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EP0977908B1 - Conditionnement de surfaces metalliques prealablement a la phosphatation - Google Patents

Conditionnement de surfaces metalliques prealablement a la phosphatation Download PDF

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Publication number
EP0977908B1
EP0977908B1 EP98908792A EP98908792A EP0977908B1 EP 0977908 B1 EP0977908 B1 EP 0977908B1 EP 98908792 A EP98908792 A EP 98908792A EP 98908792 A EP98908792 A EP 98908792A EP 0977908 B1 EP0977908 B1 EP 0977908B1
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Prior art keywords
phosphate
surface conditioning
concentration
divalent
microparticulate
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EP98908792A
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German (de)
English (en)
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EP0977908A4 (fr
EP0977908A1 (fr
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Takaomi Nakayama
Yasuhiko Nagashima
Kensuke Shimoda
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Henkel Corp
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Henkel Corp
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    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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

Definitions

  • This invention relates to a surface conditioning pretreatment bath and surface conditioning process for use prior to the phosphate conversion coating treatments that are executed on the surfaces of metals such as iron and steel, zinc-plated steel sheet, aluminum, and the like.
  • the subject surface conditioning pretreatment bath and process have the effect of accelerating the conversion reactions and shortening the reaction time in the ensuing conversion treatment, while also producing finer crystals in the phosphate coating.
  • a typical phosphate conversion coating process that produces fine-sized, dense phosphate coating crystals can be exemplified as having the following steps:
  • the surface conditioning step is carried out in order to render the phosphate coating crystals fine-size and dense.
  • Compositions for this purpose are known, for example, from United States Patent Numbers 2,874,081, 2,322,349, and 2,310,239.
  • Disclosed therein as the main constituents of the surface conditioner are titanium, pyrophosphate ions, orthophosphate ions, sodium ions, and the like.
  • These surface conditioning compositions known as Jernstedt salts, provide titanium ions and colloidal titanium in their aqueous solutions. The colloidal titanium becomes adsorbed to the metal surface when the degreased and water-rinsed metal is dipped in an aqueous solution of such a surface conditioning composition or when the metal is sprayed with the surface conditioning pretreatment bath.
  • the adsorbed colloidal titanium functions in the ensuing phosphate conversion coating treatment step as nuclei for deposition of the phosphate coating crystals, thereby accelerating the conversion reactions and causing the phosphate coating crystals to be finer-sized and denser.
  • the surface conditioning compositions in current industrial use all employ Jernstedt salts. However, the use in the surface conditioning step of colloidal titanium generated from Jernstedt salts is associated with a variety of problems.
  • the first problem is a deterioration with time in the surface conditioning pretreatment bath. While the heretofore employed surface conditioning compositions do provide remarkable fine-sizing and densifying effects on the phosphate coating crystals immediately after preparation of the aqueous solution of the composition, this activity can be lost several days after preparation because of aggregation of the colloidal titanium. This loss in activity, which manifests as a coarsening of the phosphate coating crystals, occurs regardless of whether the surface conditioning pretreatment bath has actually been used during this several day period.
  • Japanese Patent Application Laid Open (Kokai or Unexamined) Number Sho 63-76883 (76,883/1988) teaches a process for managing and maintaining the surface conditioning activity by measuring the average particle size of the colloidal titanium in the surface conditioning pretreatment bath and continuously discarding bath so as to keep the average particle size below a prescribed value.
  • Fresh surface conditioning composition is also supplied to make up for the discarded portion.
  • This method does permit a quantitative management of the factors related to the activity of the surface conditioning pretreatment bath, but at the same time this method requires that large amounts of the surface conditioning pretreatment bath be discarded in order to maintain an activity level equal to that of the initially prepared aqueous solution. This creates an additional problem with respect to the waste water treatment capacity of the plant where the process is carried out. In sum, the activity is maintained by the combination of continuously discarding the surface conditioning pretreatment bath and make up of the entire quantity.
  • the second problem is that the activity and life of the surface conditioning pretreatment bath are substantially affected by the quality of the water used for bath buildup.
  • Industrial-grade water is generally used to make up the surface conditioning pretreatment bath.
  • industrial-grade water contains cationic components which are a source of total hardness, e.g., magnesium and calcium, and the content of these components varies as a function of the source of the industrial-grade water used for bath buildup.
  • colloidal titanium which is the principal component of the heretofore used surface conditioning pretreatment baths, bears an anionic charge in aqueous solution and that the resulting mutual electrical repulsion prevents its sedimentation and supports the maintenance of its disperse state.
