WO1999060186A1 - Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages - Google Patents

Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages Download PDF

Info

Publication number
WO1999060186A1
WO1999060186A1 PCT/US1999/010450 US9910450W WO9960186A1 WO 1999060186 A1 WO1999060186 A1 WO 1999060186A1 US 9910450 W US9910450 W US 9910450W WO 9960186 A1 WO9960186 A1 WO 9960186A1
Authority
WO
WIPO (PCT)
Prior art keywords
zirconium
titanium
manganese
treatment
magnesium
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.)
Ceased
Application number
PCT/US1999/010450
Other languages
English (en)
Other versions
WO1999060186A8 (fr
Inventor
Kazuya Nakada
Motoki Kawaguchi
Kazuhiro Maeda
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
Henkel Corp
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
Priority claimed from JP13788698A external-priority patent/JP3930640B2/ja
Application filed by Henkel Corp filed Critical Henkel Corp
Priority to CA002332620A priority Critical patent/CA2332620A1/fr
Priority to EP99952062A priority patent/EP1177329A4/fr
Priority to US09/700,733 priority patent/US6485580B1/en
Priority to AU43080/99A priority patent/AU4308099A/en
Publication of WO1999060186A1 publication Critical patent/WO1999060186A1/fr
Publication of WO1999060186A8 publication Critical patent/WO1999060186A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/57—Treatment of magnesium or alloys based thereon
    • 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
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon

