WO1993001332A1 - Procede et composition acide permettant de nettoyer l'aluminium - Google Patents

Procede et composition acide permettant de nettoyer l'aluminium Download PDF

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Publication number
WO1993001332A1
WO1993001332A1 PCT/US1992/005448 US9205448W WO9301332A1 WO 1993001332 A1 WO1993001332 A1 WO 1993001332A1 US 9205448 W US9205448 W US 9205448W WO 9301332 A1 WO9301332 A1 WO 9301332A1
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WO
WIPO (PCT)
Prior art keywords
ion
ions
cleaning
aluminum
acidic aqueous
Prior art date
Application number
PCT/US1992/005448
Other languages
English (en)
Inventor
Wataru Ishibashi
Yasuo Iino
Shinichiro Asai
Original Assignee
Henkel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corporation filed Critical Henkel Corporation
Publication of WO1993001332A1 publication Critical patent/WO1993001332A1/fr

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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • the present invention relates to an acidic cleaning composition, also called a bath for brevity, and a cleaning method for use to obtain an optimal etching and cleaning of the surface of aluminum and aluminum alloys that are at least 65 percent by weight aluminum (pure aluminum and its alloys hereinafter being jointly designated by the simple term "aluminum” unless the context implies otherwise) in the form of sheets, cans, containers, and the like.
  • an acidic cleaning composition also called a bath for brevity
  • a cleaning method for use to obtain an optimal etching and cleaning of the surface of aluminum and aluminum alloys that are at least 65 percent by weight aluminum (pure aluminum and its alloys hereinafter being jointly designated by the simple term "aluminum" unless the context implies otherwise) in the form of sheets, cans, containers, and the like.
  • a process lubricating oil is normally used when aluminum sheet is formed into, for example, beverage containers by the drawing and ironing forming process (DI process) , lubricating oil and aluminum fines smut will usu- ally adhere to the aluminum surface.
  • a cleaning bath is employed in order to remove these contaminants and provide a clean aluminum surface.
  • Chromic acid-based and hydrofluoric acid-based clean ⁇ ing agents have been widely, employed for. removal of the lubricating oil and smut thus deposited on the surface of aluminum.
  • chromic acid systems and hydrofluoric acid-based compounds are toxic, which necessitates waste water treatment facilities in order to meet the require ⁇ ments for maintaining the working and general environments. Since the costs of these waste water treatment facilities make a substantial contribution to product cost, the art has been witness to the development of non-chromium, non- fluorine cleaners for the surface of aluminum.
  • Japanese Patent Application Laid Open [Kokai or Unexamined] Numbers 61-106783 [106,783/86] and 61-231188 [231,188/86] teach that an entirely satisfactory surface cleaning can be achieved using an aluminum surface cleaner comprising ferric ion in an acidic aqueous solution with pH adjusted to ⁇ 2 by sulfuric acid and/or nitric acid. It is reported that the ferric ion acts to promote the aluminum etching activity of the sulfuric acid and nitric acid.
  • Japanese Patent Publication Number 52-22330 also describes the activity of ferric ion, although in relation to a fluorine-containing cleaning bath for the surface of aluminum.
  • ferric ion when ferric ion is absent, the aluminum etch rate is high in the presence of a high fluorine ion titer.
  • ferric ion when ferric ion is present, the etch rate due to the fluorine ion is inhib ⁇ ited, and a suitable etch rate by, e.g., sulfuric acid, is obtained. This results in a satisfactory surface cleaning.
  • microparticulate mercury metal provides a suitable etching activity in acidic aqueous so ⁇ lution with pH adjusted to ⁇ 2 by sulfuric acid or by a combination of sulfuric acid and dilute nitric acid.
  • the same effect was also confirmed for the oxidized diphenyl ⁇ amine ion, oxidized diphenylbenzidine ion, oxidized diphen ⁇ ylamine sulfonate ion, and oxidized diphenylbenzidine sulfonate ion.
  • the aforesaid compounds and elements that exhibit a satisfactory etching effect for aluminum have a standard redox potential at 25° C of + 0.77 + 0.09 volt against the standard hydrogen electrode.
  • the present invention was achieved based on this discovery that elements or compounds with a potential in this range provide a suitable aluminum etching activity in acidic aqueous solution with pH ad ⁇ justed to ⁇ 2 by sulfuric acid or sulfuric acid and dilute nitric acid.
  • the toxicity of mercury militates against its use in practical applications, but organic redox agents such as the oxidized diphenylamine ion, oxidized diphenyl ⁇ benzidine ion, oxidized diphenylamine sulfonate ion, and oxidized diphenylbenzidine sulfonate ion can be employed in this application individually or in a mixture.
  • ferric ion can be employed in combination with said oxidized diphenylamine ion or other compounds mentioned.
  • the quantity of ferric ion used should be very small in order to avoid reducing the surfactant concentra ⁇ tion.
  • the color of the cleaning agent bath converts from violet to colorless at a redox potential in the vicinity of +0.76 V in the case of oxidized diphen ⁇ ylamine ion or oxidized diphenylbenzidine ion.
  • Management of the efficacy of the cleaning agent by direct measurement of the redox potential is thereby rendered unnecessary, and bath management can be characteristically executed based on the color-conversion point.
  • the violet color is retained as long as nitric acid remains.
  • the color-conversion potential for diphenylamine sulfonate is +0.83 V. Since its oxidized form is violet and its reduced form is colorless, the surface cleaning bath can also be managed in this case by monitoring the color-conversion point.
