EP0516700B1 - Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium - Google Patents

Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium Download PDF

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Publication number
EP0516700B1
EP0516700B1 EP91904950A EP91904950A EP0516700B1 EP 0516700 B1 EP0516700 B1 EP 0516700B1 EP 91904950 A EP91904950 A EP 91904950A EP 91904950 A EP91904950 A EP 91904950A EP 0516700 B1 EP0516700 B1 EP 0516700B1
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Prior art keywords
ions
conversion
aluminum
acid
conversion treatment
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EP91904950A
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German (de)
English (en)
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EP0516700A1 (fr
Inventor
Masayuki Nihon Parkerizing Kibogaoka Yoshida
Kazuya Nihon Parkerizing Hiratsuka Nakada
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Henkel Corp
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Henkel Corp
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Priority claimed from JP2040168A external-priority patent/JPH07100872B2/ja
Priority claimed from JP4016990A external-priority patent/JPH0747828B2/ja
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
    • C23C22/38—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates

Definitions

  • the present invention relates to a novel conversion treatment solution for aluminum and aluminum alloys which imparts an excellent corrosion resistance and paint adherence to the surface of aluminum and aluminum alloys prior to their being painted and to a process of treating surfaces with such a solution.
  • the conversion treatment solution is particularly well suited for application to the surface of, for example, the lid material for beverage cans (i.e., can end stock) and the like.
  • Conversion treatment solutions for aluminum and aluminum alloys may be roughly classified into chromate-type treatments and nonchromate-type treatments.
  • Typical examples of chromate-type treatments are chromic acid/chromate treatments and phosphoric acid/chromate treatments.
  • Chromic acid/chromate treatments came into practical application in about 1950, and are still widely used at present on, for example, the fin material of heat exchangers.
  • the principal components of this type of conversion treatment solution are chromic acid (CrO3) and hydrofluoric acid (HF), and an accelerator may also be present.
  • CrO3 chromic acid
  • HF hydrofluoric acid
  • a film which contains some quantity of hexavalent chromium is formed.
  • the phosphoric acid/chromate conversion treatment is disclosed in United States Patent Number 2,438,877.
  • This conversion treatment solution is composed of chromic acid (CrO3), phosphoric acid (H3PO4), and hydrofluoric acid (HF).
  • the principal component of the resulting film is hydrated chromium phosphate (CrPO4 ⁇ 4H2O. Since this film does not contain much if any hexavalent chromium, it is widely used at present as a paint undercoating treatment for beverage cans and the associated lid stock.
  • Nonchromate-type treatments are recognized in the art as a distinct category from the chromate-type treatment solutions explained above, and are exemplified by the invention disclosed in Japanese Patent Application Laid Open [Kokai] Number 52-131937 [131,937/77].
  • the treatment solution disclosed therein comprises an acidic (pH approximately 1.0 to 4.0) aqueous coating solution which contains zirconium or titanium or a mixture thereof as well as phosphate and fluoride.
  • Treatment with the disclosed conversion treatment solution produces on the aluminum surface a conversion film whose main component is zirconium and/or titanium oxide.
  • this type of treatment solution nevertheless suffers from a corrosion resistance and paint adherence inferior to those for chromate-type treatments.
  • Aluminum alloy in sheet or coil form, is widely used after painting for beverage can lid material, i.e., can end stock. It is subjected to a conversion treatment in order to raise the corrosion resistance and paint adherence, and the phosphoric acid/chromate treatment is employed in almost all commercial can lid manufacturing in Japan.
  • the phosphoric acid/chromate conversion treatment of can end stock generally employs a treatment solution which contains 10.0 to 40.0 g/L phosphate ion, 2.0 to 4.0 g/L hexavalent chromium, and 0.7 to 1.5 g/L fluoride ion.
  • vinyl chloride paint is generally used to coat can end stock.
  • the production of can ends normally includes a phosphoric acid/chromate treatment of aluminum alloy in coil or sheet form, followed by coating with a vinyl chloride paint and then forming.
  • a beverage can thus normally consists of a can end formed from aluminum alloy coil or sheet treated as described above and of a can body filled with, for example, juice or beer.