  • a fourth problem concerns the limitation on the degree of fine-sizing of the phosphate coating crystals that can be achieved through the activity of the surface conditioning pretreatment bath.
  • the surface conditioning activity is generated by the adsorption of colloidal titanium on the metal surface, which creates nuclei for the deposition of the phosphate coating crystals.
  • the phosphate coating crystals become denser and finer as the number of colloidal titanium particles adsorbed on the metal surface during the surface conditioning step increases. This would upon initial analysis lead to the idea of increasing the number of colloidal titanium particles in the surface conditioning pretreatment bath, i.e., increasing the colloidal titanium concentration.
  • the current normally used upper limit on the colloidal titanium concentration is 100 parts by weight of colloidal titanium (measured as its stoichiometric equivalent as elemental titanium) per million parts of the total composition, a concentration unit that may be used hereinafter for any ingredient in any mixture and is usually abbreviated as "ppm", in the surface conditioning pretreatment bath, and the prior art has been unable to provide finer-sized phosphate coating crystals by increasing the colloidal titanium concentration above this limit.
  • Japanese Patent Application Laid Open (Kokai or Unexamined) Numbers Sho 56-156778 (156,778/1981) and Sho 57-23066 (23,066/1982) have proposed a surface conditioning process which employs the insoluble phosphate of a divalent or trivalent metal as the surface conditioner rather than a Jernstedt salt.
  • a suspension containing the insoluble phosphate of a divalent or trivalent metal is blown under elevated pressure onto the surface of a steel band or ribbon.
  • this surface conditioning technology is effective only when the suspension is blown onto the workpiece under elevated pressure and thus cannot be used for surface conditioning in phosphate conversion coating treatments in which surface conditioning is generally carried out by dipping or spraying.
  • Japanese Patent Publication (Kokoku) Number Sho 40-1095 (1,095/ 1965) teaches a surface conditioning process in which galvanized steel sheet is dipped in a highly concentrated suspension of an insoluble phosphate of a divalent or trivalent metal.
  • the working examples provided for this process are limited to galvanized steel sheet, and in addition this process uses a highly concentrated insoluble phosphate suspension with a minimum concentration of 30 grams of insoluble phosphate particles per liter of total suspension, a concentration unit that may be used hereinafter for other materials in addtion to colloidal phosphates that are dissolved or dispersed in any liquid phase and is generally abbreviated "g/L".
  • German Patent Application No. 27 32 385 discloses an activating pretreatment before the phosphatising step, using an aqueous composition having a pH of from 5-10.
  • the composition is based on magnesium orthophosphate, which is present in an amount of from 0.1-10 g/l, and of which at least 50% of the orthophosphate particles have a size of less than 4 ⁇ m.
  • the composition further contains condensed alkali metal phosphates, preferably present in a concentration of 1-5 g/l.
  • British Patent No. 1,367,605 discloses a pretreatment for cold deformation of steel, which utilises an aqueous suspension of 0.1-8 g/l of secondary and/or tertiary manganese phosphate, ground as finely as possible, and 0.1-5 g/l alkali phosphates.
  • British Patent No. 1,137,449 discloses a process for making manganese phosphate coatings on iron or steel.
  • the process uses a pretreatment with an aqueous suspension of finely divided insoluble manganese (II) orthophosphate, formed by precipitation at pH 7.5, of which 50% preferably has a particle size of less than 3.5 ⁇ m.
  • the suspension preferably comprises sodium pyrophosphate, and its stability can be increased by adding surface active agents, particularly of non-ionic type.
  • surface active agents particularly of non-ionic type.
  • the addition of iron orthophosphate and calcium pyrophosphate are also described.
  • British Patent Application No. 2,057,512 discloses an alkali degreasing bath having a pH of from 9-12 and including a suspension of divalent manganese in orthophosphate form of fine particle size.
  • the particle size is less than 50 ⁇ m at a concentration of higher than 0.5 g/l.
  • the bath preferably also includes an alkali agent selected from soda, borates, meta- or orthosilicates, sodium orthophosphate, a surface active agent of anionic or non-ionic type, and a sequestering agent selected from condensed phosphates.
  • An object of the present invention is to solve the problems described above for the prior art by providing a novel surface conditioning pretreatment bath that evidences an excellent stability over time, that can accelerate the conversion reactions and shorten the conversion reaction time in an ensuing phosphate conversion coating treatment, and/or that can provide finer-sized crystals in the ultimately obtained phosphate coating.
