EP0866888A1 - Procede pour la phosphatation de surfaces metalliques - Google Patents

Procede pour la phosphatation de surfaces metalliques

Info

Publication number
EP0866888A1
EP0866888A1 EP96938047A EP96938047A EP0866888A1 EP 0866888 A1 EP0866888 A1 EP 0866888A1 EP 96938047 A EP96938047 A EP 96938047A EP 96938047 A EP96938047 A EP 96938047A EP 0866888 A1 EP0866888 A1 EP 0866888A1
Authority
EP
European Patent Office
Prior art keywords
metal surfaces
phosphating
phosphating solutions
contact
brought
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
EP96938047A
Other languages
German (de)
English (en)
Other versions
EP0866888B1 (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
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 filed Critical Metallgesellschaft AG
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
Expired - Lifetime legal-status Critical Current

Links

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 at least partially iron or steel metal surfaces according to the low zinc technology and its use for preparing the metal surfaces for electrocoating, in particular for cathodic electrocoating.
  • the zinc phosphating process is widely used in the metalworking industry. As a pretreatment for painting, phosphating processes that use low-zinc technology bring special advantages.
  • the phosphating solutions used here contain zinc in concentrations of only about 0.4 to 2 g / 1 and produce phosphate layers on steel which offer very good paint adhesion and high resistance to paint infiltration when exposed to corrosion.
  • REPLACEMENT BLA ⁇ (RULE 26) Proven nitro compounds. These baths deliver high-quality, uniformly covering phosphate layers in a short time. It is also known to use peroxides as accelerators in low-zinc phosphating baths. Although these would be preferable to the use of the aforementioned accelerators for reasons of workplace hygiene and environmental protection, they are
  • 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 s increases Total P 2 0 5 is set to a value in the range from 0.04 to 0.2.
  • H 2 0 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 0 2 ) or the maximum Fe (II) concentration 60 mg / l (calculated as Fe).
  • REPLACEMENT BLA ⁇ (RULE 26) given up. Phosphate layers with a relatively low layer weight and a coarse crystalline structure are also obtained. In addition, if zinc is present at the same time, specks are formed on zinc surfaces, in particular because of the nitrate content. In the presence of aluminum, no crystalline phosphate layers can be created on the aluminum surfaces.
  • the object of the invention is to provide a method for the phosphating of at least partially iron or steel metal surfaces, which leads to sufficiently thick and fine crystalline phosphate layers, with possible simultaneous presence of zinc and / or aluminum surfaces, also leads to perfect phosphate layers thereon and the has no disadvantage associated with the addition of chlorate.
  • 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 from 30 to 65 ° C. for from 1 to 8 minutes. in contact with aqueous acid phosphating solutions, the
  • Contain that are free of chlorate and added nitrite in which the weight ratio of free P 2 0 5 to total P 2 0 5 to a value in the range of 0.03 to 0.20 and the content of Free acid is set to a value in the range of 0.5 to 2.5.
  • Free of added nitrite means that no nitrite should be added to the phosphating solutions, but - if the process is designed with the addition of nitrate - low levels may be present due to formation from nitrate.
  • the method according to the invention is intended in particular for the surface treatment of iron and steel.
  • galvanized steel e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum, zinc and their alloys.
  • alloy galvanized steel i.e. e.g. steel coated with ZnAl, ZnFe and ZnNi, aluminized steel, aluminum, zinc and their alloys.
  • Oxidizing agents are called hydrogen peroxide or peroxide compounds. Apart from the fact that in addition to H 2 0 2 or peroxide compounds, various other oxidizing agents are designated as suitable, it is emphasized as a particular advantage of the process that it leaves steel sides shiny metallic on substrates galvanized on one side. Because of this, it was to be expected that phosphating solutions which contain peroxide and formic acid and which work according to the low-zinc technology would not be able to produce flawless, high-quality phosphate layers on surfaces of iron and steel. In particular, it was not to be assumed that the use of formic acid would significantly increase the rate of phosphating.
  • the phosphating process according to EP-A-361375 also provides for adding phosphating solutions, which preferably work in accordance with the low-zinc technology, to formic acid, optionally in combination with nitrate, chlorate, nitrite and nitrobenzenesulfonate.
  • phosphating solutions which preferably work in accordance with the low-zinc technology
  • formic acid optionally in combination with nitrate, chlorate, nitrite and nitrobenzenesulfonate.