Definitions

  • the invention relates to a novel water-based liquid composition, often called a "bath” hereinafter for brevity, even though it may be used with other methods than immersion for establishing contact between the composition and the surface to be
  • This invention can be applied in a particularly advantageous manner to the surface treatment of aluminum fin stock for heat exchangers, aluminum alloy coil, aluminum alloy sheet, and magnesium and 0 magnesium alloy automotive and aerospace components and electronic devices and instruments.
  • the baths used to treat aluminum and aluminum alloy surfaces can be broadly classified into chromate-type baths and non-chromate-type baths. Chromic acid chro- mate conversion baths and phosphoric acid chromate conversion baths are typical ex- 5 amples of the chromate-type treatment baths.
  • Chromic acid chromate conversion baths first reached practical application in about 1950 and even now are widely used for the surface treatment of aluminum (the word "aluminum” and all of its grammatical variations being understood hereinafter, unless the context indicates otherwise, to apply to alloys that contain at least, with 0 increasing preference in the order given, 45, 60, 75, 85, 90, 95, or 99 % by weight of aluminum) fin stock for heat exchangers and aluminum wheels, building materials, and aerospace materials.
  • the main components in chromic acid chromate conversion baths are chromic acid and a fluoride-type reaction accelerator. This type of bath produces a conversion coating containing moderate amounts of hexavalent chromium on the metal
  • Phosphoric acid chromate conversion baths originated with the invention disclosed in United States Patent No.2,438,877.
  • the main components in phosphoric acid chromate conversion baths are chromic acid, phosphoric acid, and hydrofluoric acid.
  • a conversion coating whose main component is hydrated chromium phosphate is formed
  • this type of bath is in wide used at the present time as an underpaint treatment for the body stock and lid stock of beverage cans.
  • Patent Application Number Sho 57-41376 (41 ,376/1982) involves treating the surface of aluminum, magnesium, or an alloy thereof with an aqueous solution containing at least one selection from titanium salts and zirconium salts and at least one selection from imidazole derivatives.
  • Sho 57-41376 have an anticorrosion performance corresponding to no rusting at 48 hours according to Japanese Industrial Standard (hereinafter usually abbreviated as "JIS") Z-2371. This performance, while satisfactory 15 years ago, is not unequivocally satisfactory at present.
  • JIS Japanese Industrial Standard
  • This patent application also describes the supplementary addition, at from 0.01 to 100 g/L as the compound, of an oxidizer such as nitric acid, hydrogen peroxide, or potassium permanganate, but does not provide a working example supporting the use of a potassium permanganate oxidizer.
  • Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 8- 144063 teaches a surface treatment method for the formation of conver- sion coatings on the surface of aluminum stock.
  • This method uses an aqueous solution that contains potassium permanganate or potassium manganate or both in addition to a coating-forming accelerator such as a mineral acid (HNO 3 , H 2 SO 4 , HF), an alkali (KOH, NaOH, NH 4 OH), a neutral fluoride (KF, NaF), an acidic fluoride (NH 4 HF 2 , NaHF 2 , KHF 2 ), or a fluorosilicate (MnSiF 6 , MgSiF 6 ).
  • a coating-forming accelerator such as a mineral acid (HNO 3 , H 2 SO 4 , HF), an alkali (KOH, NaOH, NH 4 OH), a neutral fluoride (KF, NaF), an acidic fluoride (NH 4
  • SUBST ⁇ UTE SHEET (RULE 26) type surface treatment baths remains associated with problems with the corrosion resistance of the produced conversion coatings and pollution abatement of the effluent from the surface treatment bath. It is for these reasons that at present non-chromate- type surface treatment baths are little used on surface treatment lines where a particularly good corrosion resistance is required, for example, for aluminum fin stock for heat exchangers and aluminiferous metal coil and sheet stock.
  • MIL magnesium and magnesium alloy surfaces
  • the conversion coatings generated by these chromate-type surface treatment baths exhibit an excellent corrosion resistance and an excellent adherence to paint films, but these treatment baths also contain highly toxic hexavalent chromium.
  • the associated environmental problems have made it desirable to use treatment baths that are entirely free of hexavalent chromium.
  • Application Number Hei 3-6994 is an invention typical of the chromium-free non-chromate-type surface treatment baths for magnesium and its alloys.
  • This is a phosphate surface treatment method, and while it does not employ hexavalent chromium, it also does not have the ability to generate high-level properties. More specifically, this treatment method requires the execution of a silicate treatment after the phosphate treatment and the execution of a silicone treatment after the silicate treatment.
  • the phosphate treatment coating by itself provides a low level of corrosion resistance and paint adherence when used as an underpaint treatment for magnesium and magnesium alloy surfaces.
  • This treatment method also requires a multistage treatment process, uses high treatment temperatures, and requires long treatment times.
  • the known phosphate-based surface treatment methods include methods that employ treatment baths based on zinc phosphate, iron phosphate, calcium phosphate, or zirconium phosphate. However, these methods essentially cannot provide a corrosion resistance that is satisfactory at the level of practice.
  • a manganese phosphate treatment is disclosed in category 7 of JIS H-8651.
  • this treatment bath contains chromium, requires high treatment temperatures of 80 °C to 90 °C, and requires long treatment times of 30 to 60 minutes and thus is not acceptable from a practical standpoint.
  • Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 8- 35073 (35,073/1996) teaches a surface treatment method for the formation of conversion coatings on the surface of magnesium stock.
  • This method uses an aqueous solution that contains permanganic acid or manganic acid or both in addition to a coating-forming accelerator such as a mineral acid (HNO 3 , H 2 SO 4 , HF), an alkali (KOH, NaOH, NH 4 OH), or a neutral fluoride (MnSiF 6 , MgSiF 6 ).
  • a coating-forming accelerator such as a mineral acid (HNO 3 , H 2 SO 4 , HF), an alkali (KOH, NaOH, NH 4 OH), or a neutral fluoride (MnSiF 6 , MgSiF 6 ).
  • the conversion coating formed by this treatment bath has not been found to have a corrosion resistance in long-term corrosion- resistance testing equal to or greater than that of chromat
  • the object of the present invention is to provide a surface treatment bath that can coat light metal and light metal alloy surfaces with a film that imparts an excellent corrosion resistance and excellent paint adherence to the treated surface.
  • a highly corrosion-resistant, highly paint-adherent conversion coating can be formed on the surfaces of light metals and light metal alloys by the use of a surface treatment bath that has a pH of 1.0 to 7.0 and that contains specific amounts of permanganic acid or salt thereof and specific amounts of at least one compound selected from water-soluble titanium compounds and water-soluble zirconium compounds.
  • a surface treatment bath according to the present invention has a pH from 1.0 to 7.0 and comprises, preferably consists essentially of, or more preferably consists of: 0.01 to 50 grams of permanganic acid and/or salt thereof per liter of the total treatment bath, this concentration unit being freely applied hereinafter to any constituent of the surface treatment bath and being hereinafter usually abbreviated as "g/L"; and 0.01 to 20 g/L of at least one compound selected from water-soluble titanium compounds and water-soluble zirconium compounds; and, optionally, one or more of a pH adjustment agent, a sequestering agent, a supplemental oxidizing agent, and a component of water- soluble manganese compounds other than permanganic acid and its salts.
  • Such a bath is believed to form a manganese-containing composite coating comprising compounds of at least two of the heavy metal elements, i.e., manganese + titanium, or manganese + zirconium, or manganese + titanium + zirconium, and a conversion coating of this type preferably is formed in a process according to this invention, because this type of conversion coating exhibits the desired improved corrosion resistance.
  • a composition according to this invention does not contain more than, with increasing preference in the order given, 1.0, 0.5, 0.2, 0.10, 0.070, 0.030, 0.010, 0.007, 0.003, 0.001 , 0.0007, 0.0003, or 0.0001 percent by weight of chromium in any chemical form.
  • a single selection or several selections from the group consisting of permanganic acid and its salts can be used to furnish permanganic acid or permanganate salt to the surface treatment bath according to the present invention.
  • the particular species used is not crucial.
  • the concentration of permanganic acid and/or salt(s) thereof in a surface treatment bath according to the invention preferably is at least, with increasing preference in the order given, 0.01 , 0.05, 0.15, 0.25, 0.35, or 0.45 g/L, and unless the surface treatment bath also comprises a concentration of other manganese containing solutes that is at least as great as the concentration of permanganic acid and/or its salts more preferably is at least, with increasing preference in the order given, 0.55, 0.65, 0.75, 0.85, 0.95, 1.5, 2.0, 3.0, 4.0, or 4.5 g/L.
  • the concentration of permanganic acid and/or its salt(s) preferably is not more than, with increasing preference in the order given, 50, 35, 20,
  • concentrations above 50 g/L but higher concentrations than this and even the moderately preferred concentrations lower than 50 g/L are almost always uneconomical, because insufficient increases in corrosion resistance or paint adhesion result to offset the higher costs of the treatment bath.
  • One or more selections from, for example, the sulfates, oxysulfates, acetates, ammonium salts, and fluorides of titanium and zirconium can be used to furnish the water-soluble titanium compound or water-soluble zirconium compound to the surface treatment bath according to the present invention.
  • the particular species used is not crucial as long as it is a water-soluble compound.
  • This component preferably is present in a treatment bath according to the invention at a concentration that is at least, with increasing preference in the order given, 0.01 , 0.03, 0.05, 0.07, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 g/L and independently preferably is not more than, with increasing preference in the order given, 20, 10, 5, 3, 2.0, 1.5, 1.2, 1.0, 0.80, 0.70, 0.60, or 0.55 g/L.
  • Conversion coatings can be formed when this component is present at a concentration of less than 0.01 g/L, but such coatings usually have a poor corrosion resistance.
  • the pH of the surface treatment bath according to the present invention must be from 1.0 to 7.0.
  • the bath preferably has a pH that is at least, with increasing preference in the order given, 1.5, 2.0, 2.2, or 2.4 and independently preferably is not more than, with increasing preference in the order given, 6.0, 5.5, 5.0, or 4.6.
  • the pH is strongly preferred to be at least 2.0.
  • the metal substrate being treated normally will undergo excessive etching when the pH is below the given lower limit, so that an uneven appearance will be produced. A pH above the given upper limit can produce various problems, all of which are undesirable.
  • the pH of the surface treatment bath according to the present invention can be adjusted to a preferred value by using a suitable selection as known to those skilled in the art, from acids such as nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and fluorosilicic acid, and bases such as sodium hydroxide, sodium carbonate, potassium hydroxide, and ammonium hydroxide.