  • the can may be subject d to sterilization at relatively high temperatures after filling. If it is, steam is formed from vaporization of the contents, the steam penetrates through the paint film, and the permeated steam then condenses at the interface between the paint film and conversion film. As a result, sterilization tends to reduce the adherence of the paint film.
  • defects enamel feathering
  • US-A-2 868 682 discloses aqueous solutions and a process for forming coatings particularly on surfaces of aluminum, iron or alloys thereof.
  • the solutions contain condensed phosphate compounds in a concentration not exceeding about 0.5 % by weight based on condensed phosphate of sodium compound (corresponding to a PO43 ⁇ -value of a about 3.6 g/l) hexavalent chromium within the range of from 0.42 to 13 g/l Cr6+ (0.08 to 2.5 % CrO3), between 0.1 to 20 g/l fluoride expressed as sodiumbifluoride, and up to 16 g/l fluoborate (preferably between 6 to 7 g/l) and optionally K2TiF6 and K2ZrF6 up to about 1 g/l.
  • the present invention introduces an aqueous conversion treatment solution for aluminum and aluminum alloys that has a pH in the range from 1.0 to 3.0 and consists essentially of, water and 5.0 to 40.0 grams per liter ("g/L") of phosphate ions, 1.0 to 4.0 g/L of hexavalent chromium (in the form of chromium containing anions), 0.1 to 2.0 g/L of fluoride ions, and a complex fluoride ion component selected from the group consisting of (i) 4.0 to 15.0 g/L of fluosilicate ion, (ii) 0.5 to 3.0 g/L of fluoborate ion, (iii) 2.0 to 8.0 g/L of fluozirconate ions, and (iv) 2.0 to 8.0 g/L of fluotitanate ions.
  • This conversion treatment solution is capable of forming a highly paint-adherent conversion film which imparts an excellent corrosion resistance to the surface of aluminum and aluminum alloys.
  • the present invention seeks to offer a conversion treatment solution which imparts an excellent corrosion resistance and paint adherence to the surface of aluminum and aluminum alloy prior to their being painted.
  • the conversion treatment solution of the present invention is an acidic treatment solution which contains complex fluoride ion, phosphate ion, hexavalent chromium, and fluoride ion as its essential components.
  • the complex fluoride ions are selected from fluosilicate (SiF6 ⁇ 2) ions, fluotitanate (TiF6 ⁇ 2), fluozirconate (ZrF6 ⁇ 2), and fluoborate (BF4 ⁇ 2) ions, and may be added in the form of fluosilicic acid, fluoboric acid, fluozirconic acid, fluotitanic acid, or any soluble salt thereof. Mixtures of these ions may also be used.
  • a range of 4.0 to 15.0 g/L is indicated for the fluosilicate ion. Values less than 4.0 g/L cannot normally generate good paint adherence, while values exceeding 15.0 g/L may cause substantial etching of an aluminum surface and prevent the formation of a satisfactory film.
  • a range of 0.5 to 3.0 g/L is indicated for the fluoborate ion. Values less than 0.5 g/L again cannot usually generate a good paint adherence, while values in excess of 3 0 g/L increase waste water pollution and are uneconomical.
  • a range of 2.0 to 8.0 g/L is indicated for fluozirconate ions, fluotitanate ions, or mixtures of these two ions. Concentrations of these two complex fluoride ions that are less than 2.0 g/L cannot usually generate good paint adherence, while concentrations exceeding 8.0 g/L cause substantial etching and usually prevent the formation of a satisfactory film.
  • Phosphoric acid is the preferred source for the phosphate ion, and the phosphoric acid content falls into the range of 5.0 to 40.0 g/L. When this value is less than 5.0 g/L, the resulting film will normally contain only small quantities of chromium phosphate and the paint adherence may be inadequate. While good films are formed at concentrations exceeding 40.0 g/L, the cost of the treatment solution is also increased and the economics become less favorable.
  • Chromic acid is the source for the hexavalent chromium, and the preferred chromic acid content is that which will result in a concentration of its stoichiometric equivalent as hexavalent chromium in the range from 1.0 to 4.0 g/L. Values less than 1 g/L result in an inferior corrosion resistance because a satisfactory conversion film is not formed. Values in excess of 4.0 g/L can cause increased pollution from and/or pollution abatement cost for waste water from the treatment solution and thus create environmental and economic problems.
  • the fluoride ion content is an important component for controlling the film growth rate of the conversion film.
  • the fluoride ion source may be, for example, hydrofluoric acid (HF), sodium fluoride (NaF), potassium fluoride (KF), and the like.
  • the fluoride ion concentration in the conversion solutions was determined as follows: An ion-selective electrode (Fluorine F-125 electrode, reference HS-305DP from Toa Denpa Kogyo Kabushiki Kaisha) and an ion meter (Type IM-40S from Toa Denpa Kogyo Kabushiki Kaisha) were used.