  • An additional object of the invention is to provide a surface conditioning process with these same features.
  • a pretreatment bath that characteristically has a pH adjusted to 4 to 13 and contains alkali metal salt or ammonium salt or a mixture thereof, at least one selection from phosphates that contain at least one type of divalent or trivalent metal cations and that include particles with a particle size ⁇ 5 micrometres (hereinafter usually abbreviated as " ⁇ m") and microparticulate oxides that disperse in aqueous solution in an anionically-charged state.
  • the concentration of the ⁇ 5- ⁇ m particles is preferably from 0.001 to 30 g/L, and the aforesaid divalent or trivalent metal is preferably at least one selection from Zn, Fe, Mn, Ni, Co, Ca, and Al.
  • the aforesaid alkali metal salt or ammonium salt independently is preferably at least one salt selected from the orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, and borates and independently is preferably present in a concentration of 0.5 to 20 g/L.
  • the bath preferably additionally contains at least one selection from the group consisting of water-soluble anionic organic polymers, water-soluble nonionic organic polymers, anionic surfactants, nonionic surfactants.
  • This microparticulate oxide that disperses in an anionically charged state preferably has an average particle size ⁇ 0.5 ⁇ m and is preferably present in a concentration from 0.001 to 5 g/L.
  • the subject microparticulate oxide that disperses in an anionically charged state is desirably at least one selection from the oxides of Si, B, Ti, Zr, Al, Sb, Mg, Se, Zn, Sn, Fe, Mo, and V.
  • a metal surface conditioning process according to the present invention that precedes phosphate conversion coating treatment is characterized by contacting the metal surface with the surface conditioning pretreatment bath described above.
  • a surface conditioning pretreatment bath according to the present invention has a much better stability at high pH's and high temperatures than the prior art products, it can be combined with builder and nonionic or anionic surfactant(s) or mixtures thereof and used to effect a process that can simultaneously clean and activate the metal surface.
  • Phosphates containing at least one divalent or trivalent metal are an essential component in the present invention. These dispersed divalent or trivalent metal phosphate particles with a suitable particle size, through adsorption on the surface of the workpiece from an aqueous solution containing other specific ingredients, form nuclei for ensuing phosphate coating crystal deposition and also increase the rate of the phosphate conversion reactions.
  • the particle size of the divalent and trivalent metal phosphate particles dispersed in a pretreatment composition according to the invention preferably is not more than, with increasing preference in the order given, 4.5, 3.5, 2.5, 1.5, 0.50, 0.40, 0.25, or 0.10 ⁇ m.
  • the corrosion resistance after zinc phosphating and painting is better, the smaller the particle size of dispersed phosphate used in a composition according to the invention, and the phosphate coating weight is smaller when smaller particle size phosphate dispersates are used.
  • the dispersed phosphate particles preferably contains at least some of the same chemical type(s) of divalent or trivalent metal cation(s) as does the phosphate coating to be formed after the pretreatment according to the invention is used.
  • zinc cations preferably predominate also among the cations in the phosphates dispersed in a pretreatment composition according to this invention.
  • a manganese phosphate conversion coating is to be used, predominantly manganese phosphates are preferably used as the dispersates in a pretreatment composition according to the invention.
  • divalent or trivalent metal phosphate component resembles one component in phosphate conversion treatment baths and phosphate conversion coatings
  • another advantage of the subject divalent or trivalent metal phosphate is that it will not negatively affect the conversion treatment bath when carried over into that bath and will not adversely affect the performance of the phosphate conversion coating when taken into the conversion coating as nuclei.
  • the divalent or trivalent metal phosphate used in the present invention is exemplified by the following: Zn 3 (PO 4 ) 2 , Zn 2 Fe(PO 4 ) 2 , Zn 2 Ni(PO 4 ) 2 , Ni 3 (PO 4 ) 2 , Zn 2 Mn(PO 4 ) 2 , Mn 3 (PO 4 ) 2 , Mn 2 Fe(PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Zn 2 Ca(PO 4 ) 2 , FePO 4 , AlPO 4 , CoPO 4 , and Co 3 (PO 4 ) 2 .
  • the presence of divalent or trivalent metal phosphate particles with sizes in excess of 5 ⁇ m in the surface conditioning pretreatment bath according to the present invention does not harm the advantageous effects of the present invention, provided that the concentration of the ⁇ 5- ⁇ m microparticles in the surface conditioning aqueous composition is suitable.
