EP0219779B1 - Procédé de phosphatation de pièces métalliques zinguées électrolytiquement - Google Patents

Procédé de phosphatation de pièces métalliques zinguées électrolytiquement Download PDF

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Publication number
EP0219779B1
EP0219779B1 EP86114075A EP86114075A EP0219779B1 EP 0219779 B1 EP0219779 B1 EP 0219779B1 EP 86114075 A EP86114075 A EP 86114075A EP 86114075 A EP86114075 A EP 86114075A EP 0219779 B1 EP0219779 B1 EP 0219779B1
Authority
EP
European Patent Office
Prior art keywords
zinc
range
content
phosphating
ratio
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
EP86114075A
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German (de)
English (en)
Other versions
EP0219779A3 (en
EP0219779A2 (fr
Inventor
Raschad Mady
Cäcilie Daniel
Detlev Bohnhorst
Karl-Heinz Gottwald
Roland Dr. Morlock
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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Filing date
Publication date
Application filed by Gerhard Collardin GmbH filed Critical Gerhard Collardin GmbH
Priority to AT86114075T priority Critical patent/ATE70314T1/de
Publication of EP0219779A2 publication Critical patent/EP0219779A2/fr
Publication of EP0219779A3 publication Critical patent/EP0219779A3/de
Application granted granted Critical
Publication of EP0219779B1 publication Critical patent/EP0219779B1/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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • 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
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations

Definitions

  • the invention relates to an improved method for producing fine crystalline, closed conversion layers, consisting predominantly of zinc phosphate, with a low mass per unit area in very short treatment times on electrolytically galvanized metal products, in particular ferrous metals, for example on electrolytically galvanized steel strips.
  • the process is not limited to "pure zinc layers". Steel strips that have been given a zinc alloy coating can also be treated. In addition to zinc, iron, nickel and cobalt are examples of alloy components.
  • the treatment times were over 5 seconds; targeted belt speeds of 90 to 120 m / min, for example, were impossible or difficult to achieve and with quality losses, such as non-closed layers.
  • DE-A-21 00 021 proposes to form thin closed phosphate layers with mass per unit area of ⁇ 1.0 g / m 2 to treat the metal surfaces with phosphating solutions which essentially contain nickel ions as layer-forming cations.
  • nickel ions in addition to the nickel ions, further metal ions, in particular zinc ions, can be present.
  • the molar ratio of the nickel ions to the other divalent metal ions should be in the range from 1: 0.001 to 1: 0.7.
  • nickel phosphate layers are deposited. In contrast to the desired zinc phosphate layers, they always require a subsequent coating with, for example, a varnish in order to achieve acceptable corrosion protection. This is a serious disadvantage.
  • the weight ratio of Zn2+ / NO3 ⁇ is kept in the range of 1 / (1 to 8), the weight ratio PO43 ⁇ / NO3 ⁇ in the range of 1 / (0.1 to 2.5).
  • DE-A-32 45 411 uses nickel ions, the Zn2+ content preferably always predominating. Ratios of 20 to 2 parts by weight of Zn2+ ions to one part by weight of Ni2+ ions can be particularly useful. Most of the time, nickel cannot be detected analytically in the deposited layer, so it is only present in the layer in traces that remain below the detection limit.
  • the phosphating takes place in the temperature range from 50 to 70 ° C., preferably in the range from 60 to 65 ° C. The process is suitable for both spray and dip application.
  • electrolytically galvanized steel strip is also increasingly being used in body construction; in many cases the phosphating is already applied in combined galvanizing and pre-treatment lines and the material is supplied as galvanized, "pre-phosphated" steel.
  • the phosphating should therefore also be suitable for subsequent cathodic electrocoating. Since iron cannot be built into the phosphate layer in the present case, layers with a cubic or cuboid structure must be created.
  • the object of the invention is a method described below which fulfills the requirement.
  • Acid phosphating solutions which, in addition to zinc, manganese and phosphate ions, can contain further metal cations and / or anions of oxygen-containing acids with accelerating action.
  • the phosphate layers produced have mass per unit area of less than 2 g / m2, the preferred range is 0.9 to 1.6 g / m2. Layers in the range of 0.6 to 1.9 g / m2 can be deposited.
  • the acidic phosphating solutions are characterized in that the zinc cation content is in the range from 0.1 to 0.8 g / l, preferably 0.25 to 0.6 g / l.
  • the content of manganese II cations is kept in the range of 0.5 to 2 g / l, preferably 0.75 to 1.25 g / l.
  • the free acid content is kept in a range from 4 to 8 points, preferably 5 to 7 points.
  • the acid ratio (total acid / free acid) is kept in the range of 2.5 to 5 points, the preferred range is 2.8 to 4.5.
  • the free acid score is defined as the number of milliliters of 0.1 N NaOH required to titrate 10 ml bath solution against dimethyl yellow, methyl orange or bromophenol blue.
  • the total acid score is the number of milliliters of 0.1 N NaOH required to titrate 10 ml bath solution against phenolphthalein as an indicator until the first pink color.
  • the process according to the invention is further characterized in that the phosphating baths contain nitrate.
  • the cobalt content is preferably one part of cobalt per 100 to 150 parts of Zn2+ and Mn2+.
  • treatment times are deliberately kept short in view of the modern systems for the electrolytic galvanizing and phosphating of steel strips, 90 to 120 m / min speed of the strip. 5 seconds are not significantly exceeded, treatment times of 2.5 to 5 seconds are generally used.
  • the phosphating is expediently carried out at elevated temperatures, in particular in the temperature range from 40 to 70 ° C., the temperature range from 45 to 55 ° C. being particularly suitable. Any technically useful way of applying the treatment solution is applicable. It is particularly interesting that the process according to the invention can be carried out both by spraying technology and by immersion.
  • the electrolytically galvanized surface Before the phosphating solution is applied, the electrolytically galvanized surface must be completely water wettable. This is usually the case in conveyor systems. If the surface of the electrolytically galvanized strip is oiled for the purpose of temporary corrosion protection, this oil must be removed by known, suitable means and methods before phosphating.
  • the water-wettable electrolytically galvanized metal surface is expediently treated with activating solutions known per se before phosphating.
  • the activators essentially contain titanium salts and phosphates, together with organic components. Information on suitable activation methods can be found in DE-A-20 38 105 and DE-A-20 43 085.
  • the process according to the invention can also be advantageous for the process according to the invention to passivate the deposited conversion layers with dilute chromic acid and / or phosphoric acid.
  • the chromic acid concentration is generally between 0.01 and 1 g / l. It is also possible to passivate the protective layers with dilute chromic acid, which contains chromium III ions.
  • the concentrations generally used are 0.2 to 4.0 g / l CrO3 (hexavalent chromium) and 0.5 to 7.5 g / l Cr2O3 (trivalent chromium).
  • phosphate layers are produced on electrolytically galvanized steel, which clearly show a cuboid or cuboid structure. This is proven by scanning electron microscope images. This was not possible with the previously known method, including the method described in DE-A-32 45 411. Crystals with a needle-like shape were deposited.
  • the method according to the invention thus achieves the object of providing a conversion layer suitable for the subsequent cathodic electrocoating on electrolytically galvanized steel produce.
  • the type of layer described is also achieved on steel galvanically coated with a zinc-nickel alloy.
  • a lighter colored conversion layer is produced. This is particularly desirable when the electrolytically galvanized and phosphated steel is used without further coating. In this case, phosphating is expected to significantly delay or suppress both the occurrence of the so-called “white rust” (formation of zinc corrosion products) and the “red rust” (iron corrosion products).
  • the layers deposited from the acidic phosphating solutions according to the invention fulfill this task significantly better than layers deposited from conventional treatment baths.
  • the acidic phosphating baths according to the invention work very low in sludge. This is a not insignificant advantage for practical use.
  • the deposited layers consist predominantly of Zn phosphate.
  • the small amounts of cobalt contained in the phosphating baths lead one to expect that, given the low surface masses deposited according to the invention, cobalt can no longer be detected in the layers, since the content is below the detection limit. It is surprising, however, that manganese is only found in very small amounts in the layers deposited from the acid phosphating solutions according to the invention.
  • An electrolytically galvanized surface was treated at 30 ° C. with a solution which contained an activating agent containing titanium, as described in DE-A-20 38 105, in an amount of 3 g / l.
  • the activated surface was then treated with a solution of the following composition at 50 ° C: 1.1 g / l Mn2+, 0.50 g / l Zn2+, 0.01 g / l Co2+, 11.2 g / l H2PO4 ⁇ , 1.5 g / l NO3 ⁇ .
  • the free acidity was 6 points and the total acidity was 19.6 points.
  • the sheet was rinsed with water and then passivated with a solution containing Cr6+ + Cr3+ and dried.
  • the mass per unit area of the phosphate coating was 1.15 g / m2.
  • a sheet treated in the same way was cathodically electrocoated and provided with a filler and topcoat that are common in the automotive industry.
  • the painted surface was bombarded with steel granules under defined conditions and then stored at 40 ° C. for 40 h in a 5% saline solution. Then the sheet was again bombarded with steel granules.
  • the sheet according to Example 1 was given characteristic values 3 to 4.
  • Example 1 The activation of the sheets was carried out as shown in Example 1, as was the passivation following the phosphating.
  • the phosphating time and the temperatures also correspond to example 1.
  • the same amounts g / l as in example 1 were used, but the solution contained no cobalt.
  • Free acid and total acid as in Example 1.
  • the weight per unit area of the phosphate coating was 1.3 g / m2.
  • Test sheets made using conventional methods e.g. according to the method proposed in DE-A-32 45 411, show a significantly poorer behavior after the tests described.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (12)

