joerg 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/fr
Application granted granted Critical
Publication of EP0478648B1 publication Critical patent/EP0478648B1/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
    • C23C22/34—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 angan 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.
  • 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 for the purpose of formation uniform phosphate layers with a high degree of coverage, a phosphating solution is used which, in addition to zinc, phosphate and fluoride, can also contain other cations from the group consisting of 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 component 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 extraordinarily low area-related masses of the phosphate layers could be obtained without any loss in the 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. Zinc plating on electrolytic and on the melt-dip path and relates 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 disruptive 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 suspensions containing titanium salt.
  • the activating agent can usually be introduced in the cleaning bath or as a separate process stage.
  • 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-mentioned object is achieved by a process for the production of zinc phosphate coatings containing manganese and magnesium on steel, zinc, aluminum and / or their alloys by spraying, splash-dipping and / or dipping with an aqueous solution
  • the aqueous solution containing of free acid from 0.6 to 1.8 points and a total acid content of 15 to 30 points and Na + is present in the amount necessary to adjust the free acid.
  • nitrate ions are due to the use of metal nitrates, for example Zn (N ⁇ 3) 2, for the production of the underlying concentrates and therefore the result of the selected (inexpensive) raw materials.
  • metal nitrates for example Zn (N ⁇ 3) 2
  • 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 produced which, in addition to zinc and magnesium, also contain manganese as cations.
  • the addition of Ni ions can be advantageous.
  • improved phosphating results are obtained by the presence of nickel, while a positive effect was not observed in the case of steel surfaces.
  • the process for producing zinc phosphate coatings on steel, zinc, aluminum and / or their alloys is modified by dipping, spray-dipping and / or dipping with an aqueous solution in such a way that an aqueous solution is obtained
  • 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 / 1, in particular 0.25 to 0.5 g / 1, 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 a layer-forming manner in the course of 1 to 5 minutes.
  • 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.
  • the surface treatment was carried out on cold-rolled steel St.1405, electrolytically galvanized steel (coating on both sides 7.5 ⁇ m Zn) and hot-dip galvanized steel (coating on both sides 10 ⁇ m Zn).
  • Time s 150 150 30 S / 180 T
  • Typical layer analysis determination quantitatively by atomic absorption spectroscopy, AAS) of the method for:
  • blistering that occurs in paints is defined by specifying the degree of blistering.
  • the degree of blistering according to this standard is a measure of a blistering that has occurred on a coating according to the frequency of the blisters per unit area and size of the blisters.
  • 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 identification letter and the identification number mO mean 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 53209.
  • 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 serves 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 is preferably infiltrated from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic substrate.
  • 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 was maintained, which consists of a 4-hour salt spray test in accordance with DIN 50021, a 4-hour rest period at room temperature and a 16-hour condensation water constant in accordance with DIN 50017.
  • 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 invisible corrosion, while with a key figure 10 the entire surface is practically corroded.
  • a round (7 days) test cycle of the VDA change limit test consists of

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

Abstract

Procédé de production d'enduits en phosphate de zinc contenant du manganèse et du magnésium sur de l'acier, du zinc, de l'aluminium et/ou leurs alliages par pulvérisation d'une solution aqueuse, par pulverisation et immersion et/ou par immersion dans une solution aqueuse.
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
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 (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 true EP0478648A1 (fr) 1992-04-08
EP0478648B1 EP0478648B1 (fr) 1995-01-18

Family

ID=6383236

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Families Citing this family (19)

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Publication number Priority date Publication date Assignee Title
DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
JP3348856B2 (ja) * 1993-09-06 2002-11-20 日本パーカライジング株式会社 ニッケルを含まないリン酸塩処理方法
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
TW475002B (en) * 1999-07-08 2002-02-01 Kawasaki Steel Co Perforative corrosion resistant galvanized steel sheet
EP1146145B1 (fr) * 1999-09-17 2008-01-02 JFE Steel Corporation Feuille d'acier traitee en surface et son procede de production
DE10109480A1 (de) * 2001-02-28 2002-09-05 Volkswagen Ag Verfahren zur Beschichtung einer Aluminiumoberfläche
US20050205166A1 (en) 2002-07-10 2005-09-22 Jurgen Specht Method for coating metallic surfaces
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

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Title
See references of WO9015889A1 *

Also Published As

Publication number Publication date
WO1990015889A1 (fr) 1990-12-27
ES2067031T3 (es) 1995-03-16
KR920702731A (ko) 1992-10-06
JPH04506233A (ja) 1992-10-29
DE59008322D1 (de) 1995-03-02
EP0478648B1 (fr) 1995-01-18
US5207840A (en) 1993-05-04
CA2062952A1 (fr) 1990-12-22
BR9007437A (pt) 1992-04-14
ZA904795B (en) 1991-02-27
KR0171219B1 (ko) 1999-02-18
ATE117381T1 (de) 1995-02-15
DE3920296A1 (de) 1991-01-10
PT94426B (pt) 1997-02-28
PT94426A (pt) 1991-02-08

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