  • the treatment bath may suffer from a substantial reduction in stability due to cations of the alloying component(s) that elute into the surface treatment bath.
  • a sequestering agent may be added in such cases in order to chelate these metal alloy components.
  • This sequestering agent can be, for example, an organic acid such as gluconic acid, heptogluconic acid, oxalic acid, tartaric acid, an organophosphonic acid, and ethylenediaminetetraacetic acid or an alkali metal salt thereof.
  • These sequestering agents can also advantageously be used in the case of magnesium alloys containing, for example, aluminum or zinc.
  • a supplemental oxidizer other than permanganic acid and its salts may also be used in the present invention in order to accelerate formation of the conversion coating.
  • This supplemental oxidizer can be exemplified by tungstic acid, molybdic acid, and their salts and by water-soluble organoperoxides such as tert-butyl hydroperoxide.
  • a conversion coating formed by the hereinabove described method preferably comprises manganese and at least one selection from titanium and zirconium.
  • the Mn/(Ti + Zr) weight ratio in such a conversion coating is preferably from 0.05 to 100.
  • this weight ratio is more preferably, with increasing preference in the order given, from 0.1 to 20.0, from 0.2 to 5.0, or from 0.2 to 1.5.
  • the aforementioned weight ratio is more preferably from 0.1 to 20 and most preferably is from 0.2 to 20.
  • the corrosion resistance becomes increasingly poor as this weight ratio declines below the specified lower limit, while the long-term corrosion resistance becomes increasingly poor as this weight ratio increases above the specified upper limit.
  • the total coating weight for Mn, Ti, and Zr is preferably at least, with increasing preference in the order given, 5, 10, 20, or 30 milligrams of the metals per square meter of substrate surface treated, this unit of coating weight being hereinafter usually abbreviated as "mg/m 2 ", and independently preferably is not more than, with increasing preference in the order given, 500, 300, 270, or 240 mg/m 2 .
  • a coating weight below 5 mg/m 2 can cause an inadequate corrosion resistance and paint adherence.
  • the chemical characteristics of the metal in the coating e.g., occurrence as the oxide or phosphate, etc., are not particularly critical for the manganese, titanium, and zirconium constituent components of the conversion coating according to the present invention.
  • a surface treatment bath according to the present invention in a preferred embodiment, is used as part of the following sequence of process operations: (1 ) surface cleaning: degreasing (acidic, basic, or solvent degreasers can be used);
  • a surface treatment bath according to the present invention is preferably brought into contact with the surface of the light metal or light metal alloy at a temperature that is at least, with increasing preference in the order given, 10, 15, or 20 °C and independ- ently preferably is not more than 80, 75, or 70 °C.
  • the time of contact between the treatment bath according to this invention and the substrate being treated in a process according to the invention preferably is at least, with increasing preference in the order given, 1 , 3, 5, 7, 9, 13, 16, 20, 25, or 28 seconds and independently preferably is not more than, with increasing preference in the order given, 300, 250, 220, 200, 180, 160, 140, or 120 seconds.
  • the reactivity between the treatment bath and metal surface is usually inadequate at a contact temperature below 10 °C, so that a good-quality conversion coating will not usually be formed at such temperatures.
  • a conversion coating is still formed at a contact temperature above 80 °C, but the increased energy costs associated with such temperatures make them uneconomical.
  • Sufficient reaction to form a conversion coating that will exhibit a high level of corrosion resistance does not usually occur in a treatment time of less than 1 second. Times in excess of 300 seconds provide no additional improvement in the corrosion resistance or paint adherence of the resulting conversion coating.
  • Techniques such as immersion and spraying can be used to effect contact with the surface treatment bath according to the present invention.
  • the method used for the present invention preferably provides a conversion coating add-on on the light metal or light metal alloy surface of from 5 to 300 mg/m 2 as manganese and from 3 to 100 mg/m 2 as titanium and/or zirconium.
  • the conversion coating will usually exhibit an inadequate corrosion resistance and paint adherence at a manganese add-on below 5 mg/m 2 , while substantial irregularities in the external appearance of the conversion coating usually occur at values in excess of 300 mg/m 2 .
  • the conversion coating will often suffer from an inadequate corrosion resistance at a titanium or zirconium add-on below 3 mg/m 2 .
  • Highly corrosion-resistant conversion coatings are formed at a titanium or zirconium add-on above 100 mg/m 2 , but such values are uneconomical since no additional performance is produced by the additional add-on.
  • the aluminum and aluminum alloys that may be subjected to surface treatment according to the present invention encompass pure aluminum and its alloys. Examples of the latter are alloys such as Al-Cu, Al-Mn, Al-Mg, and Al-Si.
  • the magnesium and magnesium alloys that may be subjected to surface treatment according to the present invention encompass materials of magnesium and magnesium alloy metals.
  • the latter can be exemplified by Mg-AI-Zn, Mg-Zn, and Mg-AI-Zn-Mn.
  • the shape and dimensions of the light metal or light metal alloy used in the present invention are not critical, and, for example, the present invention encompasses both sheet stock and various formed products.
  • Substrate A was treated using the following processes in the sequence (1 ) - (2) - (3) - (4) - (5) - (6) to give the surface-treated sheet.
