EP0324395B1 - Procédé de phosphatisation de surfaces métalliques - Google Patents

Procédé de phosphatisation de surfaces métalliques Download PDF

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Publication number
EP0324395B1
EP0324395B1 EP89100228A EP89100228A EP0324395B1 EP 0324395 B1 EP0324395 B1 EP 0324395B1 EP 89100228 A EP89100228 A EP 89100228A EP 89100228 A EP89100228 A EP 89100228A EP 0324395 B1 EP0324395 B1 EP 0324395B1
Authority
EP
European Patent Office
Prior art keywords
ions
metal surfaces
zinc
brought
solutions
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
EP89100228A
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German (de)
English (en)
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EP0324395A1 (fr
Inventor
Kurt Hosemann
Reinhard Opitz
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.)
Gerhard Collardin GmbH
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Gerhard Collardin GmbH
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Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Priority to AT89100228T priority Critical patent/ATE83509T1/de
Publication of EP0324395A1 publication Critical patent/EP0324395A1/fr
Application granted granted Critical
Publication of EP0324395B1 publication Critical patent/EP0324395B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—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
    • C23C22/22—Orthophosphates containing alkaline earth metal 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
    • C23C22/367—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 alkaline earth metal cations

Definitions

  • the present invention relates to a method for phosphating metal surfaces, in particular the zinc-calcium phosphating of surfaces made of iron, steel, zinc and / or aluminum as a pretreatment for cold forming.
  • 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 sequence consists of two reactions, the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
  • the alkali phosphating processes clean and degrease the metal surface and form a corrosion-protective cover layer, which mainly consists of iron phosphate.
  • the layer formation is initiated by a pickling reaction in which a small amount of the base metal is removed.
  • the majority of the dissolved surface material reacts with the phosphate ion of the solution to form poorly soluble phosphates, which deposit as a firmly adhering coating on the surface.
  • the layer-forming cation originates from the base metal itself.
  • iron phosphate layers with a low layer weight of around 0.2 to 0.4 g / m2 and iron phosphate layers with higher basis weights from 0.6 to 1.2 g / m2.
  • the thin phosphate layers are particularly suitable for painting; they ensure excellent paint adhesion, offer good protection against rust, electrical insulation, reduction of sliding resistance and facilitate cold forming.
  • phosphate layers with a layer weight of up to 40 g / m2 are usually deposited.
  • the metal soaps are known to be produced.
  • Aluminum, calcium, lithium, zinc and magnesium stearates are water-repellent and, as solid lubricants in wire drawing, result in lower coefficients of friction at higher surface pressures than conventional alkali soaps.
  • Metal soaps have the advantage over alkali soaps that they hardly absorb moisture from the air, remain unchanged in their lubricating effect due to their high compressive strength and allow higher overall cross-sectional decreases, while with alkaline soaps the lubricating effect can decrease significantly due to moisture absorption.
  • EP-A-0 045 110 describes a process for the production of phosphate coatings on iron or steel surfaces by immersion or flooding with a rather aqueous acidic zinc phosphate solution, the surfaces being brought into contact with a solution which, in addition to Zn2+, PO43 ⁇ , NO3 ⁇ or a similarly acting iron (II) non-oxidizing accelerator, in which the weight ratio Zn: PO4 is greater than 0.8, the ratio of total acid to free acid is at least 5 and in which, by suitable measurement of ClO3 ⁇ or the like acting iron (II) to iron (III) oxidizing accelerator sets an iron (II) content of 0.05 to 1 wt .-%.
  • the phosphating solutions described here contain 0.3 to 2.2 wt .-% Zn, 0.3 to 2.2 wt .-% PO4 and 0.75 to 5.5 wt .-% NO3, the weight ratio of Zn to PO4 is in the range of (0.8 to 4): 1 and the ratio of total acid to free acid is in the range of (5 to 30): 1.
  • such phosphating solutions can contain calcium in amounts of 0.01 to 0.88% by weight, the weight ratio of Zn to Ca being 1.5 to 4.
  • Other additives can be: copper, cobalt, nickel and simple or complex fluoride.
  • nitroguanidine for example, is suitable as the iron (II) non-oxidizing accelerator.
  • the metal surfaces to be phosphated can be subjected to an activation treatment beforehand.
  • the phosphating process described is particularly suitable as a preparation for non-cutting cold forming.
