EP0578670A1 - Procede de phosphatation de surfaces metalliques. - Google Patents

Procede de phosphatation de surfaces metalliques.

Info

Publication number
EP0578670A1
EP0578670A1 EP92907188A EP92907188A EP0578670A1 EP 0578670 A1 EP0578670 A1 EP 0578670A1 EP 92907188 A EP92907188 A EP 92907188A EP 92907188 A EP92907188 A EP 92907188A EP 0578670 A1 EP0578670 A1 EP 0578670A1
Authority
EP
European Patent Office
Prior art keywords
range
phosphating
cations
solutions
anions
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
EP92907188A
Other languages
German (de)
English (en)
Other versions
EP0578670B1 (fr
Inventor
Reinhard Seidel
Horst-Dieter Speckmann
Karl-Dieter Brands
Gerard Veldman
Raschad Mady
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 EP0578670A1 publication Critical patent/EP0578670A1/fr
Application granted granted Critical
Publication of EP0578670B1 publication Critical patent/EP0578670B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the present invention relates to a process for phosphating metal surfaces, preferably electrolytically or hot-dip galvanized steel strip surfaces, by treating the same in immersion or spray-immersion with acidic, aqueous solutions which, in addition to zinc, phosphate and nitrate ions, are also present Contain ions of at least one other divalent metal, the workpieces being simultaneously treated cathodically with a direct current.
  • JP-A-87/260 073 Phosphate layers with high abrasion resistance are produced (JP-A-87/260 073).
  • JP-A-85/211 080 relates to a method for producing corrosion protection layers on metal surfaces
  • 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. It is also stated that the nickel content of the solution to be used must be at least 1.0 g / 1. The ratio to be used between low zinc and high nickel content is an essential part of technical teaching.
  • the present invention relates to a method for phosphating metal surfaces, preferably electrolytically or hot-dip galvanized steel strip surfaces, by treating them in immersion or spray-immersion with acidic, aqueous solutions which, in addition to zinc, phosphate and nitrate io ⁇ also contain ions of at least one other divalent metal, which is characterized in that a) working with phosphating solutions which contain the following components:
  • N03 anions in the range from 0.1 to 50 g / 1, and
  • the term steel is understood to mean unalloyed to low-alloy steel, as is used, for example, in the form of metal sheets for body construction.
  • This also includes alloy-coated steels, which are surface-coated with zinc / nickel alloys, for example.
  • the method according to the invention is suitable for phosphating steel or galvanized steel strip surfaces.
  • galvanized steel especially electrolytically galvanized steel in strip form, has become very important in recent years.
  • the term "galvanized steel” encompasses both galvanizing by electrolytic deposition and by hot-dip application and generally relates to so-called "pure zinc layers" as well as to known zinc alloys, in particular zinc / nickel alloys.
  • the method according to the invention is preferably carried out in the so-called immersion method; in general, however, it is also possible to apply the phosphating solutions according to the invention to the substrate surfaces by spray dipping.
  • the workpieces to be treated are connected cathodically for the phosphating treatment, an electrode made of stainless steel preferably being used as the counter electrode.
  • a metal container of the phosphating bath can also serve as a counterelectrode; graphite electrodes or, in principle, all of them can also be used Electrode materials known from the relevant prior art are suitable as counterelectrodes.
  • phosphating solutions which contain the following components:
  • Zn 2+ cations in the range from 0.5 to 2 g / 1, PO ⁇ 'anions in the range from 10 to 20 g / 1, N ⁇ 3 "anions in the range from 1 to 30 g / 1 and
  • Ni 2+ cations in the range of 0.5 to 2 g / 1 and / or
  • pH of the phosphating solutions in the range from 2 to 3 pH of the phosphating solutions in the range from 2 to 3, temperature of the phosphating solutions in the range from 40 to 70 ° C, treatment time in the range from 2 to 10 seconds.
  • the workpieces are treated cathodically with a direct current with a density in the range from 1 to 50 mA / cm 2 .
  • the phosphating baths can also additionally contain manganese and / or magnesium cations.