  • a 3 % aqueous solution of a commercial alkaline degreaser (FINECLEANER® 315 from Nihon Parkerizing Company, Limited) was used.
  • Substrate B was treated using the following processes in the sequence (1 ) - (2) - (3) - (4) - (5) - (6) to give the surface-treated sheet.
  • the 3 % aqueous solution of a commercial alkaline degreaser (FINECLEANER® 315 from Nihon Parkerizing Company, Limited) was used.
  • Comparative Example 1 is a comparative example that used a permanganate salt by itself as the treatment bath component to form a manganese-containing coating.
  • Comparative Example 2 is a comparative example that used a Zr compound by itself as the treatment bath component to form a zirconium-containing coating.
  • Table 3
  • Comparative Example 3 produced a very low-Ti (Mn/Ti) coating, while Comparative Example 4 produced a very low-Mn (Mn/Ti) coating. Comparative Example 5
  • This comparative example used a 7 % aqueous solution of a commercial zircon- ium phosphate-based surface treatment agent (ALCHROME® 713 from Nihon Parkerizing Company, Limited) for conversion treatment.
  • This bath was used to treat the Al-Mn alloy sheet specified above using the following treatment conditions: 40 °C, 60 seconds, immersion. Treatment was followed by evaluation of the corrosion resistance and paint adherence.
  • ACHROME® 713 commercial zircon- ium phosphate-based surface treatment agent
  • This comparative example used a 7 % aqueous solution of a commercial chromic acid chromate conversion treatment agent (ALCHROME® 713 from Nihon Parkerizing Company, Limited) for surface treatment. This bath was used to treat the Al-Mn alloy sheet specified above using the following treatment conditions: 40 °C, 60 seconds, immersion. Treatment was followed by evaluation of the corrosion resistance and paint adherence. Comparative Example 7 This comparative example used a 3 % aqueous solution of a commercial phosphoric acid chromate conversion treatment agent (mixed aqueous solution of 4 % ALCHROME® K702SL and 0.3 % ALCHROME® K702AC, both from Nihon Parkerizing Company, Limited) for the conversion treatment. This bath was used to treat the Al-Mn alloy sheet specified above using the following treatment conditions: 50 °C, 20 seconds, spray. Treatment was followed by evaluation of the corrosion resistance and paint adherence. Comparative Example 8
  • This comparative example used a 7 % aqueous solution of a commercial chromic acid chromate conversion treatment agent (ALCHROME® 713 from Nihon Parkerizing Company, Limited) for surface treatment. This bath was used to treat the magnesium alloy sheet specified above using the following treatment conditions: 30 °C, 60 seconds, immersion. Treatment was followed by evaluation of the corrosion resistance and paint adherence. Comparative Example 13 This comparative example used a treatment bath formulated according to MIL-M-
  • a larger number of unpeeled squares in this procedure is indicative of a better paint adherence, and a score of 98 or more unpeeled squares corresponds to a satisfactory performance at the level of practice.
  • Tables 2 and 3 demonstrate that the conversion coatings afforded by the treatment bath according to the present invention exhibit the same corrosion resistance as commercial chromic acid chromate and phosphoric acid chromate treatments. These tables also confirm that highly corrosion-resistant coatings can be realized by the formation of composite coatings in which suitable amounts of Mn and Ti/Zr are both present. As the preceding explanation makes clear, a hexavalent chromium-free, highly corrosion-resistant, and highly paint-adherent conversion coating is produced by the application of the surface treatment bath according to the present invention to light metals and light metal alloys.
  • This performance makes the surface treatment bath according to the present invention very useful at a practical level for application to light metals and light metal alloys.
  • the materials used for the casings and shells of, for example, computers and portable phones have recently shifted from plastics to magnesium alloys based on considerations of recyclability, thermal radiation, and relative strength per unit weight.
  • the electromagnetic radiation generated by electronic devices known as noise
  • this noise problem has created desire for the appearance of a surface treatment method that provides an excellent electromagnetic shielding performance in addi- tion to an excellent corrosion resistance and excellent paint adherence.
  • the coating formed by the surface treatment bath according to the present invention does not contain toxic chromium, exhibits excellent corrosion resistance and excellent paint adherence, and also has a low surface resistance and thereby can also provide an excellent electromagnetic shielding performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un bain aqueux permettant de traiter les surfaces des métaux légers et des alliages de métaux légers. Ce bain ne contient pas de chrome hexavalent ou ne produit pas d'autre effluent très polluant. Il forme une couche de conversion très résistante à la corrosion et qui adhère bien à la peinture. Son pH est compris entre 1,0 et 7,0. Il contient 0,01 à 50 g/l d'acide permanganique et/ou de ses sels, et 0,01 à 20 g/l d'au moins un composé hydrosoluble de titane ou de zirconium.
PCT/US1999/010450 1998-05-20 1999-05-20 Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages Ceased WO1999060186A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002332620A CA2332620A1 (fr) 1998-05-20 1999-05-20 Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages
EP99952062A EP1177329A4 (fr) 1998-05-20 1999-05-20 Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages
US09/700,733 US6485580B1 (en) 1998-05-20 1999-05-20 Composition and process for treating surfaces or light metals and their alloys
AU43080/99A AU4308099A (en) 1998-05-20 1999-05-20 Composition and process for treating surfaces of light metals and their alloys