  • the average size of the ultimately produced phosphate coating crystals can be controlled in the present invention by adjusting the average particle size of the divalent or trivalent metal phosphate particles that are less than 5 ⁇ m in size.
  • the use of very finely divided divalent or trivalent metal phosphate will cause the deposition of very finely-sized phosphate crystals.
  • the divalent or trivalent metal phosphate concentration preferably falls in the range from 0.001 to 30 g/L.
  • the divalent or trivalent metal phosphate concentration is below 0.001 g/L, usually so little divalent or trivalent metal phosphate becomes adsorbed on the metal surface that accelerating the phosphate conversion reactions hardly occurs.
  • little or no additional acceleration of the phosphate conversion reactions is obtained at divalent or trivalent metal phosphate concentrations in excess of 30 g/L; this makes such concentrations uneconomical.
  • the concentration of dispersed divalent or trivalent phosphate particles in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.010, 0.10, 0.50, 0.75, 1.0, 1.2, 1.6, or 1.8 g/L and independently preferably is not more than, with increasing preference in the order given, 25, 20, 15, 10, 7.5, 5.0, 4.0, 3.5, 3.0, or 2.5 g/L.
  • alkali metal salt or ammonium salt or mixture thereof is the alkali metal salt or ammonium salt or mixture thereof (abbreviated below simply as the "alkali metal salt or ammonium salt”).
  • alkali metal salt or ammonium salt As explained above with reference to the prior art, surface conditioning by blowing insoluble divalent or trivalent metal phosphate under elevated pressure has already been pursued in a previously disclosed process. However, this previously disclosed process requires a vigorous and persistent spray of insoluble divalent or trivalent metal phosphate under elevated pressure. The reason for the use of the elevated-pressure spray is that, in order for surface conditioning activity to be produced, this process requires reaction by striking the metal surface with the insoluble phosphate or requires abrasion of the metal surface as in shot peening. In order, on the other hand, to obtain surface conditioning activity by dipping, the prior-art process requires extremely high concentrations of the insoluble divalent or trivalent metal phosphate.
  • the present inventors have discovered that, in the presence of dissolved alkali metal salt or ammonium salt, surface conditioning activity can be generated even by dipping in low concentrations of the insoluble divalent or trivalent metal phosphate and without the application of physical force to the metal surface.
  • the present invention requires nothing more than simple contact between the workpiece and the surface conditioning pretreatment bath and thus has a reaction mechanism completely different from that in the prior art. It is for this reason that the alkali metal salt or ammonium salt is an essential component.
  • alkali metal salt or ammonium salt is not crucial as long as it is selected from the group consisting of orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, and borates. Combinations of two or more of these alkali metal salts or ammonium salts may also be used unproblematically.
  • the desirable concentration range for the alkali metal salt or ammonium salt is from 0.5 to 20 g/L. Concentrations below 0.5 g/L often fail to provide surface conditioning activity by simple contact between the workpiece and surface conditioning pretreatment bath. Concentrations in excess of 20 g/L do not provide additional benefits and are therefore uneconomical.
  • the concentration of dissolved alkali metal or ammonium salt in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.010, 0.10, 0.50, 1.0, 2.0, 3.0, 4.0, or 4.9 g/L and independently preferably is not more than, with increasing preference in the order given, 25, 20, 15, 10, 7.5, or 5.5 g/L.
  • the surface conditioning pretreatment bath according to the present invention must be adjusted into the pH range from 4.0 to 13.0. At a pH below 4.0, the metal usually corrodes in the surface conditioning pretreatment bath with the production of an oxide coating, which raises the possibility of defective phosphate conversion treatment. At a pH in excess of 13.0, neutralization of the acidic phosphate conversion bath by surface conditioning pretreatment bath carried over into the phosphate conversion treatment step can throw the phosphate conversion bath out of balance.
  • the pH value in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, or 7.5 and independently preferably is not more than, with increasing preference in the order given, 12.0, 11.0, 10.5, 10.0, 9.5, 9.0, or 8.5.
  • microparticulate oxide that disperses in an anionically charged state is essential for a composition according to this invention.
  • the microparticulate oxide adsorbs to the metal surface with the formation of nuclei that can function as microcathodes for phosphate crystal deposition, and thus forms a starting point for the phosphate conversion reactions.
  • the microparticulate oxide functions to improve the dispersion stability of the divalent or trivalent metal phosphate in the surface conditioning pretreatment bath.