  • the object of the present invention was to provide an improved method for phosphating metal surfaces made of iron, steel, zinc and their alloys and aluminum as a pretreatment for cold forming.
  • the objects of the present invention are achieved by the improved phosphating process based on zinc-calcium-phosphate layers.
  • the phosphating solution with which the surfaces to be coated are brought into contact can Zn2+ and Ca2+ ions in a weight ratio of 1: 1 contain.
  • preferred embodiments of the present phosphating solution contain further cations of transition metal ions in addition to the above Ca2 und and Zn2+ cations.
  • Ni2+ ions are particularly preferred at this point.
  • the phosphating solutions contain Ni2+ ions, an amount of 0.01 to 10 g / l of Ni2+ ions is preferred.
  • phosphating solutions according to the invention can contain further additional anions.
  • simple and / or complex fluorides can be used as further anions which may be used. These can be used in the phosphating solutions in particular in amounts of 0.01 to 10 g / l.
  • a preferred embodiment of the present invention is to set the temperature range in the range from 50 to 70 ° C. and to bring the metal surfaces into contact with the phosphating solutions.
  • phosphating solutions according to the invention can contain 0.1 to 2.0 g of organic nitro compounds.
  • Organic nitro compounds in the sense of the present invention are selected from m-nitrobenzenesulfonates and / or nitroguanidine.
  • the organic nitro compounds can also be present in amounts of 0.1 to 2.0 g / l in addition to 10 to 100 g / l NO3 ⁇ ions in the phosphating solutions.
  • the process for phosphating metal surfaces made of iron, steel, zinc and their alloys as well as aluminum, zinc-calcium-phosphate layers (Scholzit) with a basis weight of 3 to 9 g / m2 is produced.
  • the zinc-calcium-phosphate layers can be created on the metal surfaces by dipping, spraying and flooding as well as by combined processes.
  • the surfaces to be phosphated are degreased by the processes known in the prior art.
  • Oil, grease and lubricant residues or grinding dust from previous manufacturing processes can be removed by organic solvents or aqueous cleaners.
  • the chlorinated hydrocarbons are the most frequently used organic solvents because they dissolve oils and fats excellently and are not flammable. Solids and inorganic contaminants, however, are removed only inadequately. Water-based cleaners have a very high cleaning ability.
  • the advantage of the present invention is that zinc calcium phosphate layers are suitable for producing low layer weights on the order of 3 to 9 g / m 2 on wire.
  • the zinc-calcium-phosphate layers formed mostly contain the mineral scholzite.
  • a mixed soap of zinc-calcium stearate is formed in addition to zinc stearate and calcium stearate.
  • zinc calcium stearate has the advantage that the durability of the drawing dies is increased many times over. Pulling tests in the technical center also showed that the wire surfaces, in particular during a subsequent polishing pull, achieve a substantially brighter and more uniform appearance than can be achieved with conventional methods operated on the accelerator side.
  • Another product advantage is the fact that the new zinc-calcium phosphating process for cold working works in a temperature range of preferably 50 to 70 ° C.
  • the sludge behavior in this process can be classified as particularly favorable, since even after a bath load of 1.5 m2 steel surface per liter of bath solution, only minimal quantities in the order of a few milliliters of bath sludge are produced.
  • Another advantage of the present invention is that the Sales with drawing soap (sodium stearate) resulting zinc-calcium stearate mixed soaps allow a longer service life of the drawing dies due to the improved properties.
  • a phosphating solution was prepared that 10.3 g of 1 ⁇ 1 Ca2+ ions 14.0 g of 1 ⁇ 1 Zn2+ ions 27.8 g of 1 ⁇ 1 PO43 ⁇ ions 46.5 g of 1 ⁇ 1 NO3 ⁇ ions contained.
  • the phosphating solution had the following characteristics: pH: approx.2.6 Acid ratio: approx. 1:21 (free acid to total acid)
  • Steel wires which had previously been immersed in an alkaline cleaning solution at 80 ° C. for 10 minutes by immersion treatment and rinsed with water, were immersed in the aforementioned phosphating solution at 50 ° C. for 7 minutes. It was then rinsed with water and a reactive soap was applied. Then the wires were drawn over drawing dies. The result was a very bright and shiny surface.
  • the pH was 2.5 and the ratio of free acid to total acid was 1: 17.6.
  • the wire coated in this way could easily be reduced to the desired size using several drawing dies connected in series.
  • the result was a bright and shiny surface.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (8)

