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WO1998032894A1 - Composition aqueuse de phosphatation et procede pour surfaces metalliques - Google Patents

Composition aqueuse de phosphatation et procede pour surfaces metalliques Download PDF

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Publication number
WO1998032894A1
WO1998032894A1 PCT/US1998/000903 US9800903W WO9832894A1 WO 1998032894 A1 WO1998032894 A1 WO 1998032894A1 US 9800903 W US9800903 W US 9800903W WO 9832894 A1 WO9832894 A1 WO 9832894A1
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Prior art keywords
ions
phosphate
zinc
concentration
liquid composition
Prior art date
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Ceased
Application number
PCT/US1998/000903
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English (en)
Inventor
Masahiko Kawakami
Naoyuki Kobayashi
Kazuyuki Oyama
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Henkel Corp
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Henkel Corp
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Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Priority to US09/355,050 priority Critical patent/US6179934B1/en
Priority to CA002277967A priority patent/CA2277967A1/fr
Priority to EP98905967A priority patent/EP0966554A4/fr
Publication of WO1998032894A1 publication Critical patent/WO1998032894A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C23C22/07—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
    • C23C22/12—Orthophosphates containing zinc 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
    • 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
    • C23C22/362—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 zinc 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
    • C23C22/34—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
    • C23C22/34—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
    • C23C22/365—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 containing also zinc and nickel cations