  • the microparticulate oxide either by adsorbing to the divalent or trivalent metal phosphate dispersed in the surface conditioning pretreatment bath or by preventing collisions among the divalent or trivalent metal phosphate particles, improves the stability by preventing the aggregation and precipitation of the divalent or trivalent metal phosphate.
  • the particle size of the microparticulate oxide must be smaller than the particle size of the divalent or trivalent metal phosphate.
  • the microparticulate oxide preferably has a particle size ⁇ 0.5 ⁇ m.
  • the metal in the microparticulate oxide used by the present invention is not crucial as long as the microparticulate oxide satisfies the particle size and anionicity conditions.
  • An initially cationic microparticulate oxide can be used after its surface charge has been converted to anionic by a surface treatment.
  • the same increase in the dispersion stability of the divalent or trivalent metal phosphate in the surface conditioning pretreatment bath according to the present invention can be obtained using anionic water-soluble organic polymer, nonionic water-soluble organic polymer, anionic surfactant, or nonionic surfactant.
  • the concentration of the microparticulate oxide is preferably from 0.001 to 5 ppm.
  • a microparticulate oxide concentration below 0.001 ppm cannot usually provide the increase in dispersion stability by the divalent or trivalent metal phosphate in the surface conditioning pretreatment bath that is the main purpose for using the microparticulate oxide in the present invention.
  • An economically motivated upper concentration limit can be established at 5 g/L because concentrations in excess of 5 g/L provide no additional increase in the dispersion stability of the divalent or trivalent metal phosphate.
  • the concentration of microparticulate oxide particles in a conditioning pretreatment according to the invention more preferably is at least, with increasing preference in the order given, 0.003, 0.005, 0.007, or 0.009 ppm and independently preferably is not more than, with increasing preference in the order given, 4.0, 3.0, 2.0, 1.5, 1.0, 0.50, 0.25, 0.12, 0.080, 0.060, 0.040, or 0.020 ppm.
  • the surface conditioning pretreatment bath according to the present invention retains its activity regardless of its use conditions.
  • the surface conditioning pretreatment bath according to the present invention offers the following advantages over the prior art technology: (1) It has a long storage stability; (2) its activity is not impaired by the admixture of hardness components such as Ca, Mg, and the like; (3) it can be used at high temperatures; (4) it tolerates the addition of various alkali metal salts; (5) it is very stable over a broad pH range; and (6) it provides for adjustment of the size of the ultimately obtained phosphate crystals.
  • the bath according to the present invention can also be used as a simultaneous cleaner/degreaser and surface conditioner, whereas the prior technology in this area has been unable to continuously maintain stable quality.
  • the known inorganic alkali builders, organic builders, surfactants, and the like may be added in this application in order to improve the cleaning capacity in the degreasing and surface conditioning step.
  • the known chelating agents, condensed phosphates, and the like that are used for degreasing/cleaning may be added to a conditioning composition according to this invention in order to negate the effects of cationic components that may be carried into the surface conditioning pretreatment bath.
  • a surface conditioning process according to the present invention involves simply contacting the metal surface with the surface conditioning pretreatment bath.
  • the contact time and bath temperature are not critical.
  • the surface conditioning process according to the present invention can be applied to any metal on which a phosphate treatment can be executed, e.g., iron, steel, galvanized steel sheet, aluminum, and aluminum alloys.
  • FINECLEANER® L4460 concentrate (commercially available from Nihon Parkerizing Company, Limited), diluted to 2 % with tapwater to provide a concentration of 2 % of the concentrate in the diluted working degreasing solution, was used in the working and comparative examples.
  • compositions of the surface conditioning pretreatment baths used in the working examples are reported in Table 1.
  • compositions of the surface conditioning pretreatment baths used in the comparative examples are reported in Table 2.
  • the time-elapsed testing was run after holding the surface conditioning pretreatment bath at room temperature for one week after preparation.
  • Example 1 Na 3 PO 4 ⁇ 12H 2 O, 5 g/L none Zn 3 (PO 4 ) 2 ⁇ 4H 2 O, 2 g/L 0.31 10.0
  • Example 2 Na 3 PO 4 ⁇ 12H 2 O, 5 g/L SiO 2 , 10 ppm Zn 3 (PO 4 ) 2 ⁇ 4H 2 O, 2 g/L 0.31 10.0
  • Example 3 Na 3 PO 4 ⁇ 12H 2 O, 5 g/L SiO 2 , 10 ppm Zn 3 (PO 4 ) 2 ⁇ 4H 2 O, 2 g/L 4.2 10.0
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 1 minute in a mortar and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper.
  • Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 4.2 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 1 hour in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.09 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • a precipitate was produced by alternately adding 100 milliliters (hereinafter usually abbreviated as "mL”) of a 1 mole per liter (hereinafter usually abbreviated as "mol/L”) zinc sulfate solution and 100 mL of a 1 mol/L sodium monohydrogen phosphate solution to 1 liter (hereinafter usually abbreviated as "L") of a 0.5 mol/L iron(II) sulfate solution heated to 50 °C.
  • the aqueous solution containing the precipitate was then heated at 90 °C for 1 hour in order to ripen the precipitate particles. This was followed by washing 10 times by decantation.
  • the precipitate was recovered by filtration and dried and then analyzed by x-ray diffraction. The results indicated that the precipitate was primarily phosphophyllite (i.e., Zn 2 Fe(PO 4 ) 2 ⁇ 4H 2 O) containing some trivalent iron phosphate. This phosphophyllite was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate. This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.29 ⁇ m.
  • a submicron particle analyzer Coulter Model N4 from the Coulter Company
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • This Zn X Mn Y (PO 4 ) 2 was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.32 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • a precipitate was produced by the addition of 200 mL of a 1 mol/L zinc nitrate solution and then 200 mL of a 1 mol/L sodium monohydrogen phosphate solution to 1 L of a 0.1 mol/L calcium nitrate solution heated to 50 °C.
  • the aqueous solution containing the precipitate was then heated at 90 °C for 1 hour in order to ripen the precipitate particles. This was followed by washing 10 times by decantation.
  • the precipitate was recovered by filtration and dried and was analyzed by x-ray diffraction. The results indicated that the precipitate was scholzite (Zn 2 Ca(PO 4 ) 2 ⁇ 4H 2 O).
  • This scholzite was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.30 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m. The concentration of the divalent metal phosphate in the filtrate was also adjusted to 0.02 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the ZrO 2 sol (microparticulate oxide, NZS-30B from Nissan Kagaku Kogyo Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • ZrO 2 sol microparticulate oxide, NZS-30B from Nissan Kagaku Kogyo Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 30 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the Sb 2 O 5 sol (microparticulate oxide, A-1530 from Nissan Kagaku Kogyo Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • Sb 2 O 5 sol microparticulate oxide, A-1530 from Nissan Kagaku Kogyo Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the sodium metasilicate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • sodium metasilicate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the sodium sesquicarbonate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • sodium sesquicarbonate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • the surface conditioning pretreatment was run using the treatment bath described in Example 2 at a treatment temperature of 40 °C.
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate. The concentration of this divalent metal phosphate was brought to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 1 was prepared by addition of the SiO 2 (a microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 a microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 2 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was used as the divalent metal phosphate.
  • This divalent metal phosphate was made into a suspension and the suspension was filtered through 5- ⁇ m filter paper. The particles remaining on the filter paper were redispersed in water to prepare a suspension. Measurement of the average particle size in the suspension using a Coulter Counter (Coulter Company) gave a value of 6.5 ⁇ m. The concentration of the divalent metal phosphate in the suspension was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 2 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • Zn 3 (PO 4 ) 2 ⁇ 4H 2 O reagent was ground for 10 minutes in a ball mill using zirconia beads and was then used as the divalent metal phosphate.
  • This divalent metal phosphate was converted into a suspension and then filtered through 5- ⁇ m filter paper. Measurement of the average particle size in the filtrate using a submicron particle analyzer (Coulter Model N4 from the Coulter Company) gave a value of 0.31 ⁇ m.
  • the concentration of the divalent metal phosphate in the filtrate was also adjusted to 2 g/L.
  • the surface conditioning pretreatment bath reported in Table 2 was prepared by addition of the SiO 2 (microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha) and then the trisodium phosphate reagent (an alkali metal salt) to the concentration-adjusted suspension and subsequent adjustment of the pH to the specified value.
  • SiO 2 microparticulate oxide, Aerosil #300 from Nippon Aerosil Kabushiki Kaisha
  • trisodium phosphate reagent an alkali metal salt
  • PALBOND® L3020 concentrate (commercially available from Nihon Parkerizing Company, Limited), diluted with tapwater to give 4.8 % of the concentrate in the diluted solution and to adjust total acidity, free acidity, and accelerator concentration to the concentrations in general use for automotive zinc phosphate treatment, was used as the zinc phosphate treatment bath.
