EP0866888B1 - Procede pour la phosphatation de surfaces metalliques - Google Patents

Procede pour la phosphatation de surfaces metalliques Download PDF

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Publication number
EP0866888B1
EP0866888B1 EP96938047A EP96938047A EP0866888B1 EP 0866888 B1 EP0866888 B1 EP 0866888B1 EP 96938047 A EP96938047 A EP 96938047A EP 96938047 A EP96938047 A EP 96938047A EP 0866888 B1 EP0866888 B1 EP 0866888B1
Authority
EP
European Patent Office
Prior art keywords
phosphating
metal surfaces
process according
brought
contact
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
EP96938047A
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German (de)
English (en)
Other versions
EP0866888A1 (fr
Inventor
Horst Gehmecker
Thomas Kolberg
Rüdiger Rein
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.)
Chemetall GmbH
Original Assignee
Metallgesellschaft AG
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Filing date
Publication date
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Publication of EP0866888A1 publication Critical patent/EP0866888A1/fr
Application granted granted Critical
Publication of EP0866888B1 publication Critical patent/EP0866888B1/fr
Anticipated expiration legal-status Critical
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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
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
    • 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 a method for phosphating consisting at least partially of iron or steel Metal surfaces according to the low zinc technology as well as its Application to prepare the metal surfaces for the Electrocoating, especially for the cathodic Electro dip painting.
  • the Phosphating solutions used here contain zinc in Concentrations of only about 0.4 to 2 g / l and produce Steel phosphate layers that have a very good paint adhesion and high Resistance to paint infiltration Offer corrosion stress.
  • EP-A-414296 proposes a method for phosphating iron and steel surfaces according to the low zinc technology with nitrite-free, zinc, phosphate and nitrate-containing phosphating solutions in which the weight ratio of free P 2 O 5 increases Total P 2 O 5 is set to a value in the range of 0.04 to 0.2.
  • H 2 O 2 or alkali perborate should be added to the phosphating solution in such an amount that - in the incorporated state - the maximum peroxide concentration 17 mg / l (calculated as H 2 O 2 ) or the maximum Fe (II) concentration 60 mg / l (calculated as Fe).
  • the object of the invention is to provide a method for Phosphating of at least partially iron or steel to provide existing metal surfaces that too leads to sufficiently thick and fine crystalline phosphate layers, in the event of the simultaneous presence of zinc and / or Aluminum surfaces thereon too Leads phosphate layers and that with the addition of chlorate associated disadvantage does not have.
  • the object is achieved in that, according to the invention, a method of the type mentioned at the outset is used, in which the metal surfaces are kept at 30 to 65 ° C. for a period of 1 to 8 minutes. in contact with aqueous acid phosphating solutions, the 0.4 to 2.0 g / l Zn 7 to 25 g / l P 2 O 5 0.005 to 0.5 g / l peroxide (calculated as H 2 O 2 ) 0.01 to 10 g / l formate (calculated as formation) Contain that are free of chlorate and added nitrite, in which the weight ratio of free P 2 O 5 to total P 2 O 5 to a value in the range of 0.03 to 0.20 and the content of free acid to a value is set in the range from 0.5 to 2.5.
  • Free of added nitrite means that the No nitrite should be added to phosphating solutions, but - if the process is designed with nitrate addition, if necessary low levels due to nitrate formation can.
  • the inventive method is particularly for Surface treatment of iron and steel determined. Together with iron and steel, however, galvanized steel, alloy galvanized steel, i.e. e.g. with ZnAl, ZnFe and ZnNi coated steel, aluminized steel, aluminum, zinc and their alloys are treated.
  • phosphating baths for phosphating metal surfaces, in particular galvanized or alloy-galvanized steel strips, with treatment times of 2 to 20 seconds.
  • phosphate and certain contents of free acid and total acid they are water-soluble, organic acids contain a pK value between the dissociation constants of the first and the second stage of the phosphoric acid contained in the phosphating bath for the first dissociation constant, formic acid being mentioned as an example of suitable organic acids and hydrogen peroxide or peroxide compounds as an example of an additional oxidizing agent.
  • the phosphating process according to EP-A-361375 also provides Phosphating solutions, which preferably correspond to the Low zinc technology work, formic acid, if necessary in combination with nitrate, chlorate, nitrite and Nitrobenzenesulfonate to add.
