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EP0069950A1 - Procédé de phosphatation de surfaces métalliques - Google Patents

Procédé de phosphatation de surfaces métalliques Download PDF

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Publication number
EP0069950A1
EP0069950A1 EP82105960A EP82105960A EP0069950A1 EP 0069950 A1 EP0069950 A1 EP 0069950A1 EP 82105960 A EP82105960 A EP 82105960A EP 82105960 A EP82105960 A EP 82105960A EP 0069950 A1 EP0069950 A1 EP 0069950A1
Authority
EP
European Patent Office
Prior art keywords
metal surfaces
contact
brought
phosphating solution
phosphating
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
EP82105960A
Other languages
German (de)
English (en)
Other versions
EP0069950B1 (fr
Inventor
Hugh Thomas Springstead
Gary Dennis Kent
Bernhard Norbert Intorp
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.)
Henkel Corp
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 EP0069950A1 publication Critical patent/EP0069950A1/fr
Application granted granted Critical
Publication of EP0069950B1 publication Critical patent/EP0069950B1/fr
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16Sulfur-containing compounds
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • C23C22/36Chemical 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
    • C23C22/362Chemical 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 zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/14Orthophosphates containing zinc cations containing also chlorate anions

Definitions

  • the invention relates to a method for applying phosphate coatings on metal surfaces by means of phosphating solutions based on zinc phosphate as an essential layer-forming component, which are accelerated with chlorate and water-soluble aromatic nitro compound.
  • GB-PS 1 542 222 provides for the use of chlorate and nitrobenzenesulfonate as accelerators in zinc phosphate processes.
  • the weight ratio of chlorate to nitrobenzenesulfonate should be 3: 1 to 5: 1.
  • DE-OS 30 04 927 also describes a process for phosphating metal surfaces with zinc phosphate solutions, which may contain nitrite and / or organic nitro compound and optionally additionally chlorate.
  • the amounts of nitrite should be 0.01 to 0.2 g / 1
  • the amounts of organic nitro compound and optionally chlorate should be in the range of 0.05 to 2 g / 1.
  • the active bath components can be introduced in the form of water-soluble or acid-soluble salts or compounds or as acids in water. Suitable are e.g. Zinc nitrate, zinc oxide, zinc carbonate, acid zinc phosphate as well as phosphoric acid, mono- or disodium phosphate and alkali chlorate.
  • the water-soluble aromatic nitro compound should have no more than two nitro groups.
  • nitrobenzoic acid is suitable.
  • Another preferred embodiment of the invention consists in bringing the metal surface into contact with a solution which contains 2 to 7 g / l of nitro compound.
  • Optimum phosphate film forming chichta respect fine grain, and S is generally obtained if according to a further preferred embodiment the ratio between C10 3 to nitro compound is set to a value in the range from (0.5 to 1.25): 1.
  • the solutions used to produce the phosphate coating can have further components if necessary. For example, it is advantageous to bring solutions in contact with the metal surfaces that additionally contain 2 to 9 g / 1 NO 3 .
  • phosphating solutions used additionally contain 0.2 to 4 g / 1 fluoride ions.
  • the fluoride can be present in the phosphating solution as free or as a complex-bound fluorine ion.
  • Suitable complex fluorides are, for example, fluoborates and / or fluosilicates.
  • phosphating solutions which contain an additional content of Ni, Co and / or Fe ions are advantageous. These ions should preferably be present in a total amount of 0.1 to 2.5 g / l. Such additives can expediently be used in conjunction with 0.2 to 4 g / l of the aforementioned simple or complex fluorides. Such phosphating solutions with contents of Ni, Co and / or Fe ions and simple and / or complex fluorine ions are also advantageous for the treatment of surfaces consisting of several metals. Fluorine contents of up to 1 g / l are generally sufficient.