Definitions

  • This invention relates to a treatment composition, more particularly a liquid solution in water, that forms a zinc phosphate-type conversion coating on metal surfaces and to a method for treating metal surfaces with such a treatment composition.
  • the invention is particularly effective when applied to iron and steel, but in addition it can also be applied to a variety of surfaces that are constituted of zinc or an alloy thereof and/or aluminum or an alloy thereof, such alloys containing at least 55 atomic percent of zinc or of aluminum.
  • Description of Related Art o Zinc phosphate treatments are carried out in order to impart corrosion resistance to metals such as iron and steel, as an undercoating for painting operations, and to provide lubrication in forging and wire drawing operations.
  • This treatment is carried out by bringing the workpiece into contact with the treatment composition, often called a "bath” hereinafter, even though not necessarily contacted by immersion of the metal substrates s in it, for a sufficient period of time at an appropriate temperature. Spraying and/or dipping are typically employed to effect this contact.
  • the overall process generally proceeds through the following steps.
  • a water rinse is typically used between each of these steps and the next successive one of these steps, except between steps (2) and (3), in order to avoid dragging material from an upstream step into a downstream step.
  • 5 Cleaning step (1) is carried out in order to remove grease and other contaminants adhering to the workpiece and thereby provide for the smooth execution of the downstream steps.
  • An alkaline cleaner is typically used in this cleaning step.
  • the workpiece is typically brought into contact with a treatment bath that contains colloidal titanium.
  • This treatment results in a 0 substantial acceleration of the film-forming reactions during the phosphate conversion treatment and in this manner makes possible the formation of a uniform, fine, and dense conversion coating in a short period of time.
  • phosphate coatings as paint- base coatings on automotive components requires high-quality phosphate coatings that must exhibit paint adherence and corrosion resistance, and the surface conditioning step has been considered essential for the production of coatings of this type.
  • Phosphate conversion treatment step (3) is run using a variety of treatment bath compositions and treatment conditions whose particular selection will depend on the specific objective.
  • the ingredients present in a zinc phosphate-type treatment bath will be phosphate ions, zinc ions, and other metal ions (e.g., nickel, manganese), and each of these components will provide specific properties to the final film.
  • Other components typically present in baths of this type are nitrate, nitrite, chlorate, fluoroborate, and fluoro- silicate.
  • a lowering of the treatment temperature has been pursued over the last few years, and at present these treatments are run at temperatures of 40 °C to 50 °C for treatment times of about 1.5 to 3 minutes.
  • Post-treatment step (4) is carried out, for example, in order to improve the corrosion resistance and paint adherence.
  • a treatment bath either containing hexavalent chromium or chromium-free, is used as the post-treatment agent. This step may be omitted depending on the particular objective or application.
  • the high-quality zinc phosphate-type conversion films used as paint-base coatings on iron and steel can be evaluated through (1) the appearance of the conversion coating, (2) the coating weight, and (3) the P/(P + H) ratio as defined below.
  • the following characteristics are essential, or if so stated, preferred, for rating as "good” the appearance of a conversion coating:
  • the conversion coating must be free of defects such as rust, blue color, and thin or incomplete coverage, and in addition is preferably a columnar and/or nodular crystalline coating whose crystals are preferably microcrystalline, with sizes from about 1 to 5 micrometres (hereinafter usually abbreviat-
  • the mass of the coating formed divided by the area of the surface being coated a value also denoted as “coating weight” hereinafter, as a general rule is preferably from about 1 to 3 grams per square meter (hereinafter usually abbreviated as “g/m 2 ").
  • P/(P + H) ratio lp/(lp + Ih)
  • Ih represents the X-ray diffraction intensity from the (020) surface of hopeite (zinc phosphate)
  • Ip represents the X-ray diffraction intensity from the (100) surface of phosphophyllite (zinc iron phosphate) or one of its analogs in which manganese, nickel, cobalt, calcium, magnesium, copper and/or the like cations that were dissolved in the phosphating solution can replace some or all of the iron cations in phosphophyllite itself.
  • the P/(P + H) ratio is widely recognized as a characterizing value for the zinc phosphate-type films used as paint-base coatings on iron and steel P/(P + H) values of 0 8 to 1 are generally considered to provide good conversion coatings for paint-base coatings
  • Hei 1-123080 (123,080/1989) uses hydroxylamine sulfate (HAS) as an accelerator
  • HAS hydroxylamine sulfate
  • Ni and Mn are mentioned as general supplementary ions, neither the Detailed Description nor the Examples provide an explanation of how their quantity of addition should be determined
  • This reference also describes a relatively large number of other patents in which hydroxylamine sulfate is added to zinc phosphate solutions and in addition describes patents in which oxidizing agent is present, including United States Patent Nos 2,743,204 and 2,298,280