  1. Procédé pour la phosphatation de surfaces métalliques à base de fer, d'acier, de zinc et de leurs alliages ainsi que d'aluminium, en tant que prétraitement pour la formage à froid, avec formation de couches de phosphate de calcium-zinc (scholzite) ayant un poids par unité de surface allant de 3 à 9 g/m², procédé dans lequel on nettoie et/on décape les surfaces d'une façon connue en soi et on les traite ensuite par des solutions aqueuses acides qui contiennent des ions Ca²⁺, Zn²⁺, PO₄³⁻ et NO₃⁻, procédé caractérisé en ce que l'on met les surfaces, sans activation, dans la plage de températures de 30 à 70°C, en contact avec une solution aqueuse qui contient :
    (a) de 10 à 40 g/l d'ions Ca²⁺,
    (b) de 10 à 40 g/l d'ions Zn²⁺,
    (c) de 10 à 100 g/l d'ions PO₄³⁻,
    ainsi que, en tant qu'accélérateur,
    (d) de 10 à 100 g/l d'ions NO₃⁻ et/ou
    (e) de 0,1 à 2,0 g/l de composés nitrés organiques, la solution contenant des ions Zn²⁺ et Ca²⁺ en rapport pondéral de 1 : 0,5 à 1 : 1,5 et présentant un pH dans l'intervalle de 2,0 à 3,8, ainsi qu'un rapport de l'acidité libre à l'acidité totale allant de 1 : 4 à 1 : 100.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on met les surfaces métalliques en contact avec une solution qui contient des ions Zn²⁺ et Ca²⁺ dans le rapport pondéral de 1 : 1.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on met les surfaces métalliques en contact avec des solutions, qui contiennent en outre les ions Ni²⁺ en une quantité de 0,01 à 10 g/l.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on met les surfaces métalliques en contact avec des solutions qui contiennent en outre des fluorures simples et/ou complexes en quantités de 0,01 à 10 g/l.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on met les surfaces métalliques en contact avec les solutions à 50-70°C.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on met les surfaces métalliques en contact avec des solutions qui contiennent des composés nitrés organiques, qui sont choisis parmi des m-nitrobenzènesulfonates et/ou la nitroguanidine.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on traite des surfaces métalliques par des solutions par trempage, pistolage ou aspersion ou des procédés mixtes.
  8. Utilisation du procédé selon l'une quelconque des revendications 1 à 7, pour le prétraitement de surfaces métalliques à base de fer, acier, zinc et de leurs alliages, ainsi que d'aluminium, dans l'industrie du formage à froid.
EP89100228A 1988-01-14 1989-01-07 Procédé de phosphatisation de surfaces métalliques Expired - Lifetime EP0324395B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89100228T ATE83509T1 (de) 1988-01-14 1989-01-07 Verfahren zur phosphatierung von metalloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3800835 1988-01-14
DE3800835A DE3800835A1 (de) 1988-01-14 1988-01-14 Verfahren zur phosphatierung von metalloberflaechen

Publications (2)

Publication Number Publication Date
EP0324395A1 EP0324395A1 (fr) 1989-07-19
EP0324395B1 true EP0324395B1 (fr) 1992-12-16

Family

ID=6345237

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89100228A Expired - Lifetime EP0324395B1 (fr) 1988-01-14 1989-01-07 Procédé de phosphatisation de surfaces métalliques

Country Status (9)