  • the present invention relates to an aluminum surface cleaning agent which characteristically comprises a chromate free, fluor ⁇ ide free acidic aqueous solution with pH ⁇ 2, containing sulfuric acid, or a mixed acid of sulfuric acid and dilute nitric acid, that also contains 0.5 to 5 g/L of an organic redox agent selected from the group consisting of oxidized diphenylamine ion, oxidized diphenylbenzidine ion, oxidized diphenylamine sulfonate ion, oxidized diphenylbenzidine sulfonate ion, and mixtures of any two or more of these.
  • the content of the organic redox agent is preferably kept within the aforementioned range because a satisfactory effect is not usually obtained at less than 0.5 g/L, while exceeding 5 g/L is problematic in terms of economic effi- ciency and solubility.
  • the aluminum surface cleaner may also contain 0.05 to 0.5 g/L ferric ion.
  • the basis for this preferred range is that no acceleration of aluminum etching is obtained at below 0.05 g/L ferric ion while exceeding 0.5 g/L ferric ion causes problems such as sludge generation and a reduction in the surfactant concentration.
  • the cleaning agent according to the present invention may contain non- ionic, cationic, anionic, and/or amphoteric surfactant(s) , preferably within the concentration range of 0.1 to 10 g/L. Concentrations within the range of 0.5 to 2 g/L are used most frequently.
  • the temperature of the treatment bath should preferably fall within the range from room tempera ⁇ ture to 80° C, and the range from 60 to 75 ° c is generally more preferred.
  • the treatment time, both for immersion and spray, preferably should be 10 to 120 seconds, while the range of 50 to 60 seconds is generally most preferred.
  • the.sulfuric acid bath converts from violet to colorless and the nitric acid-containing bath also converts from violet to color- less.
  • the color converts from red-violet to colorless in the case of diphenylamine sulfonate. This conversion to an almost colorless condition indicates that the organic redox agent can no longer fulfill its function.
  • At least one species of oxidant selected from hydrogen per- oxide, nitrite ion, peroxysulfate ion, metavanadate ion, and cerium ion, all of which can oxidize the reduced forms of the preferred organic potential controlling redox ag ⁇ ent(s) used, is preferably added in order to restore the color.
  • a preferred aluminum cleaning method accord- ing to the present invention is characterized in that, at the point at which the color of said cleaning bath has been extinguished or almost extinguished, there is added thereto at least one species of oxidant selected from the group comprising hydrogen peroxide, nitrite ion, peroxysulfate ion, metavanadate ion, and cerium ion, in sufficient amount to restore the color, and cleaning is subsequently contin ⁇ ued.
  • the color of the cleaning bath can be quite easily and unambiguously determined by visually comparing and compar ⁇ ing a sample taken from the bath against a standard solu ⁇ tion prepared in advance.
  • A3004 aluminum alloy sheet was Dl-processed to afford aluminum can body (can container without lid) car ⁇ rying lubricant oil and smut, and this was submitted to testing.
  • the stock solutions for preparation of the aforesaid cleaning baths were 94.0 % sulfuric acid (containing 17.6 moles/liter ⁇ "mol/L" ⁇ of H 2 S0 4 ) , 69.0 % nitric acid (15.4 mol/L of HN0 3 ) , and 35.0 % hydrogen peroxide.
  • the diphen ⁇ ylamine was used in the form of 5 g dissolved in 90 g of sulfuric acid.
  • the iron was brought to 0.2 g/L by the addition of 3.6 mL 20 % aque ⁇ ous ferric sulfate solution.
  • Nonionic surfactant in the concentration range of 1 g/L was used in the cleaning agent samples A, B, C, and D reported in Table 1.
  • the following, for example, were used as the surfactant: hydrocarbon derivatives, abietic acid derivatives, ethoxylated primary alcohol, and modified pol- yethoxylated alcohol.
  • the can container comprising the test specimen was cleaned by spraying with the particular cleaning agent for 60 seconds at a treatment temperature of 60 to 70 ° C. This was followed by a 15 second spray with tap water at ambient temperature, then a 5 second spray with deionized water, and finally drying in a current of hot air at 95° C. Evaluation of the cleaning performance
  • the treatment solutions of the present invention are free of both the chromium ions and fluoride ions that pollute the working and general environments. Furthermore, they remove the lubricating oil and aluminum smut adhering on the sur ⁇ face of the aluminum, thus providing a cleaning effect which positively supports conversion treatments and coating operations. Moreover, an entirely satisfactory cleaning of the surface of aluminum is achieved even when iron ions, which can degrade surfactant in the presence of hydrogen peroxide, are not present in the aluminum surface cleaning bath. Finally, the acid wash can be managed with increased accuracy due to the simplicity with which the need for re ⁇ plenishment of the oxidant in the acidic cleaning bath can be monitored by observing the loss of color in the bath.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Bain de nettoyage acide servant à nettoyer l'aluminium ne contenant pas d'ions chrome ou de fluorure de chrome mais présentant cependant une excellente performance d'attaque sans utiliser d'ions ferriques ou en utilisant seulement une faible quantité d'ions ferriques. Ce bain contient de l'acide sulfurique ou de l'acide sulfurique plus de l'acide nitrique, et de 0,5 à 5 g/L d'une ou plusieurs espèces de produits d'oxydation d'ions sélectionnés entre des ions diphénylamine, des ions diphénylbenzidine oxydée, des ions sulfonate de diphénylamine oxydé, et des ions sulfonate de diphénylbenzidine oxydé. L'indication du moment où l'agent d'oxydation doit être régénéré est fournie par la décoloration du bain initial et par conséquent l'entretien du bain est particulièrement facile.
PCT/US1992/005448 1991-07-04 1992-07-02 Procede et composition acide permettant de nettoyer l'aluminium WO1993001332A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3189496A JPH059765A (ja) 1991-07-04 1991-07-04 アルミニウム用酸性洗浄液及び洗浄方法
JP3/189496 1991-07-04

