EP0042631B1 - Procédé de phosphatation de surfaces métalliques - Google Patents

Procédé de phosphatation de surfaces métalliques Download PDF

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Publication number
EP0042631B1
EP0042631B1 EP81200442A EP81200442A EP0042631B1 EP 0042631 B1 EP0042631 B1 EP 0042631B1 EP 81200442 A EP81200442 A EP 81200442A EP 81200442 A EP81200442 A EP 81200442A EP 0042631 B1 EP0042631 B1 EP 0042631B1
Authority
EP
European Patent Office
Prior art keywords
phosphating
metal surfaces
manganese
phosphating solution
bath
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
Application number
EP81200442A
Other languages
German (de)
English (en)
Other versions
EP0042631A1 (fr
Inventor
Han Yong Dr. Dipl.-Chem. Oei
Günter Ing. grad. Siemund
Rudolf Vey
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.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker SA
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 Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Publication of EP0042631A1 publication Critical patent/EP0042631A1/fr
Application granted granted Critical
Publication of EP0042631B1 publication Critical patent/EP0042631B1/fr
Expired 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
    • C23C22/34—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
    • C23C22/364—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 also manganese 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
    • C23C22/07—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
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations

Definitions

  • the invention relates to a process for the production of phosphate coatings with increased layer weight on metal surfaces of iron and steel using an acid nitrate accelerated zinc and manganese ions and in the incorporated state containing Fe 2 + ions phosphating solution at elevated temperatures in the immersion process.
  • z. B. in the range between 8 to 30 g / m 2 required.
  • particularly high demands are placed on corrosion protection. This can be achieved by increasing the layer weight.
  • An increase in the layer weight would also allow higher degrees of deformation in cold forming.
  • the deposition of thick zinc phosphate layers can according to DE-AS 1 287 412 and US Pat. No. 3,268,367 by bringing iron and steel into contact with a nitrate-accelerated acidic zinc phosphating solution with the addition of polycarboxylic acid in which the carbon atom adjacent to at least one carboxyl group contains a hydroxy -, Amino or carboxyl group can be achieved.
  • This phosphating solution can also contain additives such as nickel, cobalt, lithium, bismuth and manganese in small concentrations of less than 0.5 g / l. They activate the metal surface to be phosphated and promote the deposition of zinc phosphate layers.
  • the object of the invention is to provide a phosphating process that does not have the disadvantages described, in particular can be used universally, requires little chemicals and leads to higher-quality phosphate layers.
  • Such a method leads to zinc-manganese-phosphate layers which, with comparable layer thicknesses, are superior to zinc phosphate layers with regard to corrosion protection and cold-forming properties.
  • the metal surfaces are preferably brought into contact with a phosphating solution in which the manganese ion content is at least 1 g / l.
  • the metal surfaces are brought into contact with a phosphating solution in which the weight ratio of Mn: Zn is 1: (0.8 to 12).
  • Manganese ion contents in the phosphating solution above the range of 1: 0.2 lead to non-closed, perforated layers.
  • the total acid number can be determined by titration of a 10 ml bath sample with 0.1 N NaOH against phenolphthalein as an indicator until the color changes from colorless to pink.
  • nickel and / or cobalt and / or copper ions and the like can be added to the bath.
  • these metal ions in a concentration of z. B. 0.02 to 0.10 g / 1 added to the bath.
  • the anion belonging to the metal ions can e.g. B. nitrate or sulfate.
  • a phosphating solution which contains simple and / or complex fluorides, such as NaF, NaHF 2 , and / or Na 2 SiFe.
  • a certain reduction in the layer weight can be brought about if condensed phosphates are added to the phosphating bath.
  • the workpieces to be phosphated should be free of grease, scale and rust.
  • the degreasing can e.g. B. by means of aqueous, alkaline, surface-active substances containing cleaners.
  • Descaling is conveniently carried out using sulfuric acid or hydrochloric acid.
  • the workpieces After cleaning and / or pickling, the workpieces should be rinsed well with water.
  • the workpieces can be formed in a manner known per se, e.g. B. with titanium orthophosphate or manganese orthophosphate suspensions in water. It has been found in practice that in some cases a pre-rinse with water at 50 to 98 ° C activates the surface.
  • the phosphating bath is operated between 50 and 98 ° C depending on the type of workpiece, the alloy and the type of application. It has been shown that a diving time of 5 to 15 minutes is sufficient for most applications.
  • iron II will accumulate in the phosphating bath in the course of the throughput. This does not affect the way the bath works. In special cases, e.g. B. at high nitrate concentrations or at high bath temperatures, it can also happen that the bath: due to the oxidation of fur to Felll remains iron-II-free. This also does not affect the way the bathroom works.
  • the addition of the bath is expediently carried out on a constant total acid number.
  • the layer weight of the zinc-manganese-phosphate layers obtained is normally between about 5 and about 30 g / m 2, depending on the composition of the phosphating bath and the alloy of the workpiece to be treated .
  • z. B. be treated with chromic acid solutions, followed by treatment with anti-corrosion oil emulsions.
  • the workpieces can be used for cold forming e.g. B. Treated with soap solutions.-The workpieces treated in this way are superior to the workpieces treated with conventional nitrate-accelerated zinc phosphating systems in terms of corrosion protection and cold forming properties.
  • composition of baths F and G is shown in the following table.
  • the total acid score of the baths was 90 points each.
  • sample sheets were branched off for the determination of the layer weight and for the corrosion test in the salt spray test according to DIN 50021 SS.
  • the sheets for the corrosion test were previously treated with a 15% emulsion of an anti-corrosion oil and then at 70 ° C dried in the oven.