  • Void areas and nonuniformity in the zinc phosphate coating were visually determined and were evaluated on the following scale.
  • the weight of the conversion-treated panel was measured to give W1 (g).
  • the coating on the conversion-treated panel was then stripped (stripping bath and conditions given below) and the weight was again measured to give W2 (g).
  • the deposited coating crystals were inspected using a scanning electron microscope (SEM) at 1,500 X in order to determine crystal size.
  • this value was determined only on the SPC steel panels by measuring the x-ray intensity of the phosphophyllite crystals (P) and x-ray intensity of the hopeite crystals (H) in the zinc phosphate conversion coating using an x-ray diffraction instrument.
  • test panels after completion of the phosphate treatment and rinsing thereafter, some of the test panels were first painted with a cationic electrodeposition paint (ELECRONTM 2000 from Kansai Paint Kabushiki Kaisha) so as to provide a coating thickness of 20 ⁇ m and were baked at 180 °C for 25 minutes. Some of the panels were then submitted in this condition to salt spray testing and testing of resistance to hot salt water. The remaining electrocoated panels were painted with a middle coat paint (Automotive Middle Coat Paint from Kansai Paint) so as to provide a middle coat thickness of 40 ⁇ m and were baked at 140 °C for 30 minutes.
  • a middle coat paint Automotive Middle Coat Paint from Kansai Paint
  • the middle-coated test panels were then painted with a topcoat (Automotive Topcoat Paint from Kansai Paint) so as to provide a topcoat thickness of 40 ⁇ m and were baked at 140 °C for 30 minutes.
  • Table 3 reports the properties of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the working examples
  • Table 4 reports the properties of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the comparative examples
  • Table 5 reports the results for evaluation of the post-paint performance of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the working examples
  • Table 6 reports the results for evaluation of the post-paint performance of the conversion coatings obtained by zinc phosphate treatment using the surface conditioning pretreatment baths of the comparative examples.
  • Tables 3 and 4 confirm a major improvement in the storage time stability of the surface conditioning pretreatment baths according to the present invention.
  • the storage time stability has been a problem with prior art products.
  • Examples 1 and 2 confirm the effect of the microparticulate oxide on the timewise stability. Furthermore, the effects did not vary even in the face of changes in the type of microparticulate oxide and alkali metal salt and in the treatment temperature, and in each case fine-sized, dense crystals were obtained that were equal or superior to those afforded by the prior art products.
  • Tables 5 and 6 confirm that the surface conditioning pretreatment baths according to the present invention gave a paint performance equal or superior to that of the prior art products.
  • Test Identification Substrate Identifi- cation Test Result for Treatment with Conditioning Pretreatment of: CE 1 CE 2 CE 3 CE 4 CE 5 CE 6 CE 7 CE 8 Immediately after making up the surface conditioning pretreatment bath Saltwater spray, 960 hours, electro-coated panel SPC 1.0 1.0 2.5 3.5 ⁇ 5.0 ⁇ ⁇ ⁇ EG 2.0 2.0 3.5 4.0 ⁇ 5.0 ⁇ ⁇ ⁇ GA ⁇ 0.5 ⁇ 0.5 2.5 3.0 3.5 ⁇ ⁇ ⁇ Al ⁇ 0.5 ⁇ 0.5 1.0 1.0 2.0 ⁇ ⁇ ⁇ Zn-Ni 2.0 1.5 3.0 3.5 ⁇ 5.0 ⁇ ⁇ ⁇ Hot salt water resistance, 240 hours, electro-coated panel SPC 1.0 1.0 3.0 4.0 ⁇ 5.0 ⁇ ⁇ ⁇ EG 2.5 2.0 3.0 4.0 ⁇ 5.0 ⁇ ⁇ ⁇ GA

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Claims (7)

  1. Composition de pré-traitement liquide, apte au conditionnent de surfaces métalliques avant son traitement de revêtement par conversion au phosphate, ladite composition de pré-traitement ayant une valeur de pH dans la plage de 4 à 13 et comprenant les composants suivants :
    (A) un composant dissous étant un ou plusieurs sel(s) d'ammonium /métaux alcalins;
    (B) un composant dispersé étant un ou plusieurs phosphate(s) de métaux divalents et/ou trivalents, lesdits phosphates comprenant des particules dispersées ayant une taille particulaire qui n'est pas supérieure à 5 µm; et
    (C) un composant choisi à partir d'un ou de plusieurs oxyde(s) microparticulaire(s) qui se disperse(nt) en solution aqueuse dans un état chargé anioniquement.