Country Link
US (1) US4944813A (fr)
EP (1) EP0324395B1 (fr)
JP (1) JPH01219172A (fr)
AT (1) ATE83509T1 (fr)
AU (1) AU604395B2 (fr)
BR (1) BR8900148A (fr)
DE (2) DE3800835A1 (fr)
MX (1) MX169762B (fr)
TR (1) TR26644A (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5189720A (en) * 1989-04-03 1993-02-23 Sumitomo Electric Industries, Ltd. Method for manufacturing steel wire material for reinforcing optical fiber
JPH03215684A (ja) * 1990-01-18 1991-09-20 Nippon Parkerizing Co Ltd アルミニウムの潤滑皮膜処理法
DE4029985A1 (de) * 1990-09-21 1992-03-26 Bohnacker Tegometall Verfahren zum pulverbeschichten von metalloberflaechen
DE19634685A1 (de) * 1996-08-28 1998-03-05 Metallgesellschaft Ag Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen
US5968240A (en) * 1997-08-19 1999-10-19 Sermatech International Inc. Phosphate bonding composition
DE19808440C2 (de) * 1998-02-27 2000-08-24 Metallgesellschaft Ag Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens
JP2000119862A (ja) * 1998-10-07 2000-04-25 Nippon Parkerizing Co Ltd 鉄鋼の冷間塑性加工用潤滑処理方法
US6902766B1 (en) 2000-07-27 2005-06-07 Lord Corporation Two-part aqueous metal protection treatment
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
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
JP5153063B2 (ja) * 2005-07-15 2013-02-27 日本発條株式会社 鋼材の表面処理方法
CN101232960A (zh) * 2005-08-31 2008-07-30 爱信艾达株式会社 环状部件的制造方法以及带腿环状部件
EP4121580A1 (fr) * 2020-03-19 2023-01-25 ThyssenKrupp Steel Europe AG Procédé de génération d'un revêtement de conversion de phosphate et solution de phosphatation exempte de nickel

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0045110A1 (fr) * 1980-07-25 1982-02-03 Metallgesellschaft Ag Procédé pour la production de revêtements de phosphate sur les surfaces de fer et d'acier et son usage

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3090709A (en) * 1953-08-10 1963-05-21 Lubrizol Corp Phosphate coating of metals
US3161549A (en) * 1955-04-08 1964-12-15 Lubrizol Corp Solution for forming zinc phosphate coatings on metallic surfaces
US3104177A (en) * 1961-12-12 1963-09-17 Lubrizol Corp Phosphating process
DE2540685C2 (de) * 1975-09-12 1985-06-27 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Herstellung von Phosphatüberzügen
JPS5558376A (en) * 1978-10-21 1980-05-01 Nippon Paint Co Ltd Calsium modified zinc phosphate film treating solution
DE3407513A1 (de) * 1984-03-01 1985-09-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur zink-calcium-phosphatierung von metalloberflaechen bei niedriger behandlungstemperatur
JPS60204890A (ja) * 1984-03-28 1985-10-16 Nippon Parkerizing Co Ltd 鉄鋼線材のリン酸塩処理方法
DE3571562D1 (en) * 1984-05-21 1989-08-24 Sumitomo Metal Ind Method for continuous drawing of wire rod
CA1257527A (fr) * 1984-12-20 1989-07-18 Thomas W. Tull Procede de deformation a froid avec enduction lubrifiante amelioree

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0045110A1 (fr) * 1980-07-25 1982-02-03 Metallgesellschaft Ag Procédé pour la production de revêtements de phosphate sur les surfaces de fer et d'acier et son usage

Also Published As

Publication number Publication date
TR26644A (tr) 1994-05-25
US4944813A (en) 1990-07-31
JPH01219172A (ja) 1989-09-01
DE58902980D1 (de) 1993-01-28
ATE83509T1 (de) 1993-01-15
AU2850889A (en) 1989-07-20
BR8900148A (pt) 1989-09-12
DE3800835A1 (de) 1989-07-27
EP0324395A1 (fr) 1989-07-19
AU604395B2 (en) 1990-12-13
MX169762B (es) 1993-07-23

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