EP0351771B1 - Système de nettoyage/désoxydation sans chrome - Google Patents

Système de nettoyage/désoxydation sans chrome Download PDF

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Publication number
EP0351771B1
EP0351771B1 EP89113143A EP89113143A EP0351771B1 EP 0351771 B1 EP0351771 B1 EP 0351771B1 EP 89113143 A EP89113143 A EP 89113143A EP 89113143 A EP89113143 A EP 89113143A EP 0351771 B1 EP0351771 B1 EP 0351771B1
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EP
European Patent Office
Prior art keywords
solution
hydrogen peroxide
aluminum
cleaning
deoxidizing
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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.)
Expired - Lifetime
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EP89113143A
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German (de)
English (en)
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EP0351771A1 (fr
Inventor
Mark W. Mcmillen
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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
    • 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

  • This invention relates to a novel process for cleaning and deoxidizing aluminum prior to conversion treatment.
  • the process is based on an acid or alkaline cleaning system and a chromate-free deoxidizer system.
  • chromated deoxidizers have been used to enable aluminum samples to pass designated corrosion tests, as for example, MIL-C-5541C.
  • the aluminum is first-cleaned in a relatively non-etching alkaline soak cleaner, deoxidized in an acidic chromate solution and subsequently chromated.
  • an alkaline etch or alkaline chemical milling solution was used. This step was followed by a deoxidation step which usually employed a chromated deoxidizer, to remove "smut" produced by etching.
  • the aluminum was then chromated.
  • attempts to replace chromate in the deoxidizing step have generally involved the use of iron salts such as ferric sulfate.
  • iron based deoxidizers have never provided results equal to the chromate containing deoxidizer systems.
  • U.S. Patent 4,451,304 to Batiuk provides a treatment for aluminum which employs an alkaline cleaning step and a deoxidizer step.
  • the deoxidizer step employs a non-chromate deoxidizer which is an aqueous solution of sodium or potassium nitrite.
  • This patent includes a detailed discussion of the prior art in this area.
  • US-A-4 459 216 discloses an aqueous acidic dissolving solution for metals: e.g. aluminum and aluminum alloys comprising hydrogen peroxide, an inorganic acid, and at least one aromatic compound, said solution can be used at a temperature of from 10 to 80°C and for a treating time of from 5 sec. to 15 min.
  • metals e.g. aluminum and aluminum alloys comprising hydrogen peroxide, an inorganic acid, and at least one aromatic compound
  • GB-A-2 186 292 describes a process for cleaning aluminum surfaces employing:
  • GB-A-2100 757 is related to a fluoride-free, low-temperature solution for cleaning aluminum comprising sulfuric acid, phosphoric acid and surfactants.
  • the present invention is advantageous in that it eliminates the use of hexavalent chromium in the cleaning and deoxidizing step and further provides enhanced performance over previously disclosed non-chromium processes for the cleaning and deoxidizing of aluminum prior to chemical conversion treatments.
  • aluminum is cleaned in an aqueous acidic or alkaline solution.
  • the preferred acidulants are acids such as sulfuric acid, mitric acid, hydrofluoric acid, phosphoric acid, citric acid, oxalic acid, acetic acid, gluconic acid, hydroxyacetic acid and the like or mixtures of two or more such acids.
  • the acidic solution is a dilute solution which provides low etching.
  • the alkaline cleaning solutions useful in the present invention generally contain alkali metal hydroxides or other water soluble alkaline materials such as trisodium phosphate, alkali silicates, tetrasodium pyrophosphate and the like.
  • the etchants can also comprise acidic solutions of fluoride compositions such as hydrogen fluoride and fluoride salts, fluoride complexes and the like, such as ammonium bifluoride, fluorosilicic acid, fluorophosphonic acid, its salts, and the like.
  • fluoride compositions such as hydrogen fluoride and fluoride salts, fluoride complexes and the like, such as ammonium bifluoride, fluorosilicic acid, fluorophosphonic acid, its salts, and the like.
  • the aluminum is then immersed in an aqueous acidic deoxidizer solution containing at least one of the following deoxidizer compositions hydrogen peroxide or heteropoly vanadic acids or its salts.
  • the aluminum can be rinsed before contact with the deoxidizer solution. The use of a rinse is preferred.
  • the aluminum article can be cleaned and deoxidized in a single step by including a deoxidizer compound such as hydrogen peroxide in the acid cleaning solution.
  • a deoxidizer compound such as hydrogen peroxide
  • the term "aluminum" used in connection with the substrate metal to be treated includes aluminum metal per se and also those aluminum alloys which are generally subjected to a cleaning and deoxidizing treatment prior to chromating or other chemical or electrochemical conversion treatment.
  • impurity metals are copper, manganese, nickel, zinc, titanium, vanadium, sodium and gallium.
  • Aluminum alloys generally contain larger amounts of other metals.
  • Such alloying metals include silicon, chromium, lead, iron, copper, magnesium, manganese, and zinc.