Publications (1)

Publication Number Publication Date
WO1993001332A1 true WO1993001332A1 (fr) 1993-01-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/005448 WO1993001332A1 (fr) 1991-07-04 1992-07-02 Procede et composition acide permettant de nettoyer l'aluminium

Country Status (5)

Country Link
JP (1) JPH059765A (fr)
AU (1) AU2297492A (fr)
MX (1) MX9203934A (fr)
WO (1) WO1993001332A1 (fr)
ZA (1) ZA924936B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514293A (en) * 1993-03-26 1996-05-07 Nippon Paint Co., Ltd. Acidic cleaning aqueous solution for aluminum and aluminum alloy and process for cleaning the same
EP0714456A1 (fr) * 1993-07-09 1996-06-05 Henkel Corp Compose et procede de decrassage/desoxydation sans reencrassage
EP1126048A2 (fr) * 2000-02-15 2001-08-22 Nippon Paint Co., Ltd. Procédé de décapage d'aluminium
FR2941241A1 (fr) * 2009-01-22 2010-07-23 Airbus France Procede et solution de decapage sans chrome hexavalent d'une surface en aluminium ou en alliage d'aluminium et procede de traitement comprenant au moins une etape de decapage par ce procede.
US11807942B2 (en) 2015-05-01 2023-11-07 Novelis Inc. Continuous coil pretreatment process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0741972A (ja) * 1993-07-26 1995-02-10 Nippon Paint Co Ltd アルミニウム系金属の酸性洗浄水溶液
JP4757042B2 (ja) * 2006-01-26 2011-08-24 日本ペイント株式会社 アルミニウム系金属材料用酸性洗浄剤及びその洗浄方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0196668A1 (fr) * 1985-04-04 1986-10-08 Nippon Paint Co., Ltd. Méthode de contrôle d'une composition de nettoyage d'une surface d'aluminium
EP0241415A1 (fr) * 1986-03-25 1987-10-14 Sandoz Ag Electrolyte acide comportant de l'étain (II)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0196668A1 (fr) * 1985-04-04 1986-10-08 Nippon Paint Co., Ltd. Méthode de contrôle d'une composition de nettoyage d'une surface d'aluminium
EP0241415A1 (fr) * 1986-03-25 1987-10-14 Sandoz Ag Electrolyte acide comportant de l'étain (II)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514293A (en) * 1993-03-26 1996-05-07 Nippon Paint Co., Ltd. Acidic cleaning aqueous solution for aluminum and aluminum alloy and process for cleaning the same
EP0714456A1 (fr) * 1993-07-09 1996-06-05 Henkel Corp Compose et procede de decrassage/desoxydation sans reencrassage
EP0714456A4 (fr) * 1993-07-09 1996-06-12
EP1126048A2 (fr) * 2000-02-15 2001-08-22 Nippon Paint Co., Ltd. Procédé de décapage d'aluminium
EP1126048A3 (fr) * 2000-02-15 2003-05-02 Nippon Paint Co., Ltd. Procédé de décapage d'aluminium
FR2941241A1 (fr) * 2009-01-22 2010-07-23 Airbus France Procede et solution de decapage sans chrome hexavalent d'une surface en aluminium ou en alliage d'aluminium et procede de traitement comprenant au moins une etape de decapage par ce procede.
US11807942B2 (en) 2015-05-01 2023-11-07 Novelis Inc. Continuous coil pretreatment process

Also Published As

Publication number Publication date
AU2297492A (en) 1993-02-11
JPH059765A (ja) 1993-01-19
MX9203934A (es) 1993-01-29
ZA924936B (en) 1993-04-28

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