  • Standard solutions were prepared by adding a specified quantity of hydrofluoric acid (for example, 0.1 g/L, 1 g/L, or 10 g/L) to 5 g/L chromic acid and 15 g/L phosphoric acid and by adjusting the pH to 2.0 with phosphoric acid or sodium hydroxide.
  • the fluoride ion concentration was assumed to correspond to the total quantity of fluorine from hydrofluoric acid addition.
  • the meter readings obtained with these solutions of known fluoride ion concentration were then determined and plotted against the fluoride ion concentrations to generate a calibration curve.
  • the pH of the conversion solution itself was adjusted to 2.0 using phosphoric acid or sodium hydroxide and then measured using the fluorine ion meter, and the measured value was converted to the fluoride ion concentration by reference to the calibration curve.
  • the range for the fluoride ion concentration is 0.1 to 2.0 g/L. At values less than 0.1 g/L, the growth rate of the conversion film is slow, so that long treatment times must be used in order to obtain satisfactory conversion films and the productivity is therefore low. Rapid growth rates are encountered at values in excess of 2.0 g/L; this results in large film weights and an undesirable loss of the metallic luster of the workpiece. As a consequence, the concentration range is 0.1 to 2.0 g/L; the particularly preferred range is 0.4 to 1.0 g/L.
  • the pH of this conversion treatment solution is in the range of 1.0 to 3.0 and may conveniently be adjusted into that range through the use of an acid arbitrarily selected from acids such as phosphoric acid, nitric acid, and hydrochloric acid or a base arbitrarily selected from bases such as sodium hydroxide, ammonium hydroxide, and the like.
  • acids such as phosphoric acid, nitric acid, and hydrochloric acid
  • bases such as sodium hydroxide, ammonium hydroxide, and the like.
  • a pH below 1.0 causes substantial etching and therefore interferes with coat formation.
  • a pH in excess of 3.0 usually results in weak etching so that a uniform film cannot be formed.
  • the conversion treatment solution of the present invention can be used as a substitute for the currently widely used phosphoric acid/chromate treatment solutions.
  • a preliminary surface cleaning must usually be carried out when the conversion treatment solution of the present invention is used for the conversion treatment of the surface of aluminum or aluminum alloy.
  • the cleaning method in this case may consist of treatment with an acidic, alkaline, or solvent-based cleaning solution or some combination thereof.
  • the aluminum or aluminum alloy surface may be etched with alkali or acid after cleaning. Either immersion or spray treatment may be used as the method for treatment with solution according to the present invention.
  • the weight of the resulting conversion film is governed by such factors as the treatment temperature and treatment time.
  • the temperature of the treatment solution should preferably fall into the range from room temperature (about 20 degrees Centigrade) to 70 degrees Centigrade and more preferably falls into the range from 35 to 55 degrees Centigrade. Treatment times in the range of 1 to 90 seconds are preferred.
  • the conversion film weight is normally evaluated based on the deposition of chromium, and optionally zirconium, and/or titanium.
  • the quantity of deposition of each of the three metals, when present at all, preferably falls within the range of 5 to 50 mg/m2, and should be adjusted in accordance with the required degree of corrosion resistance.
  • the deposition of chromium, and optionally titanium, and/or zirconium can be controlled by suitably adjusting the treatment temperature and treatment time.
  • the conversion film formed by the conversion treatment solution according to the present invention when neither zirconium or titanium is present is believed to be chemically and physically similar to the film formed by phosphoric acid/chromate treatments, and is composed principally of hydrated chromium phosphate (CrPO4 ⁇ 4H2O).
  • the conversion film When either fluotitanate or fluozirconate is included in the treatment solution, the conversion film usually contains both hydrated chromium phosphate and zirconium oxide (ZrO2) and/or titanium oxide (TiO2).
  • the conversion treatment solution of the present invention is explained in greater detail below through the use of several illustrative examples.
  • the first group of examples are for solutions containing fluoborate or fluosilicate ions, and the effectiveness of such solutions relative to comparison examples is reported in Table 1.
  • the substrate for these examples was an aluminum/magnesium alloy (described in detail in Japanese Industrial Standard ⁇ hereinafter "JIS" ⁇ A5082).