Landscapes

  • 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)

Claims (5)

1. Procédé de préparation de revêtements de phosphate avec un poids de couche augmenté sur des surfaces métalliques de fer et d'acier en utilisant une solution de phosphatation acide accélérée au nitrate, contenant des ions zinc et manganèse et une fois qu'elle a travaillé des ions Fe2+, à des températures élevées, dans le procédé par immersion, caractérisé en ce qu'on met les surfaces métalliques, à des températures de 50 à 98°C, en contact avec une solution de phosphatation qui contient au moins 0,6 g/l d'ions manganèse, dans laquelle le rapport pondéral est de
P2O5: NO3=1: (0,3 à 3,0)
P2O5 total : P2O5 libre=1: (0,25 à 0,70)
Mn:Zn=1:(22 à 0,2)

et qui présente, une fois qu'elle a travaillé, un nombre de points d'acidité totale d'au moins 20 points.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on met les surfaces métalliques en contact avec une solution de phosphatation dans laquelle la teneur en ions manganèse est d'au moins 1 g/l.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce qu'on met les surfaces métalliques en contact avec une solution de phosphatation dans laquelle le rapport pondéral Mn : Zn = 1 : (0,8 à 12).
4. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce qu'on met les surfaces métalliques en contact avec une solution de phosphatation qui contient des fluorures simples et/ou complexes tels que NaF, NaHF2 et/ou Na2SiFe.
5. Procédé suivant la revendication 1, 2, 3 ou 4, caractérisé en ce qu'on complète le bain de phosphatation, en ce qui concerne les constituants ions zinc, manganèse, phosphate et nitrate, dans le rapport pondéral
P2O5: NO3=1: (0,3 à2,0)
P2O5 total : P2O5 libre=1: (0,3 à 0,8)
Mn:Zn=1: (2 à 80).
EP81200442A 1980-06-24 1981-04-17 Procédé de phosphatation de surfaces métalliques Expired EP0042631B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803023479 DE3023479A1 (de) 1980-06-24 1980-06-24 Phosphatierverfahren
DE3023479 1980-06-24

Publications (2)

Publication Number Publication Date
EP0042631A1 EP0042631A1 (fr) 1981-12-30
EP0042631B1 true EP0042631B1 (fr) 1984-10-31

Family

ID=6105254

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81200442A Expired EP0042631B1 (fr) 1980-06-24 1981-04-17 Procédé de phosphatation de surfaces métalliques

Country Status (6)

Country Link
EP (1) EP0042631B1 (fr)
DE (2) DE3023479A1 (fr)
ES (1) ES8305052A1 (fr)
GB (1) GB2078788B (fr)
IT (1) IT1137254B (fr)
PT (1) PT73117B (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
JPS5935681A (ja) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd カチオン型電着塗装用金属表面のリン酸塩処理方法
US6342107B1 (en) * 1982-08-24 2002-01-29 Henkel Corporation Phosphate coatings for metal surfaces
WO1985003089A1 (fr) * 1984-01-06 1985-07-18 Ford Motor Company Revetement de conversion de phosphate a resistance alcaline
CA1257527A (fr) * 1984-12-20 1989-07-18 Thomas W. Tull Procede de deformation a froid avec enduction lubrifiante amelioree
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
DE3636390A1 (de) * 1986-10-25 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
FR2618164B1 (fr) * 1987-06-25 1994-02-04 Roquette Freres Solution et procede de phosphatation mixte.
DE3840668A1 (de) * 1988-12-02 1990-06-07 Metallgesellschaft Ag Verfahren beim phosphatieren von metalloberflaechen
DE4433946A1 (de) * 1994-09-23 1996-03-28 Henkel Kgaa Phosphatierverfahren ohne Nachspülung
US20040221924A1 (en) 1999-09-30 2004-11-11 Klaus-Dieter Nittel Method for applying manganese phosphate layers
DE19947232A1 (de) * 1999-09-30 2001-04-05 Chemetall Gmbh Verfahren zum Aufbringen von Manganphosphatschichten
DE10010355A1 (de) * 2000-03-07 2001-09-13 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1287412B (de) * 1963-11-30 1969-01-16 Metallgesellschaft Ag Verfahren zur Verbesserung der Korrosionsbestaendigkeit durch Herstellung von Phosphatueberzuegen erhoehten Schichtgewichts auf Oberflaechen aus Eisen und Stahl

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086103A (en) * 1975-08-13 1978-04-25 Kevin James Woods Accelerator for phosphating solutions
JPS5910430B2 (ja) * 1976-04-19 1984-03-08 日本ペイント株式会社 リン酸塩皮膜化成処理方法
GB1591039A (en) * 1977-05-03 1981-06-10 Pyrene Chemical Services Ltd Processes and compositions for coating metal surfaces
JPS5456038A (en) * 1977-10-12 1979-05-04 Nippon Paint Co Ltd Controlling method for acidic phosphate film forming liquid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1287412B (de) * 1963-11-30 1969-01-16 Metallgesellschaft Ag Verfahren zur Verbesserung der Korrosionsbestaendigkeit durch Herstellung von Phosphatueberzuegen erhoehten Schichtgewichts auf Oberflaechen aus Eisen und Stahl

Also Published As

Publication number Publication date
IT8122510A0 (it) 1981-06-23
GB2078788B (en) 1984-10-03
EP0042631A1 (fr) 1981-12-30
ES502507A0 (es) 1983-04-16
DE3166907D1 (en) 1984-12-06
IT1137254B (it) 1986-09-03
ES8305052A1 (es) 1983-04-16
PT73117B (fr) 1982-07-15
DE3023479A1 (de) 1982-01-14
GB2078788A (en) 1982-01-13
PT73117A (fr) 1981-07-01

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