  • Purpose of the addition Formic acid is when using nickel-containing Phosphating solutions Phosphate coatings with relatively high Generate nickel levels even if the nickel concentration is comparatively low in the phosphating solution. Also from this prior art it could not be deduced that the with advantages obtained by the method according to the invention can be achieved are.
  • the used in the inventive method Phosphating solutions nitrate up to a concentration of 30 g / l included.
  • the weight ratio of Zn to P 2 O 5 in the phosphating solution is preferably (0.023 to 0.14): 1.
  • Phosphating solutions apply as a rule that for higher Bath temperatures and / or zinc concentration ratio pay in above range and for lower bath temperatures and / or zinc concentration ratio numbers in the lower range are to be chosen.
  • a preferred embodiment of the method according to the invention provides for the metal surfaces to be brought into contact with phosphating solutions which contain 0.01 to 0.1 g / l peroxide (calculated as H 2 O 2 ) and 0.3 to 2.5 g / l Formate (calc. As formation) included.
  • the surfaces are brought in with phosphating solutions Touching up to 3 g / l manganese, magnesium, Calcium, lithium, tungstate, vanadate, molybdate, if necessary also nickel and / or cobalt or combinations thereof contain. From the perspective of workplace hygiene and the Environmental protection should, however, add nickel and / or cobalt. It is also appropriate to Add phosphating solutions up to 0.030 g / l copper the addition alone or in combination with the aforementioned Cations can occur.
  • the phosphating solutions additionally manganese and / or Magnesium and / or calcium optionally also nickel and / or Contain cobalt, the weight ratio of Mn: Zn, of Mg: Zn and Ca: Zn, possibly of (Ni + Co) at most 2: 1.
  • a further advantageous embodiment of the invention consists in bringing the metal surfaces into contact with phosphating solutions which contain fluoborate in amounts up to 3 g / l (calc. As BF 4 ) and / or fluosilicate in amounts up to 3 g / l (calc. as SiF 6 ) and / or simple fluoride in amounts up to 1.5 g / l (calculated as F).
  • phosphating solutions which contain fluoborate in amounts up to 3 g / l (calc. As BF 4 ) and / or fluosilicate in amounts up to 3 g / l (calc. as SiF 6 ) and / or simple fluoride in amounts up to 1.5 g / l (calculated as F).
  • the anions fluoborate, fluosilicate and / or fluoride generally increase the rate of phosphating and are also particularly advantageous when the treatment of aluminum-containing zinc surfaces is intended.
  • the presence of free fluoride is essential for the crystalline phosphat
  • the inventive method is in the temperature range of 30 up to 65 ° C. This is sufficient below 30 ° C Phosphating speed for modern series production in generally no longer while at higher temperatures Disadvantages, e.g. occur due to increased system incrustation can.
  • the method according to the invention can be used in spraying, dipping, Spray-diving or flooding can be carried out. If that The process is used as a spray process, the Zinc concentration 0.4 to 1.2 g / l. In case of Application in the spray-immersion or immersion process is one Concentration of zinc in the range of 1.0 to 2.0 g / l advantageous.
  • Zinc carbonate, zinc oxide and / or carbonates of the other optionally added cations are expediently used to adjust the content of the phosphating solution with regard to the free acid and the ratio of free P 2 O 5 to total P 2 O 5 , which is essential to the invention.
  • the pretreatment of the metals before the actual one Phosphating takes place in a conventional manner.
  • degreasing using aqueous, alkaline cleaners which suitably contain surfactant, be made.
  • there is scale or rust by pickling treatment e.g. with sulfuric acid, phosphoric acid or hydrochloric acid.
  • the workpieces can be Phosphating to form fine crystalline phosphate coatings in a manner known per se, e.g. with a titanium phosphate containing activation bath, be rinsed.
  • Phosphate coatings are in all areas where Use phosphate coatings.
  • the process of preparing for cathodic Electrocoating of particular importance is particular the process of preparing for cathodic Electrocoating of particular importance.
  • solutions A and B degreased steel sheets were treated with an activating alkaline cleaner by spraying at 52 ° C. for 2 min.
  • the layer weight, the crystal size, the minimum phosphating time and, after painting with a cathodic electrocoat, filler and topcoat, the adhesion and resistance to infiltration at a subsequently applied scratch were measured.
  • the following values were measured: Solution A Solution B Layer weight 2.2 g / m 2 2.2 g / m 2 Crystal size 12 um 35 ⁇ m Minimum phosphating time 1.2 min 1.4 min Lacquer adhesion (cross-cut grade) 0 0-1 Infiltration in the outdoor weathering test, 12 months (mm) 1.5 1.5