  • JIS Japanese Industrial Standard
  • This aluminum alloy was degreased and conversion treated using a small sprayer designed to give spraying conditions identical to those currently encountered in typical spray treatments on commercial continuous conversion treatment lines for the conversion treatment of aluminum alloy coil.
  • Chromium content in the coating deposited by the conversion process was measured using a fluorescent X-ray analyzer (Model 3070E from Rigaku Denki Kogyo).
  • This conversion treated aluminum alloy sheet was then coated with a can end paint of a poly ⁇ vinyl chloride ⁇ type to give a paint film thickness of 12 to 14 micrometers, which was then baked at 200 degrees Centigrade for 10 minutes before the sheets were subjected to the other tests reported in Table 1.
  • Salt-spray testing was conducted in order to evaluate the corrosion resistance. Salt-spray testing was conducted in accordance with JIS Z-2371, and the value reported is the time required for the appearance of blistering at a cross form cut in the paint film on the painted test panel. Thus, longer times correspond to a better corrosion resistance. Spray times of 2000 hours or more are generally now rated as excellent.
  • the paint adherence was evaluated as follows The painted test sheet was cut into 5 x 150 millimeter (hereinafter "mm") size rectangular strips, which were then hot-press-bonded with polyamide film. The obtained test specimen was immersed in boiling deionized water for 3 hours, and the peel strength was then evaluated in a 180° peel test. High peel strength values correspond to a better paint adherence, and as a general rule a value of 3.0 kilograms of force (hereinafter "kgf") per 5 mm width is rated as excellent.
  • kgf 3.0 kilograms of force
  • Enamel feathering was evaluated in accordance with the Alcoa method, as described on page 49 of the Lecture Notes from the 73rd Fall Meeting of Keikinzoku Gakkai [Institute of Light Metals of Japan]. This evaluation is based on the maximum residual paint film width after peeling. Thus, smaller residual paint film widths correspond to a more desirable smaller amount of enamel feathering, and as a general rule residual widths not exceeding 0.5 mm are rated as excellent.
  • the surface of the aluminum alloy was cleaned by rinsing with a hot (70 degrees Centigrade) 4 % aqueous solution of a commercial strongly alkaline degreaser (FINE CLEANERTM 4418 from Nihon Parkerizing Company, Limited) and then with water. This was followed by spraying for 5 seconds with conversion treatment solution 1 heated to 50 degrees Centigrade, rinsing again with tap water, spraying with deionized water (specific resistance ⁇ 3,000,000 ohm-cm) for 10 seconds, and finally drying in a hot-air drying oven at 70 degrees Centigrade for 5 minutes. After drying, the conversion coated test panel was painted as described above, and the corrosion resistance, paint adherence, and enamel feathering were then evaluated.
  • FINE CLEANERTM 4418 commercial strongly alkaline degreaser
  • H2SiF6 7.4 g/L of SiF62 ⁇
  • H3PO4 75 phosphoric acid
  • CrO3 chromic acid
  • Cr6+ 3.0 g/L of Cr6+
  • HF hydrofluoric acid
  • NaBF4 sodium fluoborate
  • Example 1 This was identical to Example 1, except that the samples were spray treated for 10 seconds at 40 degrees Centigrade rather than for 5 seconds at 50 degrees Centigrade as in Example 1.
  • Example 1 This was identical to Example 1, except that the samples were spray treated for 10 seconds rather than for 5 seconds as in Example 1.
  • Example 1 The aluminum alloy was cleaned as in Example 1 and then spray-treated for 5 seconds with a 5 % aqueous solution of a commercial phosphoric acid/chromate treatment concentrate (ALCHROMTM K702 from Nihon Parkerizing Company, Limited) heated to 50 degrees Centigrade. After this treatment, it was rinsed with water, dried, and painted as in Example 1, and its performance was then evaluated.
  • ACHROMTM K702 commercial phosphoric acid/chromate treatment concentrate
  • Example 2 The aluminum alloy was cleaned as in Example 1 and then spray-treated for 30 seconds with a 2 % aqueous solution of a commercial non-chromate treatment concentrate (PARCOATTM K3761 from Nihon Parkerizing Company, Limited) heated to 50 degrees Centigrade. After this treatment, it was rinsed with water, dried, and painted as in Example 1, and its performance was then evaluated.
  • a commercial non-chromate treatment concentrate PARCOATTM K3761 from Nihon Parkerizing Company, Limited
  • Example 9 This was identical to Example 9, except that the samples were spray treated for 10 seconds at 40 degrees Centigrade rather than for 5 seconds at 50 degrees Centigrade as in Example 9.
  • Example 9 This was identical to Example 9, except that the samples were spray treated for 10 seconds rather than for 5 seconds as in Example 9.