  • the incorporation of these cations into the phosphating layer is not significantly promoted by the use of direct current according to the invention, but it is not disturbed in any way.
  • phosphating solutions which additionally contain Mn 2+ cations in the range from 0.1 to 5 g / 1, preferably from 0.5 to 2 g / 1.
  • phosphating solutions which additionally contain Mg 2+ cations in the range from 0.01 to 2 g / 1, preferably from 0.1 to 1 g / 1, contain.
  • the additional use of manganese and / or magnesium cations in the phosphating baths according to the invention results in an improvement in the corrosion resistance of the phosphating layers obtained therewith.
  • fluoride ions leads to a more uniform degree of coverage of the phosphating layers on the aluminum.
  • phosphating solutions which additionally contain simple or complex fluoride anions in the range from 0.1 to 50 g / 1, preferably from 0.2 to 2 g / 1
  • fluoride anions can also be in
  • Form of complex fluorine compounds for example tetrafluoroborate or hexafluorosilicate, can be used.
  • the specified range of the pH to be maintained includes, among other things, the specified range of the pH to be maintained. If the pH of the phosphating bath is not in the specified range, it is necessary to adjust the phosphating bath to pH values in the specified range by adding acid, for example phosphoric acid, or by adding an alkali, for example sodium hydroxide solution to adjust. If values for the content of free acid or total acid in the phosphating solutions are given in the examples below, these were included in the determined way described in the literature.
  • the so-called free acid score is accordingly defined as the number ml of 0.1 N NaOH which is necessary for the titration of 10 ml of bath solution against dimethyl yellow, methyl orange or bromophenol blue.
  • the total acid score is then the number ml of 0.1 N NaOH required for titration of 10 ml bath solution using phenolphthalein as an indicator until the first pink color.
  • the phosphating solutions according to the invention generally have points of free acid in the range from 0.5 to 3 and of total acid in the range from 15 to 20.
  • the phosphating baths for carrying out the process according to the invention are generally prepared in the customary manner which is known per se to the person skilled in the art.
  • the following compounds can be considered as starting products for the preparation of the phosphating bath: Zinc: in the form of zinc oxide or zinc nitrate; Nickel: in the form of nickel nitrate or nickel carbonate; Cobalt: in the form of cobalt nitrate; Manganese: in the form of manganese carbonate; Magnesium: in the form of magnesium nitrate, magnesium oxide, magnesium hydroxide or magnesium hydroxycarbonate; _Phosphate: preferably in the form of phosphoric acid; Nitrate: in the form of the salts mentioned above, optionally also in the form of the sodium salt.
  • the fluoride ions which may be used in the bath are preferably used in the form of sodium fluoride or in the form of the complex compounds mentioned above.
  • the above-mentioned compounds are - in the concentration ranges essential for the invention - dissolved in water; then, as has also been said above, the pH of the phosphating solutions is adjusted to the desired value.
  • the metal surface to be treated must be completely water-wettable. For this purpose, it is generally necessary to clean and degrease the metal surfaces to be treated by methods known per se and adequately described in the prior art.
  • the cleaned and degreased workpieces have been rinsed with water, preferably with deionized water, to subject the workpieces to be phosphated to an activation pretreatment known per se.
  • an activation pretreatment known per se.
  • titanium-containing activation solutions are used for this purpose, as are described, for example, in DE-A-20 38 105 or DE-A-20 43 085.
  • the metal surfaces to be phosphated subsequently are treated with solutions which contain, as activating agents, essentially titanium salts and sodium phosphate, optionally together with organic components, for example alkylphosphonates or polycarboxylic acids.
  • Soluble compounds of titanium such as potassium titanium fluoride and in particular titanyl sulfate, are preferred as the titanium component.
  • Disodium orthophosphate is generally used as the sodium phosphate. Titanium-containing compounds and sodium phosphate are used in such proportions that the titanium content is at least 0.005% by weight, based on the weight of the titanium-containing compound and the sodium phosphate.