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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)

Claims (9)

  1. Procédé pour le phosphatage de surfaces métalliques constituées au moins en partie de fer ou d'acier conformément à la technologie dans laquelle on utilise des bains de phosphatage à faible teneur en zinc, dans lequel on amène les surfaces métalliques à une température de 30 à 65°C pendant une durée de 1 à 8 minutes en contact avec des solutions de phosphatage acides aqueuses qui contiennent
    de 0,4 à 2,0 g/l de Zn
    de 7 à 25 g/l de P2O5
    de 0,005 à 0,5 g/l de peroxyde (calculé comme H2O2)
    de 0,01 à 10 g/l de formiate (calculé comme ion formiate)
    qui sont exemptes de chlorate et de nitrite ajouté, dans lesquelles on règle le rapport pondéral du P2O5 libre au P2O5 total à une valeur dans le domaine de 0,03 à 0,20 et on règle la teneur en acide libre à une valeur dans le domaine de 0,5 à 2,5.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage qui contiennent en outre du nitrate jusqu'à concurrence de 30 g/l.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage qui contiennent
    de 0,010 à 0,1 g/l de peroxyde (calculé comme H2O2) et
    de 0,3 à 2,5 g/l de formiate (calculé comme ion formiate)
  4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage qui contiennent en outre du manganèse, du magnésium, du calcium, du lithium, du tungstate, du vanadate, du molybdate ou leurs combinaisons, le cas échéant également du nickel et/ou du cobalt dans des quantités respectivement jusqu'à 3 g/l.
  5. Procédé selon la revendication 4, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage dans lesquels les rapports pondéraux Mn : Zn, Mg : Zn, Ca : Zn et le cas échéant (Ni et/ou Co) : Zn s'élèvent respectivement à une valeur maximale de 2 : 1.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage qui contiennent en outre du Cu jusqu'à concurrence de 0,030 g/l.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'on amène les surfaces métalliques en contact avec des solutions de phosphatage qui contiennent en outre des fluorures complexes et/ou simples.
  8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce qu'on soumet les surfaces métalliques phosphatées à un rinçage ultérieur avec de l'eau déminéralisée dont on règle la valeur de pH avec un acide minéral dans le domaine de 3,6 à 5,0.
  9. Mise en oeuvre du procédé selon une ou plusieurs des revendications 1 à 8 à des fins de préparation de surfaces métalliques pour le trempage électrophorétique ultérieur, en particulier pour le trempage électrophorétique de type cathodique.
EP96938047A 1995-11-30 1996-11-02 Procede pour la phosphatation de surfaces metalliques Expired - Lifetime EP0866888B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19544614 1995-11-30
DE19544614A DE19544614A1 (de) 1995-11-30 1995-11-30 Verfahren zur Phospatierung von Metalloberflächen
PCT/EP1996/004767 WO1997020085A1 (fr) 1995-11-30 1996-11-02 Procede pour la phosphatation de surfaces metalliques

Publications (2)

Publication Number Publication Date
EP0866888A1 EP0866888A1 (fr) 1998-09-30
EP0866888B1 true EP0866888B1 (fr) 1999-06-16

Family

ID=7778787

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96938047A Expired - Lifetime EP0866888B1 (fr) 1995-11-30 1996-11-02 Procede pour la phosphatation de surfaces metalliques

Country Status (10)

Country Link
US (1) US6168674B1 (fr)
EP (1) EP0866888B1 (fr)
AU (1) AU702478B2 (fr)
BR (1) BR9611667A (fr)
CA (1) CA2236512C (fr)
DE (2) DE19544614A1 (fr)
ES (1) ES2132966T3 (fr)
MX (1) MX9804278A (fr)
WO (1) WO1997020085A1 (fr)
ZA (1) ZA969999B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999048819A1 (fr) * 1998-03-25 1999-09-30 Henkel Kommanditgesellschaft Auf Aktien Traitement des eaux usees lors de la phosphatation
DE10006338C2 (de) * 2000-02-12 2003-12-04 Chemetall Gmbh Verfahren zur Beschichtung von Metalloberflächen, wässeriges Konzentrat hierzu und Verwendung der beschichteten Metallteile
WO2004007799A2 (fr) * 2002-07-10 2004-01-22 Chemetall Gmbh Procede de revetement de surfaces metalliques
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2493327A (en) * 1946-09-27 1950-01-03 Kelite Products Inc Aqueous composition for treating iron and steel
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
JPH0730455B2 (ja) * 1988-09-27 1995-04-05 日本パーカライジング株式会社 リン酸塩化成処理液
DE3927614A1 (de) * 1989-08-22 1991-02-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
DE4241134A1 (de) * 1992-12-07 1994-06-09 Henkel Kgaa Verfahren zur Phosphatierung von Metalloberflächen
DE4243214A1 (de) 1992-12-19 1994-06-23 Metallgesellschaft Ag Verfahren zur Erzeugung von Phosphatüberzügen
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.

Also Published As

Publication number Publication date
CA2236512C (fr) 2005-06-07
CA2236512A1 (fr) 1997-06-05
MX9804278A (es) 1998-09-30
US6168674B1 (en) 2001-01-02
ZA969999B (en) 1998-05-28
BR9611667A (pt) 1999-02-23
DE59602269D1 (de) 1999-07-22
ES2132966T3 (es) 1999-08-16
EP0866888A1 (fr) 1998-09-30
AU702478B2 (en) 1999-02-25
WO1997020085A1 (fr) 1997-06-05
DE19544614A1 (de) 1997-06-05
AU7562196A (en) 1997-06-19

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