  1. Procédé pour la phosphatation de pièces métalliques zinguées par électrolyse, de préférence de pièces en acier zinguées électrolytiquement, en particulier de bandes d'acier zingué par électrolytiquement par traitement de courte durée, n'excédant pratiquement pas 5 secondes, par des solutions de phosphatation acides qui peuvent contenir, en plus d'ions zinc, manganèse et phosphate, d'autres cations métalliques et/ou anions d'acides oxygénés à effet accélérateur, avec formation de couches constituées essentiellement de phosphate de zinc, ayant une masse par rapport à la surface inférieure à 2 g/m², caractérisé en ce que l'on opère avec des solutions de phosphatation acides dont la teneur en cations Zn(Zn²⁺) se situe dans la plage de 0,1 à 0,8 g/l et dont la teneur en cations manganèse (Mn²⁺) se situe dans la plage de 0,5 à 2,0 g/l, tandis que la teneur en acide libre est maintenue dans la plage de 4 à 8 points et le rapport d'acide (acide total/acide libre) est maintenu dans la plage de 2,5 à 5.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur en cations Zn²⁺ se situe dans la plage de 0,25 à 0,6 g/1.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la teneur en cations Mn²⁺ se situe dans la plage de 0,75 à 1,25 g/l.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la teneur en acide libre est maintenue dans la plage de 5 à 7 points et le rapport d'acide est maintenu dans la plage de 2,8 à 4,5.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que des couches essentiellement constituées de phosphate de zinc sont déposées sur une épaisseur de couche de 0,6 à 1,9 g/m².
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on utilise des bains de phosphatation contenant du nitrate dans lesquels le rapport pondéral Zn²⁺ + Mn²⁺/NO₃⁻ est maintenu dans la plage de 1/(0,5 à 1,5).
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le rapport Zn²⁺/Mn²⁺ est maintenu dans la plage de 1/(1 à 3).
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce le rapport pondéral H₂PO₄⁻/NO₃⁻ est maintenu dans la plage de (6 à 9)/1.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le rapport (Zn²⁺ + Mn²⁺)/H₂PO₄⁻ est maintenu dans la plage de 1/(6 à 9).
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on opère avec des bains contenant de faibles quantités de cobalt, la quantité de cobalt, par rapport à la teneur en (Zn²⁺ + Mn²⁺) allant de 100 à 150 parties de (Zn²⁺ + Mn²) pour 1 partie de cobalt.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la phosphatation est effectuée dans la plage de température de 40 à 70°C.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'on soumet à une phosphatation de la bande d'acier zinguée par électrolyse, qui a été préalablement soumise à un prétraitement d'activation, connu en soi, avec des solutions d'activation contenant du titane.
EP86114075A 1985-10-18 1986-10-10 Procédé de phosphatation de pièces métalliques zinguées électrolytiquement Expired - Lifetime EP0219779B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86114075T ATE70314T1 (de) 1985-10-18 1986-10-10 Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853537108 DE3537108A1 (de) 1985-10-18 1985-10-18 Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
DE3537108 1985-10-18

Publications (3)

Publication Number Publication Date
EP0219779A2 EP0219779A2 (fr) 1987-04-29
EP0219779A3 EP0219779A3 (en) 1988-12-21
EP0219779B1 true EP0219779B1 (fr) 1991-12-11

Family

ID=6283862

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86114075A Expired - Lifetime EP0219779B1 (fr) 1985-10-18 1986-10-10 Procédé de phosphatation de pièces métalliques zinguées électrolytiquement

Country Status (10)