  • the 2.9 to 3.2 has a pH value of 2 to 3.5, preferably.
  • the phosphating solution should have 5 to 30 points total acid and 0.3 to 2.5 points free acid.
  • the number of points is defined in the usual way. For example, the amount of 0.1 n sodium hydroxide solution (in ml) consumed before the bromphenol blue is handled is equal to the number of free acid and the consumption when handling phenolphthalein is equal to the total acid score.
  • the number of points can also be determined by potentiometric titration.
  • the phosphating solution can be applied in any manner. Dip and spray treatments as well as combined dip / spray treatments are particularly suitable.
  • the duration of exposure depends on the desired phosphate layer formation and on the process conditions, but also on the nature of the metal surface and the preceding treatment.
  • the treatment times are generally in the range from 0.5 to 3 minutes.
  • g ewichte layer from about 0.86 to 1.60 g / m 2 (for steel), 1.30 to 2.15 g / m 2 (for galvanized steel) and to 0.43 g / m 2 (for aluminum) adjustable.
  • the respective value results from the accelerator ratio used, the layer weight decreasing as the proportion of aromatic nitro compound increases.
  • the phosphating solution used in carrying out the process according to the invention is usually prepared from a concentrate and diluted accordingly.
  • the free acid content in the concentrate can be sufficiently high must be set in order to safely avoid solids separation during storage or transport.
  • the appropriate pH value or the free acid content is then set.
  • the working phosphating solution can be supplemented using a supplementary solution which contains all the active ingredients or using several supplementary solutions which contain all of the active ingredients in their entirety.
  • a supplemental solution can contain zinc and phosphate ions and optionally nitrate and / or fluoride and / or nickel ions and another supplementary solution can contain alkali ions, nitrobenzenesulfonate and chlorate ions.
  • the inventive process takes place within a conventional Aidsgan there g, consisting of cleaning, water rinsing, phosphate film forming, water rinse, post-treatment and rinsing with deionized water application. This can be followed by a painting treatment or another type of coating.
  • the layers produced by the process according to the invention are very fine-grained and permit excellent anchoring of a lacquer coating applied subsequently.
  • the Phosphatüberzü received g e provide good corrosion protection and have good physical properties, particularly when the subsequent coating by electrodeposition coating, specifically, is carried out by cathodic electrodeposition coating and thereby treated steel surfaces, galvanized surfaces or aluminum.
  • the method according to the invention is also characterized by reduced sludge and crust formation in the phosphating device.
  • By changing the accelerator ratio it is finally possible to adapt the quality of the phosphate layer with regard to layer weight and fine grain to the respective requirements.
  • Concentrag A was first prepared by mixing the following ingredients in a stainless steel container:
  • a phosphating solution intended for spray treatment was prepared from both concentrates by were made up to 1 1 with water.
  • the total acid score was 13 when titrating a 10 ml bath sample with 0.1N sodium hydroxide solution against phenolphthalein.
  • Examples 2 to 4 were carried out again, with the difference that the phosphating in stage 3.) according to Example 2 was carried out by immersion treatment at 49 ° C. for 1 minute.
  • the sheet qualities treated in this way also showed test results similar to those in Examples 2 to 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
EP82105960A 1981-07-13 1982-07-03 Procédé de phosphatation de surfaces métalliques Expired EP0069950B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/282,480 US4498935A (en) 1981-07-13 1981-07-13 Zinc phosphate conversion coating composition
US282480 1981-07-13