  2. Composition de pré-traitement selon la revendication 1, dans laquelle le sel des métaux alcalins et/ou le(s) sel(s) d'ammonium dissous dans le composant A est/sont un ou plusieurs orthophosphate(s), métaphosphate(s), orthosilicate(s), métasilicate(s), carbonate(s), bicarbonate(s), et/ou borate(s) présent(s) dans une concentration dans la plage de 0,5 à 20 g/L.
  3. Composition de pré-traitement selon la revendication 1 ou la revendication 2, dans laquelle les particules de phosphate dispersées ayant une taille particulaire ≤ 5pm dans le composant B cent présentes dans la plage de concentration allant de 0,001 à 30 g/L et ces particules sont un ou plusieurs phosphate(s) de Zn, Fe, Mn, Ni, Co, Ca et/ou Al.
  4. Composition de pré-traitement selon l'une quelconque des revendications précédentes, dans laquelle l'oxyde microparticulaire qui se disperse dans un état chargé anioniquement formant le composant C présente une taille particulaire moyenne qui est ≤ 0,5µm et est présent dans une concentration dans la plage allant de 0,001 à 5 g/L.
  5. Composition de pré-traitement selon l'une quelconque des revendications précédentes, dans laquelle l'oxyde microparticulaire qui se disperse dans un état chargé anioniquement formant le composant C est sélectionné à partir d'un ou de plusieurs oxyde(s) de Si, B, Ti, Zr, Al, Sb, Mg, Se, Zn, Sn, Fe, Mo et/ou V.
  6. Procédé pour conditionner des surfaces métalliques avant son traitement de revêtement de conversion au phosphate, dans lequel ladite surface métallique avant de recevoir un revêtement de conversion au phosphate est mise en contact avec une composition de pré-traitement de conditionnement de surface selon l'une quelconque des revendications précédentes.
  7. Procédé selon la revendication 6, dans lequel la composition de pré-traitement de conditionnement de surface comprend de plus à la fois un ou plusieurs agents tensioactifs non ioniques ou anioniques et un adjuvant de sorte que la surface métallique est simultanément nettoyée et activée.
EP98908792A 1997-03-07 1998-03-09 Conditionnement de surfaces metalliques prealablement a la phosphatation Revoked EP0977908B1 (fr)

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JP05218197A JP3451334B2 (ja) 1997-03-07 1997-03-07 金属のりん酸塩皮膜化成処理前の表面調整用前処理液及び表面調整方法
JP5218197 1997-03-07
PCT/US1998/003934 WO1998039498A1 (fr) 1997-03-07 1998-03-09 Conditionnement de surfaces metalliques prealablement a la phosphatation

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EP4174211A1 (fr) 2021-11-02 2023-05-03 Henkel AG & Co. KGaA Traitement en plusieurs étages permettant d'activer le phosphatation au zinc des composants métalliques pourvus de surfaces en zinc
CN117535653A (zh) * 2022-08-01 2024-02-09 宝山钢铁股份有限公司 一种用于高强钢可磷化性能改善的环保水基处理剂
CZ2022448A3 (cs) * 2022-10-31 2024-03-27 ÄŚeskĂ© vysokĂ© uÄŤenĂ­ technickĂ© v Praze Způsob předúpravy povrchu ocelových komponent

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DE102008017523A1 (de) * 2008-03-20 2009-09-24 Henkel Ag & Co. Kgaa Optimierte Elektrotauchlackierung von zusammengefügten und teilweise vorphosphatierten Bauteilen
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DE69817803T2 (de) 2004-07-01
MY124633A (en) 2006-06-30
CA2283387C (fr) 2007-07-03
ID20532A (id) 1999-01-07
KR19980079984A (ko) 1998-11-25
EP0977908A4 (fr) 2000-06-07
JPH10245685A (ja) 1998-09-14
CN1198958C (zh) 2005-04-27
KR100473603B1 (ko) 2005-08-29
JP3451334B2 (ja) 2003-09-29
EP0977908A1 (fr) 2000-02-09
ES2205456T3 (es) 2004-05-01
ZA981796B (en) 1998-09-07
DE69817803D1 (de) 2003-10-09
TW371675B (en) 1999-10-11
CN1197849A (zh) 1998-11-04
WO1998039498A1 (fr) 1998-09-11
AU6673698A (en) 1998-09-22
CA2283387A1 (fr) 1998-09-11

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