  • the actual phosphating process is then carried out following this activation treatment; the phosphated metal surfaces are then rinsed again with water, again preferably with deionized water.
  • Such Passivation is always sensible and advantageous if the metal surfaces phosphated by the process according to the invention are subsequently painted or coated in another way with organic materials.
  • such passivation can be carried out, for example, with dilute chromic acid or mixtures of chromic and phosphoric acid.
  • the concentration of chromic acid is generally between 0.01 and 1 g / 1.
  • the phosphate 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, for example by spray painting or electrocoating, or for coating with organic foils.
  • Table 1 shows the compositions of the phosphating baths used, including the respective pH values and the values of the free acid and total acid content, for examples 1 to 9 according to the invention and for comparative examples 1 to 3.
  • Example 1 to 8 a cathodic direct current with a current density of 10 mA / cm 2 was applied to the test sheets - during the entire immersion treatment of the same in the respective phosphating baths; In Example 9 according to the invention, the current density was 2 mA / cm 2 . In all cases, a stainless steel electrode served as the counter electrode.
  • Comparative Examples 1 to 3 the phosphating was carried out without such a direct current treatment.
  • the phosphating baths used for comparative examples 1 and 3 contained the cations of nickel and cobalt which are relevant in connection with the present invention in significantly higher amounts than the examples according to the invention.
  • the composition of the phosphating bath in Comparative Example 2 corresponded to the "trication process" commonly used in practice today, ie the phosphating bath contained Zn, Ni and Mn.
  • test sheets were coated with an epoxy-based cathodic electrocoat (Aqualux R K, ICI, Hilden).
  • the dry film density was 18-2 ⁇ m.
  • the corrosion protection of the respective phosphating layers was then determined by determining the coating infiltration in accordance with a cathodic polarization test.
  • the respective test sheets were provided with a single cut in accordance with DIN 53 167 and then in a 10% by weight aqueous Na2SÜ4 solution with a current flow of 0.75 A and one Polarization time of 40 hours immersed.
  • the infiltration of paint was evaluated in accordance with DIN 53 167 (see Table 2, a).
  • Day 2 to 5 Alternating condensate climate according to DIN 50017 KFW; Day 6 to 7: Storage at room temperature in accordance with DIN 50014.
  • the phosphating layers on the respective test sheets were detached with chromic acid to determine their composition and analyzed by ICP spectroscopy.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Selon un procédé de phosphatation de surfaces métalliques, de préférence de surfaces de feuillards d'acier métallisées par électrolyse ou par immersion à chaud, les surfaces sont traitées par immersion ou au pistolet avec des solutions aqueuses acides de phosphatation, les pièces étant traitées cathodiquement en même temps par un courant continu. Le procédé se caractérise par (a) l'utilisation de solutions de phosphatation qui contiennent les composants suivants: des cations de Zn2+ dans une proportion comprise entre 0,1 et 5 g/l; des anions de PO43- dans une proportion comprise entre 5 et 50 g/l; des anions de NO3- dans une proportion comprise entre 0,1 et 50 g/l; ainsi que des cations de Ni2+ dans une proportion comprise entre 0,1 et 5 g/l; et/ou des cations de Co2+ dans une proportion comprise entre 0,1 et 5 g/l; (b) le respect des conditions suivantes: valeur de pH des solutions de phosphatation comprise entre 1,5 et 4,5; température des solutions de phosphatation comprise entre 10 et 80 °C; durée de traitement comprise entre 1 et 300 sec; (c) traitement cathodique des pièces pendant la phosphatation avec un courant continu ayant une densité comprise entre 0,01 et 100 mA/cm2.
EP92907188A 1991-04-06 1992-03-30 Procede de phosphatation de surfaces metalliques Expired - Lifetime EP0578670B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4111186A DE4111186A1 (de) 1991-04-06 1991-04-06 Verfahren zum phosphatieren von metalloberflaechen
DE4111186 1991-04-06
PCT/EP1992/000703 WO1992017628A1 (fr) 1991-04-06 1992-03-30 Procede de phosphatation de surfaces metalliques