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/137886 1998-05-20
JP13788698A JP3930640B2 (ja) 1997-05-22 1998-05-20 軽金属または軽合金材料用表面処理液

Publications (2)

Publication Number Publication Date
WO1999060186A1 true WO1999060186A1 (fr) 1999-11-25
WO1999060186A8 WO1999060186A8 (fr) 2000-07-27

Family

ID=15208988

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/010450 Ceased WO1999060186A1 (fr) 1998-05-20 1999-05-20 Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages

Country Status (4)

Country Link
EP (1) EP1177329A4 (fr)
AU (1) AU4308099A (fr)
CA (1) CA2332620A1 (fr)
WO (1) WO1999060186A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2825378A1 (fr) * 2001-05-31 2002-12-06 Univ Paris Curie Composition et procede pour le traitement d'alliages de magnesium
EP1612294A1 (fr) * 2004-07-02 2006-01-04 Italtecno S.R.L. Bain et méthode associée de conversion pour d'articles faits d'aluminium et de ses alliages
WO2006108655A1 (fr) 2005-04-14 2006-10-19 Chemetall Gmbh Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326894A (en) * 1979-05-13 1982-04-27 Gerhard Collardin Gmbh Process for the production of conversion layers on metal surfaces by the spray method
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
US4600447A (en) * 1984-01-07 1986-07-15 Henkel Kommanditgesellschaft Auf Aktien After-passivation of phosphated metal surfaces
US4610732A (en) * 1984-03-23 1986-09-09 Hitachi, Ltd. Method of inhibiting corrosion of zirconium or its alloy
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3816494A1 (de) * 1988-05-10 1989-11-16 Schering Ag Loesung und verfahren zum aetzen und aktivieren von isolierenden oberflaechen
JP3623015B2 (ja) * 1995-06-30 2005-02-23 日本パーカライジング株式会社 アルミニウム含有金属材料用表面処理液および表面処理方法
US5952049A (en) * 1996-10-09 1999-09-14 Natural Coating Systems, Llc Conversion coatings for metals using group IV-A metals in the presence of little or no fluoride and little or no chromium
ZA984335B (en) * 1997-05-22 1998-11-30 Henkel Corp Waster-based liquid treatment for aluminum and its alloys