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

Abstract

On améliore l'adhérence d'une peinture ainsi que la résistance à la corrosion de surfaces d'aluminium et de ses alliages, notamment lorsque l'on utilise une peinture à base de polyvinylchlorure, par l'emploi d'une solution de revêtement de conversion ayant un pH situé dans la plage comprise entre 1,0 et 3,0, et contenant: (A) une quantité d'ions phosphate stoïchiométriquement équivalente à au moins 5,0 g/L d'acide phosphorique; (B) au moins 1,0 g/L de chrome hexavalent; (C) au moins 0,1 g/L d'ions fluorure; et (D) un composant d'ions florure complexe sélectionné dans le groupe composé de: (i) au moins 4,0 g/L d'ions fluosilicate, (ii) au moins 0,5 g/L d'ions fluoborate, (iii) au moins 2,0 g/L d'ions fluozirconate, et (iv) au moins 2,0 g/L d'ions fluotitanate.

Claims (7)

  1. Une solution aqueuse de revêtement par conversion qui a un pH de 1,0 à 3,0 et est constituée essentiellement de :
    (A) une quantité d'ions phosphates qui est stoechiométriquement équivalente à 5,0 à 40,0 g/l d'acide phosphorique ;
    (B) 1,0 à 4,0 g/l de chrome hexavalent ;
    (C) 0,1 à 2,0 g/l d'ions fluorures ; et
    (D) un composant ion fluorure complexe choisi dans le groupe constitué par :
    (i) 4,0 à 15,0 g/l d'ions fluosilicates,
    (ii) 0,5 à 3,0 g/l d'ions fluoborates,
    (iii) 2,0 à 8,0 g/l d'ions fluozirconates et
    (iv) 2,0 à 8,0 g/l d'ions fluotitanates.
  2. Une solution aqueuse selon la revendication 1, caractérisée en ce qu'elle comprend de 0,4 à 1,0 g/l d'ions fluorures.
  3. Un procédé pour le traitement d'une surface d'aluminium ou d'alliage d'aluminium, ledit procédé comprenant les étapes de formation d'un revêtement par conversion sur ladite surface, puis de recouvrement de la surface revêtue par conversion avec un revêtement protecteur, caractérisé en ce que le revêtement par conversion sur ladite surface est formé par contact de ladite surface avec une solution aqueuse ayant un pH de 1,0 à 3,0 et constituée essentiellement de :
    (A) une quantité d'ions phosphates qui est stoechiométriquement équivalentes à 5,0 à 40,0 g/l d'acide phosphorique ;
    (B) 1,0 à 4,0 g/l de chrome hexavalent ;
    (C) 0,1 à 2,0 g/l d'ions fluorures ; et
    (D) un composant ion fluorure complexe choisi dans le groupe constitué par :
    (i) 4,0 à 15,0 g/l d'ions fluosilicates,
    (ii) 0,5 à 3,0 g/l d'ions fluoborates,
    (iii) 2,0 à 8,0 g/l d'ions fluozirconates, et
    (iv) 2,0 à 8,0 g/l d'ions fluotitanates.
  4. Un procédé selon la revendication 3, caractérisée en ce que ladites solution aqueuse comprend de 0,4 à 1,0 g/l d'ions fluorures.