Publications (2)

Publication Number Publication Date
EP0578670A1 true EP0578670A1 (fr) 1994-01-19
EP0578670B1 EP0578670B1 (fr) 1996-05-15

Family

ID=6428973

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92907188A Expired - Lifetime EP0578670B1 (fr) 1991-04-06 1992-03-30 Procede de phosphatation de surfaces metalliques

Country Status (5)

Country Link
US (1) US5401381A (fr)
EP (1) EP0578670B1 (fr)
JP (1) JPH06506263A (fr)
DE (2) DE4111186A1 (fr)
WO (1) WO1992017628A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645706A (en) * 1992-04-30 1997-07-08 Nippondenso Co., Ltd. Phosphate chemical treatment method
DE4232292A1 (de) * 1992-09-28 1994-03-31 Henkel Kgaa Verfahren zum Phosphatieren von verzinkten Stahloberflächen
EP0653502A3 (fr) * 1993-11-11 1995-08-09 Nihon Parkerizing Article composite d'acier plaqué d'un métal contenant du zinc et procédé de production.
US5797987A (en) * 1995-12-14 1998-08-25 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
DE19635085A1 (de) * 1996-08-30 1998-03-05 Eckart Standard Bronzepulver Korrosionsstabile, durch Physical Vapor Deposition hergestellte Aluminiumpigmente und Verfahren zu deren Stabilisierung
US6066403A (en) * 1997-12-15 2000-05-23 Kansas State University Research Foundation Metals having phosphate protective films
JP2000144494A (ja) * 1998-09-11 2000-05-26 Nippon Parkerizing Co Ltd 冷間圧造用の潤滑皮膜を形成する方法
BR9907916B1 (pt) * 1998-12-17 2011-07-26 processo de tratamento quÍmico por fosfato eletrolÍtico para formar uma pelÍcula, e, pelÍcula composta sobre uma superfÍcie de aÇo.
JP3479609B2 (ja) 1999-03-02 2003-12-15 日本パーカライジング株式会社 スラッジ発生のないリン酸亜鉛処理液およびリン酸亜鉛処理方法
TW475002B (en) 1999-07-08 2002-02-01 Kawasaki Steel Co Perforative corrosion resistant galvanized steel sheet
DE19947719A1 (de) * 1999-10-05 2001-04-12 Daimler Chrysler Ag Wärmebehandelte Karosserie - "body-in-blue"
JP4419905B2 (ja) * 2005-04-28 2010-02-24 株式会社デンソー 電解リン酸塩化成処理方法
DE102005023023B4 (de) * 2005-05-19 2017-02-09 Chemetall Gmbh Verfahren zur Vorbereitung von metallischen Werkstücken zum Kaltumformen, mit dem Verfahren beschichtete Werkstücke und ihre Verwendung
JP4419968B2 (ja) * 2005-07-15 2010-02-24 株式会社デンソー 電解リン酸塩化成処理方法ならびに温間もしくは熱間鍛造加工方法
DE102010030697A1 (de) * 2010-06-30 2012-01-05 Henkel Ag & Co. Kgaa Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion
CN102146578A (zh) * 2011-01-24 2011-08-10 重庆大学 一种在Cr、Ni元素含量高的合金钢上制备磷化膜的方法
EP2826890A1 (fr) * 2013-07-19 2015-01-21 ATOTECH Deutschland GmbH Procédé pour la protection cathodique contre la corrosion de surfaces chromées

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US3449229A (en) * 1966-08-08 1969-06-10 Hooker Chemical Corp Electrophoretic deposition on zinc enriched metal surface
JPS5429979B2 (fr) * 1974-02-22 1979-09-27
JPS5429189B2 (fr) * 1974-06-20 1979-09-21
JPS5247537A (en) * 1975-10-15 1977-04-15 Nippon Steel Corp Chemical conversion process for zinc coated steel sheet
EP0172806A4 (fr) * 1984-01-06 1986-05-16 Ford Motor Co Revetement de conversion de phosphate a resistance alcaline.
JPS60211080A (ja) * 1984-04-04 1985-10-23 Nippon Paint Co Ltd 浸漬式リン酸亜鉛処理法
JPS6148597A (ja) * 1984-08-14 1986-03-10 Nippon Paint Co Ltd リン酸亜鉛化成処理法
JPS62260073A (ja) * 1986-05-01 1987-11-12 Yamaha Motor Co Ltd リン酸塩処理方法
JPS63262500A (ja) * 1987-04-20 1988-10-28 Nippon Parkerizing Co Ltd チタン又はチタン合金の潤滑性改善処理方法
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process

Non-Patent Citations (1)

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Title
See references of WO9217628A1 *

Also Published As

Publication number Publication date
WO1992017628A1 (fr) 1992-10-15
DE59206321D1 (de) 1996-06-20
EP0578670B1 (fr) 1996-05-15
JPH06506263A (ja) 1994-07-14
US5401381A (en) 1995-03-28
DE4111186A1 (de) 1992-10-08

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