  • the purpose of the addition of formic acid is to produce phosphate coatings with relatively high nickel contents when using nickel-containing phosphating solutions, even if the nickel concentration in the phosphating solution is comparatively low. Also from this prior art it could not be deduced that the advantages obtained with the method according to the invention can be achieved.
  • Phosphating solutions contain nitrate up to a concentration of 30 g / 1.
  • the weight ratio of Zn to P 2 0 5 in the phosphating solution is preferably (0.023 to 0.14): 1.
  • the rule applies that ratios in the above range for higher bath temperatures and / or zinc concentrations and ratios in the lower range for lower bath temperatures and / or zinc concentrations are.
  • 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 / 1 peroxide (calculated as H 2 O 2 ) and 0.3 to 2.5 g / 1 Formate (calc. As formation) included.
  • the surfaces are brought into contact with phosphating solutions which additionally contain up to 3 g / 1 manganese, magnesium, calcium, lithium, tungstate, vanadate, molybdate, optionally also nickel and / or cobalt or combinations thereof . From the point of view of workplace hygiene and environmental protection, however, addition of nickel and / or cobalt should be avoided. It is also expedient to add up to 0.030 g / 1 copper to the phosphating solutions
  • REPLACEMENT BLA ⁇ (RULE 26) the addition can be carried out alone or in combination with the aforementioned cations.
  • the phosphating solutions additionally contain manganese and / or magnesium and / or calcium and also nickel and / or cobalt, the weight ratio of Mn: Zn, of Mg: Zn and Ca: Zn, possibly of (Ni + Co) should be a maximum of 2: 1.
  • the fluoborate in quantities up to 3 g / 1 (calc. As BF 4 ) and / or fluosilicate in quantities up to 3 g / 1 (calc. As SiFj and / or simple fluoride in quantities up to 1 , 5 g / 1 (calc. 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. For the crystalline phosphating of aluminum and the presence of free fluoride is essential for these alloys.
  • the process according to the invention is carried out in the temperature range from 30 to 65 ° C. Below 30 ° C the phosphating speed is generally no longer sufficient for modern series production, while at higher temperatures disadvantages, e.g. can occur due to increased system incrustation.
  • the process according to the invention can be carried out in spraying, dipping, spray-dipping or flooding. If that
  • the zinc concentration should be 0.4 to 1.2 g / 1.
  • a concentration of zinc in the range from 1.0 to 2.0 g / 1 is 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, which is essential to the invention, with regard to the free acid and the ratio of free P 2 O s to total P 2 0 5 .
  • the rinsing stages which are expediently designed as a rinsing bath cascade, work in the last rinsing bath with salt-free or low-salt water, which is supplied to the phosphating bath in the opposite direction from the rinsing stage to rinsing stage.
  • the phosphating bath it complements the above-mentioned dehydration of the phosphating solution.
  • the water extracted from the phosphating bath for example by reverse osmosis and electrodialysis, can be returned to the rinsing stages.
  • the pretreatment of the metals before the actual phosphating is done in a conventional manner.
  • degreasing can be carried out using aqueous, alkaline cleaners which expediently contain surfactant.
  • a pickling treatment e.g. with sulfuric acid, phosphoric acid or hydrochloric acid.
  • the workpieces can be known to form fine crystalline phosphate coatings prior to phosphating, e.g. with an activation bath containing titanium phosphate.
  • the phosphating treatment After the phosphating treatment, it is usually rinsed with water.
  • water For the purpose of improving corrosion protection, e.g. be treated with rinse solutions containing or containing chromic acid.
  • demineralized water instead of the aforementioned rinsing, one is carried out with demineralized water which has been adjusted to a pH in the range from 3.6 to 5.0 with mineral acid.
  • the phosphate coatings produced by the process according to the invention can be used in all fields in which phosphate coatings are used. However, it is of particular advantage in the phosphating of metal surfaces for the subsequent painting, in particular the subsequent electrocoating. The preparation process for cathodic electrocoating is particularly important.
  • Solution A 1.0 g / 1 Zn 0.7 points free acid
  • Solution B Solution A, but without formate
  • compositions were selected for the phosphating solutions for use in the dipping process
  • Solution C 1.8 g / 1 Zn 1.6 points free acid 1.0 g / 1 Mn 25 points total acid 13.0 g / 1 P 2 0 5 0.05 g / 1 H 2 0 2 1.0 g / 1 formate 3.0 g / 1 N0 3 alkali to adjust the free acidity
  • Solution D as solution C, but with 2.5 g / 1 C10 3 instead of formate
  • Solution E as solution C, but without formate
  • REPLACEMENT BLA ⁇ (RULE 26) activated and phosphated at 55 ° C in solutions C to E for 3 min while diving.
  • the layer weight, the crystal size, the minimum phosphating time and, after coating with cathodic electrocoat, filler and topcoat, the adhesion and resistance to infiltration were measured. The following results were obtained.