  5. Un procédé selon la revendication 4, caractérisée en ce que le revêtement formé par conversion contient des atomes de chrome et facultativement de zirconium et/ou de titane, respectivement en une quantité de 5 à 50 milligrammes par mètre carré.
  6. Un procédé selon la revendication 3, 4 ou 5, caractérisé en ce que le revêtement par conversion est réalisé à une température dans la gamme de 20 à 70°C.
  7. Un procédé selon la revendication 6, caractérisé en ce que le revêtement par conversion est réalisé à une température dans la gamme de 35 à 55°C pour une durée de contact dans la gamme de 1 à 90 secondes.
EP91904950A 1990-02-21 1991-02-13 Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium Expired - Lifetime EP0516700B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP40169/90 1990-02-21
JP2040168A JPH07100872B2 (ja) 1990-02-21 1990-02-21 アルミニウムおよびアルミニウム合金用化成処理液
JP40168/90 1990-02-21
JP4016990A JPH0747828B2 (ja) 1990-02-21 1990-02-21 アルミニウムおよびアルミニウム合金用化成処理液
PCT/US1991/000965 WO1991013186A1 (fr) 1990-02-21 1991-02-13 Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium

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EP0516700A1 EP0516700A1 (fr) 1992-12-09
EP0516700B1 true EP0516700B1 (fr) 1994-07-27

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EP (1) EP0516700B1 (fr)
AU (1) AU642478B2 (fr)
BR (1) BR9106049A (fr)
CA (1) CA2072592A1 (fr)
DE (1) DE69103139T2 (fr)
WO (1) WO1991013186A1 (fr)

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JP3181658B2 (ja) * 1992-01-13 2001-07-03 日本パーカライジング株式会社 金属材料の酸性化成処理における有効フッ素濃度の定量方法
US5454882A (en) * 1992-01-13 1995-10-03 Henkel Corporation Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal
US6833328B1 (en) 2000-06-09 2004-12-21 General Electric Company Method for removing a coating from a substrate, and related compositions
US6863738B2 (en) 2001-01-29 2005-03-08 General Electric Company Method for removing oxides and coatings from a substrate
KR100697354B1 (ko) 2001-12-04 2007-03-20 신닛뽄세이테쯔 카부시키카이샤 금속 산화물 및/또는 금속 수산화물 피복 금속재료와 그제조방법
US6953533B2 (en) 2003-06-16 2005-10-11 General Electric Company Process for removing chromide coatings from metal substrates, and related compositions
MX2017013713A (es) 2015-05-01 2018-03-02 Novelis Inc Proceso continuo de tratamiento previo de bobinas.
CN109440096B (zh) * 2018-10-23 2021-02-09 武汉材料保护研究所有限公司 一种铝合金表面纳米复合化学转化膜的制备方法
CN113862652A (zh) * 2021-09-06 2021-12-31 广东致卓环保科技有限公司 用于车用压铸铝合金前处理的无铬钝化液及其使用工艺

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WO1991013186A1 (fr) 1991-09-05
DE69103139T2 (de) 1995-02-02
EP0516700A1 (fr) 1992-12-09
AU642478B2 (en) 1993-10-21
AU7337091A (en) 1991-09-18
BR9106049A (pt) 1992-11-17
CA2072592A1 (fr) 1991-08-22
DE69103139D1 (de) 1994-09-01

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