  • Japanese Patent Application Laid Open Number Hei 1-123080 also teaches treatment of the metal surface with a colloidal titanium-containing surface conditioner prior to conversion treatment
  • the hydroxylamine source is taught to be added to the conversion bath taught in Japanese Patent Application Laid Open Number Hei 1-123080 in order to broaden the permissible range of zinc concentrations in the bath at which the desired conversion coatings can be obtained
  • the zinc concentration range is expressed by the zinc/phosphate ions ratio
  • the zinc/phosphate ions weight ratio is no more than 0 27 while the concentration of the zinc itself is from 0 02 to 0 2 weight %, which is equivalent to about 0 2 to 2 grams per liter of total composition (hereinafter usually abbreviated as "g/L”)
  • This reference also teaches sur- face conditioning with a colloidal titanium-containing bath prior to conversion treatment
  • Japanese Patent Application Laid Open Number Hei 5-195245 teaches nickel ions and manganese ions as essential components in its treatment bath and also stipulates about 1/25 to 1/10 as a more desirable range for the zinc ions/phosphate ions weight ratio for the treatment bath of Japanese Patent Application Laid Open (Kokai or Unexamined) Number Hei 1-123080
  • the nickel ions content in this case is specified as from 0.02 to 0.15 weight % and the manganese ions content is specified as from 0.02 to 0.15 weight %.
  • a zinc ions/(manganese ions + nickel ions) weight ratio of about 1/1.5 to 1/
  • the phosphate conversion treatment bath taught in Japanese Patent Application Laid Open (Kokai or Unexamined) Number Hei 5-195246 (195,246/1993) uses a combination of simple and complex fluoride, a chelating agent for iron, phosphate ions, a hydroxylamine source, and an oxidizing agent selected from water-soluble aromatic organic nitro compounds, molybdic acid salts, and tungstic acid.
  • This bath can efficiently form a highly corrosion-resistant phosphate conversion coating on a variety of metal surfaces without requiring the use of the divalent and higher valent metal ions used in the prior art.
  • This treatment bath may also contain a colloidal titanium compound, in which case conversion treatment and surface conditioning can be carried out in a single step.
  • the present invention provides a treatment bath that can form a high-quality phosphate coating on metal surfaces with or without the execution of a surface condi- tioning step.
  • the present invention also provides a method for treating metal surfaces.
  • the present invention specifically provides a method that even in the absence of a surface conditioning step can form high-quality zinc phosphate coatings, most importantly on articles that must exhibit corrosion resistance and for which adhesion must be generated between a paint film, rubber, or plastic and a surface of iron or steel.
  • the zinc phosphate coating afforded by the present invention can not only be used as a paint-base coating, but can also be used as an adhesion-base coating, for ex- ample, in the adhesion of resin films or rubbers to an iron or steel surface.
  • a preferable composition according to a first embodiment of the invention is an aqueous zinc phosphate solution that contains phosphate ions at from 5 to 50 g/L, zinc ions at from 0.2 to 10, or preferably from 2.0 to 10, g/L, a hydroxylamine source in a quantity that provides hydroxylamine at from 0.5 to 4.0 g/L, and 0.01 to 5.0 g/L of at least one selection from the group consisting of polycarboxylic acids, salts thereof, and starch phosphate.
  • the hydroxylamine source is believed to increase the conversion reactivity of the phosphate treatment solution.
  • the hydroxylamine source is a component that makes possible omission of the surface conditioning step.
  • the chemical nature of the hydroxylamine source added to the coating treatment solution according to the present invention is not critical and may be, for example, a salt or complex salt of hydroxylamine. Specific preferred examples are the phosphate, nitrate, and sulfate salts of hydroxylamine and mixtures thereof.
  • the hydroxylamine quantities are reported in terms of the stoichiometric equivalent of hydroxylamine as calculated from the addition of the hydroxylamine source.
  • the addition of 10 g/L of hydroxylamine sulfate provides 4.0 g/L hydroxylamine.
  • the hydroxylamine source is preferably added so as to give from 0.5 to 4.0 grams of hydroxylamine per liter. Concentrations below this range are without adequate effect and thus result in poor coating in the absence of a surface conditioning treatment. Values in excess of 4.0 g/L have a pronounced tendency to produce such defects as blue color.
  • Polycar- boxylic acid refers to compounds that contain at least two carboxyl moieties in each molecule and in the context of the present invention also encompasses hydroxycarbox- ylic acids that contain one or more hydroxyl moieties in addition to at least two carboxyl moieties.
  • Typical examples of the subject polycarboxylic acids are citric acid, tartaric acid, succinic acid, ethylenediaminetetraacetic acid, and nitrilotriacetic acid, with the first three of these constituting a preferred group and citric acid most preferred.
  • Their salts are exemplified by the sodium, potassium, ammonium, and iron ammonium salts.