Publications (2)

Publication Number Publication Date
EP0069950A1 true EP0069950A1 (fr) 1983-01-19
EP0069950B1 EP0069950B1 (fr) 1985-10-23

Family

ID=23081699

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82105960A Expired EP0069950B1 (fr) 1981-07-13 1982-07-03 Procédé de phosphatation de surfaces métalliques

Country Status (14)

Country Link
US (1) US4498935A (fr)
EP (1) EP0069950B1 (fr)
JP (1) JPS5819481A (fr)
KR (1) KR890001036B1 (fr)
AU (1) AU549517B2 (fr)
BR (1) BR8204044A (fr)
CA (1) CA1200471A (fr)
DE (2) DE3224923A1 (fr)
ES (1) ES8305051A1 (fr)
GB (1) GB2102839A (fr)
MX (1) MX157371A (fr)
PH (1) PH19127A (fr)
PT (1) PT75220B (fr)
ZA (1) ZA824588B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111223A1 (fr) * 1982-12-03 1984-06-20 Gerhard Collardin GmbH Procédé de phosphatation de surfaces métalliques et compositions appropriées à ce procédé
EP0121274A1 (fr) * 1983-03-31 1984-10-10 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
EP0141341A1 (fr) * 1983-10-26 1985-05-15 Metallgesellschaft Ag Procédé pour la formation de revêtements de phosphate
EP0155547A1 (fr) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement
WO1986004931A1 (fr) * 1985-02-22 1986-08-28 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation de surfaces metalliques
WO1986005094A1 (fr) * 1985-03-08 1986-09-12 Takeda Chemical Industries, Ltd. Agent antiobesite et composition
WO1986006276A1 (fr) * 1985-04-30 1986-11-06 Takeda Chemical Industries, Ltd. Agent et composition inhibiteurs de la digestion du sucre
EP0261704A1 (fr) * 1986-09-18 1988-03-30 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des surfaces métalliques
GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3325974A1 (de) * 1983-07-19 1985-01-31 Gerhard Collardin GmbH, 5000 Köln Verfahren und universell anwendbare mittel zum beschleunigten aufbringen von phosphatueberzuegen auf metalloberflaechen
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
DE3408577A1 (de) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
GB8523572D0 (en) * 1985-09-24 1985-10-30 Pyrene Chemicals Services Ltd Coating metals
US4673445A (en) * 1986-05-12 1987-06-16 The Lea Manufacturing Company Corrosion resistant coating
US6551417B1 (en) 2000-09-20 2003-04-22 Ge Betz, Inc. Tri-cation zinc phosphate conversion coating and process of making the same
JP5462467B2 (ja) 2008-10-31 2014-04-02 日本パーカライジング株式会社 金属材料用化成処理液および処理方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2819912A1 (de) * 1977-05-11 1978-11-23 Nippon Paint Co Ltd Verfahren zur phosphatierung von eisen
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
DE3004927A1 (de) * 1979-02-13 1980-08-21 Nippon Paint Co Ltd Verfahren zur phosphatierung von metallen
DE3016576A1 (de) * 1980-04-30 1981-11-05 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2295545A (en) * 1938-02-04 1942-09-15 Parker Rust Proof Co Treatment of metal
DE1287890B (fr) * 1961-03-23 1900-01-01
US3272664A (en) * 1963-07-25 1966-09-13 Detrex Chem Ind Composition and method for coating metal surfaces

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
DE2819912A1 (de) * 1977-05-11 1978-11-23 Nippon Paint Co Ltd Verfahren zur phosphatierung von eisen
DE3004927A1 (de) * 1979-02-13 1980-08-21 Nippon Paint Co Ltd Verfahren zur phosphatierung von metallen
DE3016576A1 (de) * 1980-04-30 1981-11-05 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111223A1 (fr) * 1982-12-03 1984-06-20 Gerhard Collardin GmbH Procédé de phosphatation de surfaces métalliques et compositions appropriées à ce procédé
EP0121274A1 (fr) * 1983-03-31 1984-10-10 Metallgesellschaft Ag Procédé de phosphatation de surfaces métalliques
EP0141341A1 (fr) * 1983-10-26 1985-05-15 Metallgesellschaft Ag Procédé pour la formation de revêtements de phosphate
EP0155547A1 (fr) * 1984-03-01 1985-09-25 Gerhard Collardin GmbH Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement
WO1986004931A1 (fr) * 1985-02-22 1986-08-28 Henkel Kommanditgesellschaft Auf Aktien Procede de phosphatation de surfaces metalliques
US4708744A (en) * 1985-02-22 1987-11-24 Henkel Kommanditgesellschaft Auf Aktien Process for phosphating metal surfaces and especially iron surfaces
WO1986005094A1 (fr) * 1985-03-08 1986-09-12 Takeda Chemical Industries, Ltd. Agent antiobesite et composition
WO1986006276A1 (fr) * 1985-04-30 1986-11-06 Takeda Chemical Industries, Ltd. Agent et composition inhibiteurs de la digestion du sucre
GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings
US4849031A (en) * 1986-09-17 1989-07-18 Metallgesellschaft Aktiengesellschaft Process of producing phosphate coatings on metal surfaces
EP0261704A1 (fr) * 1986-09-18 1988-03-30 Metallgesellschaft Ag Procédé pour produire des revêtements de phosphate sur des surfaces métalliques

Also Published As

Publication number Publication date
DE3224923A1 (de) 1983-02-17
PT75220A (fr) 1982-08-01
ZA824588B (en) 1983-05-25
JPH0331790B2 (fr) 1991-05-08
ES513841A0 (es) 1983-04-01
MX157371A (es) 1988-11-18
JPS5819481A (ja) 1983-02-04
US4498935A (en) 1985-02-12
CA1200471A (fr) 1986-02-11
PT75220B (fr) 1984-07-23
AU549517B2 (en) 1986-01-30
EP0069950B1 (fr) 1985-10-23
KR890001036B1 (ko) 1989-04-20
BR8204044A (pt) 1983-07-05
DE3267010D1 (en) 1985-11-28
GB2102839A (en) 1983-02-09
KR840000670A (ko) 1984-02-25
AU8495282A (en) 1983-01-20
PH19127A (en) 1986-01-08
ES8305051A1 (es) 1983-04-01

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