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4326894A (en) * 1979-05-13 1982-04-27 Gerhard Collardin Gmbh Process for the production of conversion layers on metal surfaces by the spray method
US4600447A (en) * 1984-01-07 1986-07-15 Henkel Kommanditgesellschaft Auf Aktien After-passivation of phosphated metal surfaces
US4610732A (en) * 1984-03-23 1986-09-09 Hitachi, Ltd. Method of inhibiting corrosion of zirconium or its alloy
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1177329A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2825378A1 (fr) * 2001-05-31 2002-12-06 Univ Paris Curie Composition et procede pour le traitement d'alliages de magnesium
WO2002097164A3 (fr) * 2001-05-31 2003-03-06 Univ Paris Curie Composition et procede pour le traitement d'alliages de magnesium
US7156905B2 (en) 2001-05-31 2007-01-02 Universite Pierre & Marie Curie Composition and method for treating magnesium alloys
EP1612294A1 (fr) * 2004-07-02 2006-01-04 Italtecno S.R.L. Bain et méthode associée de conversion pour d'articles faits d'aluminium et de ses alliages
WO2006108655A1 (fr) 2005-04-14 2006-10-19 Chemetall Gmbh Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium
US7695771B2 (en) 2005-04-14 2010-04-13 Chemetall Gmbh Process for forming a well visible non-chromate conversion coating for magnesium and magnesium alloys
RU2421545C2 (ru) * 2005-04-14 2011-06-20 Шеметалл Гмбх Способ получения хорошо различимого визуально нехроматного конверсионного покрытия для магния и магниевых сплавов

Also Published As

Publication number Publication date
EP1177329A4 (fr) 2002-06-12
AU4308099A (en) 1999-12-06
EP1177329A1 (fr) 2002-02-06
CA2332620A1 (fr) 1999-11-25
WO1999060186A8 (fr) 2000-07-27

Similar Documents

Publication Publication Date Title
US6193815B1 (en) Composition and process for treating the surface of aluminiferous metals
US6361833B1 (en) Composition and process for treating metal surfaces
EP1404894B1 (fr) Revetement anti-corrosion pour aluminium et alliages d'aluminium
US5393354A (en) Iridescent chromium coatings and method
AU684929B2 (en) Composition and process for treating the surface of aluminiferous metals
EP0664348B1 (fr) Procédé et composition de traitement de métaux
EP1433876B1 (fr) Agent chimique pour revêtement de conversion et surfaces métalliques revêtues
AU708280B2 (en) Composition and process for treating the surface of aluminiferous metals
JP3992173B2 (ja) 金属表面処理用組成物及び表面処理液ならびに表面処理方法
EP2044239B1 (fr) Procédé pour former des couches anti-corrosion sur des surfaces métalliques utilisant une composition améliorée comprenant du chrome trivalent
US5801217A (en) Chromium-free conversation coating and methods of use
WO2004055237A1 (fr) Fluide de traitement pour traitement de surface de metal et procede de traitement de surface
EP0719350B1 (fr) Traitement de metaux par une solution de nettoyage contenant des ions acides de terres rares
US5421913A (en) Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method
US6485580B1 (en) Composition and process for treating surfaces or light metals and their alloys
US6200693B1 (en) Water-based liquid treatment for aluminum and its alloys
EP0516700B1 (fr) Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium
JP3930640B2 (ja) 軽金属または軽合金材料用表面処理液
WO1999060186A1 (fr) Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages
US5888315A (en) Composition and process for forming an underpaint coating on metals
AU744557B2 (en) Water-based liquid treatment for aluminum and its alloys
CA2488199A1 (fr) Methode de revetement par conversion chimique a plusieurs etapes
JPH01225780A (ja) 高耐食性クロメート処理鋼板およびその製造方法ならびにクロメート処理液
MXPA97010210A (en) Composition and process for treating metal surface aluminife
MXPA01004311A (en) Composition and process for treating metal surfaces

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN MX SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)

Free format text: (EXCEPT PL, RU)

AK Designated states

Kind code of ref document: C1

Designated state(s): AU BR CA CN MX PL RU SG US

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i

Free format text: PAT. BUL. 47/99 UNDER (81) ADD "PL, RU"; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

ENP Entry into the national phase

Ref document number: 2332620

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 43080/99

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 09700733

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 1999952062

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1999952062

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1999952062

Country of ref document: EP