  • a composition according to a second preferred embodiment of the invention is an aqueous zinc phosphate solution that contains phosphate ions at a concentration from 7.5 to 50 g/L, zinc ions at a concentration from 2 to 10 g/L, and a hydroxylamine source in a quantity that provides hydroxylamine at a concentration from 0.5 to 4.0 g/L and in which the zinc ions/phosphate ions weight ratio is not more than 0.27.
  • the use of this treatment solution at temperatures of 40 °C to 50 °C for treatment times of at least 1 minute produces high-quality zinc phosphate coatings consisting mainly of nodular and/or columnar zinc iron phosphate crystals. Either dipping or spraying can be used as the treatment methodology.
  • At least 7.5 g/L of phosphate ions are required to avoid too high a zinc to phosphate ions ratio with even the minimum concentration of zinc suitable for this embodiment. While a conversion coating is produced at phosphate ions values in excess of 50 g/L, such levels are uneconomical due to the increased reagent consumption, for ex- ample, by drag out.
  • Suitable zinc ions concentrations for this second preferred embodiment are from 2 to 10 g/L. While a conversion coating can be obtained at zinc ions concentrations below 2 g/L even in the absence of a surface conditioning step, the coverage by such coatings has a pronounced tendency to be thin or incomplete. Zinc ions concentrations in excess of 10 g/L cause the weight of the resulting conversion film to be too large, making it unsatisfactory as a high quality paint-base coating.
  • the type of hydroxylamine source and its content range are the same as in the first preferred specific embodiment.
  • the zinc ions/phosphate ions weight ratio should be at or below 0.27. Precipitation occurs in the conversion treatment bath at values in excess of 0.27; this not only impairs the stability of the treatment bath but also prevents the production of normal conversion coatings.
  • the aqueous zinc phosphate solutions of the first and second preferred embodiments may also contain ferrous ions.
  • ferrous ions improves the conversion treatment activity.
  • ferrous ions are supplied by the etching of an iron or steel workpiece by the conversion treatment solution itself, ferrous ions are typically present to some degree even in the absence of any deliberate addition of them to the treatment bath.
  • At least one selection from the following may be added in order to obtain additional improvements in the conversion treatment activity and/or additional improvements in the quality of the conversion coating: nickel ions, manganese ions, nitrate ions, fluorine (as a chemical compound of fluorine), and complex fluoride ions.
  • the concentrations of the ferrous ions, nickel ions, manganese ions, nitrate ions, fluorine, and complex fluoride ions are preferably in the range from 0.01 to 5 g/L.
  • the treatment bath is supplied with a replenisher composition comprising an aqueous solution containing zinc ions, phosphate ions, and hydroxylamine source in which the total concentration of these species is at least 15 weight %.
  • test substrates were cold-rolled steel panels with a thickness of 0.8 millimeter, a unit hereinafter usually abbreviated in either singular or plural as "mm", and major dimensions of 70 mm * 150 mm.
  • Conversion treatment was carried out using the con- version treatment solutions reported in Table 1 and the properties of the resulting coatings were tested. Conversion-treated test panels were also painted as described below in order to test the painting performance.
  • Hydroxylamine was supplied to the bath by addition of hydroxylamine sulfate, I e , (NH 2 OH) 2 • H 2 S0 4 Fluorine was supplied to the bath by addition of hydrofluonc acid, I e , HF
  • the conditions were as follows: ambient temperature (i e. from 18 to 25 °C), 30 seconds, spray.
  • Treatment compositions were those reported in Table 1 The process conditions were as follows: 43 °C, 120 seconds, dipping
  • Kansai Paint Kabushiki Kaisha The conditions were as follows: bath temperature 28 °C voltage 200 volts current application time 180 seconds coating thickness 20 ⁇ m bake 170 °C, 20 minutes residence
  • the coating morphology was inspected and the crystal size was measured (unit ⁇ m) using a scanning electron microscope from Nippon Denshi Kabushiki Kaisha (4)
  • the P/(P + H) ratio The diffraction intensities from the (100) surface of phosphophyllite and the (020) surface of hopeite were measured using a Geiger Flex 2028 X-ray diffraction instrument from Rigaku Denki Kabushiki Kaisha Methods for evaluating the painted panels
  • Paint adherence testing (Secondary, water-resistance, adhesion testing) The test panel, after processing up to and including electropainting, was dipped in deionized water at 40 °C for 240 hours The test panel was then withdrawn from the water and a 100 unit checkerboard pattern was scribed on the panel with a sharp cutter down to the steel basis metal 11 parallel lines were first scnbed on a 1-mm interval and another 11 parallel lines also on a 1-mm interval were then scribed perpendicular to the first set The pattern was peeled with cellophane tape and the number of squares that were at least 50 % peeled was counted (2) Saltwater spray testing
  • Table 2 reports the results from the evaluations of the conversion-treated panels and the painted panels
  • results in Table 2 show that the present invention provided good results for the conversion coating on all criteria: conversion appearance, coating weight, size of coating crystals, morphology of the coating crystals, and P/(P + H) ratio.
  • results in Table 2 also confirm that the present invention provided an excellent paintability even in the absence of a surface conditioning step.