Country Link
US (1) US4762572A (fr)
EP (1) EP0219779B1 (fr)
JP (1) JPH086183B2 (fr)
KR (1) KR930010339B1 (fr)
AT (1) ATE70314T1 (fr)
AU (1) AU581789B2 (fr)
CA (1) CA1240905A (fr)
DE (2) DE3537108A1 (fr)
ES (1) ES2002422A6 (fr)
ZA (1) ZA867903B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3927131A1 (de) * 1989-08-17 1991-02-21 Henkel Kgaa Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
US5118367A (en) * 1989-09-25 1992-06-02 The Goodyear Tire & Rubber Company Process for treating a brass-plated steel wire
JPH05287549A (ja) * 1992-04-03 1993-11-02 Nippon Paint Co Ltd カチオン型電着塗装のための金属表面のリン酸亜鉛処理方法
DE4228470A1 (de) * 1992-08-27 1994-03-03 Henkel Kgaa Verfahren zur Phospatierung von einseitig verzinktem Stahlband
EP0717788B1 (fr) * 1993-09-17 1997-07-30 Brent International Plc. Rincage preliminaire destine au depot de phosphate sur des surfaces metalliques
DE19808755A1 (de) 1998-03-02 1999-09-09 Henkel Kgaa Schichtgewichtsteuerung bei Bandphosphatierung
AU1453101A (en) 1999-11-04 2001-05-14 Henkel Corporation Zinc phosphating process and composition with reduced pollution potential
US20060054248A1 (en) * 2004-09-10 2006-03-16 Straus Martin L Colored trivalent chromate coating for zinc
US20080314479A1 (en) * 2007-06-07 2008-12-25 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating
WO2009028801A2 (fr) * 2007-08-24 2009-03-05 Posco Composition de revetement destinee à des feuilles d'acier comprenant du zinc et une couche de revetement d'alliage de zinc, procede de realisation d'une couche de revêtement faisant intervenir ladite composition de revetement et feuille d'acier presentant ladite couche de revetement forme
DE202011107125U1 (de) * 2011-04-13 2011-11-30 Tata Steel Ijmuiden Bv Warmformbares Band, Blech oder Zuschnitt und warmgeformtes Produkt
CN102864446A (zh) * 2012-10-12 2013-01-09 广西工学院 一种常温磷化液及其制备方法

Family Cites Families (15)

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Publication number Priority date Publication date Assignee Title
GB526815A (en) * 1939-03-14 1940-09-26 Samuel Thomas Roberts Improvements relating to the rustproofing of ferrous surfaces prior to painting or enamelling
US3338755A (en) * 1963-09-03 1967-08-29 Hooker Chemical Corp Production of phosphate coatings on metals
GB1257947A (fr) * 1968-10-31 1971-12-22
DE2043085C3 (de) * 1970-08-31 1979-03-29 Gerhard Collardin Gmbh, 5000 Koeln Verfahren zum Aufbringen von Zinkphosphatschichten auf elektrolytisch verzinktes Material
DE2100021A1 (de) * 1971-01-02 1972-09-07 Collardin Gmbh Gerhard Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen
IT1120362B (it) * 1979-05-29 1986-03-19 Fosfa Col S A S Di A Dal Pane Soluzione per la fosfatazione a freddo di superfici metalliche
GB2072225B (en) * 1980-03-21 1983-11-02 Pyrene Chemical Services Ltd Process and composition for coating metal surfaces
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
EP0135622B1 (fr) * 1983-08-22 1988-12-07 Nippon Paint Co., Ltd. Phosphatation de surfaces métalliques
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
US4486241A (en) * 1981-09-17 1984-12-04 Amchem Products, Inc. Composition and process for treating steel
DE3245411A1 (de) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
AU1834083A (en) * 1983-08-23 1985-02-28 Nippon Paint Co., Ltd. Process for phosphating metal surfaces
JPS6050175A (ja) * 1983-08-26 1985-03-19 Nippon Paint Co Ltd 亜鉛および亜鉛合金の表面処理浴
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc

Also Published As

Publication number Publication date
CA1240905A (fr) 1988-08-23
ATE70314T1 (de) 1991-12-15
JPH086183B2 (ja) 1996-01-24
DE3537108A1 (de) 1987-04-23
ES2002422A6 (es) 1988-08-01
AU6415686A (en) 1987-04-30
JPS6299478A (ja) 1987-05-08
EP0219779A3 (en) 1988-12-21
ZA867903B (en) 1987-05-27
EP0219779A2 (fr) 1987-04-29
US4762572A (en) 1988-08-09
DE3682865D1 (de) 1992-01-23
AU581789B2 (en) 1989-03-02
KR930010339B1 (ko) 1993-10-16
KR870004164A (ko) 1987-05-07

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