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)

Abstract

L'invention concerne un procédé pour la phosphatation de surfaces métalliques, constituées au moins partiellement de fer ou d'acier, à l'aide du processus à faible teneur en zinc, dans lequel les surfaces métalliques sont mises en contact avec des solutions de phosphatation acides aqueuses à une température comprise entre 30 et 65 °C pendant une durée comprise entre 1 et 8 minutes. Ces solutions de phosphatation contiennent entre 0,4 et 2,0 g/l Zn, entre 7 et 25 g/l P2O5, entre 0,005 et 0,5 g/l de peroxyde (exprimé sous forme de H2O2), et entre 0,01 et 10 g/l de formiate (exprimé sous forme d'ion formiate). Les solutions de phosphatation sont exemptes de chlorate et de nitrite ajouté, le rapport en poids du P2O5 libre au P2O5 total contenu est fixé à une valeur comprise entre 0,03 et 0,20, et la quantité d'acide libre est fixée à une valeur comprise entre 0,5 et 2,5. En outre, les solutions de phosphatation peuvent renfermer jusqu'à 30 g/l de nitrate et de manganèse, magnésium, calcium, lithium, tungstate, vanadate, molybdate ou des associations de ceux-ci, éventuellement également du nickel et/ou du cobalt respectivement à raison de 3 g/l au maximum, et éventuellement également jusqu'à 0,030 g/l de cuivre. Les rapports en poids de Mn : Zn, Mg : Zn, Ca : Zn et éventuellement de Ni et/ou Co : Zn doivent être respectivement égaux à 2 : 1 au maximum. Ce procédé convient notamment pour préparer des surfaces métalliques en vue du trempage électrophorétique ultérieur, en particulier le trempage électrophorétique 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 true EP0866888A1 (fr) 1998-09-30
EP0866888B1 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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1929070A1 (fr) * 2005-09-30 2008-06-11 Henkel AG & Co. KGaA Solution de phosphatation contenant du peroxyde d'hydrogene et des acides carboxyliques chelateurs

Families Citing this family (3)

* 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
US20050205166A1 (en) * 2002-07-10 2005-09-22 Jurgen Specht Method for coating metallic surfaces

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.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9720085A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1929070A1 (fr) * 2005-09-30 2008-06-11 Henkel AG & Co. KGaA Solution de phosphatation contenant du peroxyde d'hydrogene et des acides carboxyliques chelateurs

Also Published As

Publication number Publication date
CA2236512A1 (fr) 1997-06-05
DE59602269D1 (de) 1999-07-22
CA2236512C (fr) 2005-06-07
DE19544614A1 (de) 1997-06-05
ES2132966T3 (es) 1999-08-16
BR9611667A (pt) 1999-02-23
ZA969999B (en) 1998-05-28
AU7562196A (en) 1997-06-19
MX9804278A (es) 1998-09-30
WO1997020085A1 (fr) 1997-06-05
US6168674B1 (en) 2001-01-02
AU702478B2 (en) 1999-02-25
EP0866888B1 (fr) 1999-06-16

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