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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)

Abstract

L'invention concerne une composition aqueuse de conversion à base de phosphate de zinc qui contient entre 5 et 50 g/L d'ions de phosphate, entre 0,2 et 10 g/L d'ions de zinc, et entre 0,5 et 4,0 g/L d'hydroxylamine d'une source d'hydroxylamine. Ladite composition aqueuse contient en outre (1) entre 0,001 et 5,0 g/L d'acide polycarboxylique ou le sel dudit acide et/ou un phosphate d'amidon; ou (2) un rapport en poids ions de zinc/ions de phosphate inférieur à 0,27 et une concentration d'ions de zinc d'au moins 2,0 g/L. La composition aqueuse donne des revêtements de phosphate-zinc de grande qualité sur des surfaces métalliques, même lorsque ces dernières ne sont pas préalablement traitées avec une dispersion de titane colloïdal.
PCT/US1998/000903 1997-01-24 1998-01-22 Composition aqueuse de phosphatation et procede pour surfaces metalliques Ceased WO1998032894A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US09/355,050 US6179934B1 (en) 1997-01-24 1998-01-22 Aqueous phosphating composition and process for metal surfaces
CA002277967A CA2277967A1 (fr) 1997-01-24 1998-01-22 Composition aqueuse de phosphatation et procede pour surfaces metalliques
EP98905967A EP0966554A4 (fr) 1997-01-24 1998-01-22 Composition aqueuse de phosphatation et procede pour surfaces metalliques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/11357 1997-01-24
JP1135797A JPH10204649A (ja) 1997-01-24 1997-01-24 金属表面のりん酸塩処理水溶液及び処理方法

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WO1998032894A1 true WO1998032894A1 (fr) 1998-07-30

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CA (1) CA2277967A1 (fr)
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WO2001055480A1 (fr) * 2000-01-31 2001-08-02 Henkel Corporation Procede et composition de phosphatation par conversion
CN100392149C (zh) * 2006-05-18 2008-06-04 武汉理工大学 含可溶性淀粉的磷化液及其制备方法

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JP2003056645A (ja) * 2001-08-10 2003-02-26 Tokai Rubber Ind Ltd ゴム圧入式トーショナルダンパー及びその製造方法
PT1433877E (pt) 2002-12-24 2009-01-08 Chemetall Gmbh Processo de pré-tratamento para revestimento
JP4526807B2 (ja) 2002-12-24 2010-08-18 日本ペイント株式会社 塗装前処理方法
TW200417420A (en) 2002-12-24 2004-09-16 Nippon Paint Co Ltd Chemical conversion coating agent and surface-treated metal
JP2006161110A (ja) 2004-12-08 2006-06-22 Nippon Paint Co Ltd 車両のシャシ用金属表面の塗装前処理方法及び粉体塗料の塗装方法
JP4473185B2 (ja) 2005-07-01 2010-06-02 本田技研工業株式会社 化成処理方法、化成処理剤、及び化成処理部材
EP1997935B1 (fr) 2006-03-01 2016-04-13 Chemetall GmbH Composition pour traitement de surface metallique, procede de traitement de surface metallique et materiau metallique
DK1997936T3 (da) 2006-03-01 2014-08-11 Chemetall Gmbh Sammensætning til behandling af metaloverflader, fremgangsmåde til behandling af metaloverflader samt metallisk materiale
EP1997934B1 (fr) 2006-03-01 2014-07-30 Chemetall GmbH Composition pour traitement de surface metallique, procede de traitement de surface metallique et materiau metallique

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Publication number Priority date Publication date Assignee Title
WO2001055480A1 (fr) * 2000-01-31 2001-08-02 Henkel Corporation Procede et composition de phosphatation par conversion
US6638370B2 (en) 2000-01-31 2003-10-28 Henkel Kommanditgesellschaft Auf Aktien Phosphate conversion coating process and composition
CN100392149C (zh) * 2006-05-18 2008-06-04 武汉理工大学 含可溶性淀粉的磷化液及其制备方法

Also Published As

Publication number Publication date
CA2277967A1 (fr) 1998-07-30
EP0966554A4 (fr) 2000-04-05
EP0966554A1 (fr) 1999-12-29
JPH10204649A (ja) 1998-08-04

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