  • Such metals in the form of ions as well as aluminum ions invariably are present in the deoxidizer solutions by virtue of the action of such solutions on the metal and smut. It is one aspect of the present invention that the deoxidizer solutions containing stabilizers can continue to function in the presence of such other metal ions, particularly iron, copper and manganese.
  • the multivalent metal ions tend to catalyze the decomposition of the hydrogen peroxide component. This is especially true with copper and manganese.
  • the aluminum substrate is subjected to cleaning and/or etching preferably with a dilute aqueous acidic solution at a pH of less than 2.
  • the pH is below 2 and most preferably below 1.5.
  • the cleaning solutions generally contain from 0.005% to 5% by volume or 10% by weight of the acids but can contain up to 50% by weight, and preferably from 0.2 to 8% by weight and more preferably from 0.4% to 2.5% by volume. It is also preferred to employ a mixture of acids such as sulfuric acid and hydrofluoric acid.
  • suitable surfactants can be included in the cleaning solutions. They can be used in amounts of from 0% to 5% by weight, and preferably up to 2% and most preferably up to 0.5% by weight. Any suitable surfactants which are compatible with the cleaning solution and do not leave an undesirable film on the aluminum's surface can be used. Such surfactants include the cationic, anionic, amphoteric and nonionic surfactants.
  • the cleaning and/or etching step can be done in an alkaline cleaner etching solution.
  • alkaline cleaning solutions which contain alkali metal hydroxide, alkali metal carbonate, trialkali metal phosphate (such as trisodium phosphate) tetralkali metal pyrophosphate (tetrasodium pyrophosphate) alkali metal silicates, alone or in combination can also be used in the cleaning step of the present invention.
  • Alkaline cleaning compositious such as Ridoline® 53, P3 Almeco® 18 and Ridoline® 322 can be used in the cleaning step.
  • an acid cleaning-etching step can be combined with the deoxidizer step by including hydrogen peroxide and a hydrogen peroxide stabilizer with an acid cleaning solution.
  • the combined cleaning and deoxidizing steps can be carried out at a temperature of from ambient to 76,6°C (170°F) and preferably from 32,2°C (90°F) to 65,5°C (150°F).
  • the pH of the solution is preferably below 3 and more preferably below 1.5 and most preferably below 0.5.
  • the cleaning-etching step can be conducted in a short period of time with substantially little etching or can be continued for a longer period of time if a deeply etched surface is desired.
  • the cleaning-etching step can be conducted at ambient temperatures but it is preferred to conduct the cleaning step at elevated solution temperatures. Higher temperatures increase the rate of cleaning and/or etching action of the cleaner solution and a certain degree of care must be exercised to ensure that the desired degree of cleaning or etch is obtained.
  • the temperature of the cleaning/etching solution is preferably from 32,2°C (90°F) to 79,4°C (175°F) and most preferably from 37,7°C (100°F) to 65,5°C (150°F).
  • the deoxidizer bath be acidic and preferably be below a pH of 4, and more preferably at or below 2.
  • the heteroploy ions can be added to the bath as such or can be generated in situ from their components.
  • the deoxidizer comprises from 0.1 gram/liter to the solubility limit of the material and an acid to form a composition having a pH below 3.
  • mineral acids are used and nitric acid is preferred.
  • the solutions contain from 0.03 to 30% by weight hydrogen peroxide and it is further preferred that one or more stabilizers for hydrogen peroxide also be employed in the solution.
  • the pH is also preferable to adjust the pH to 3 or less and preferably with nitric acid.
  • the pH is preferably not greater than 1.5 and most preferably 0.5 or below.
  • the deoxidizer solution is preferably maintained at a temperature from ambient to 65,5°C (150°F) depending on the time the aluminum article is in contact with the solution.
  • the aluminum article preferably is in contact with the deoxidizer solution from 1 to 25 minutes.
  • the contact time is generally shorter at higher temperatures.
  • Stabilizers for peroxides are well known and are exemplified in U.S. Patent 4,059,678.
  • Other suitable stabilizers for hydrogen peroxide are well known in the art and any of these can be conveniently used provided they are compatible with acidic solutions.
  • a preferred group of stabilizers is disclosed in U.S. Patent Application Serial No. 07/221,063 filed on July 19, 1988, in the name of Mark McMillen and entitled "Stabilization of Peroxide Solutions corresponding to EP 0351 772 A1.
  • the treated aluminum substrate is then chromated by chromating treatments for aluminum, which are well known in the art. Chromating with chromating compositions such Alodine® 1200S or Alodine® 600 product of Parker + Amchem a division of Henkel Corporation are useful.
  • the aluminum substrates are preferably rinsed before being treated with the chromating compositions. Rinsing is preferred to reduce contamination of the chromating composition with the components of the deoxidizing treatment composition.
  • a cleaning solution was prepared as follows:
  • Panels of aluminum alloy 2024-T3 were immersed in the cleaning solution at a temperature of 48,8°C (120°F) for a period of ten minutes. The panels were then removed, rinsed with deionized water and immersed in the deoxidizer solution at ambient temperature for 15 minutes. The panels were rinsed and subsequently chromated. The chromated panels successfully passed MIL-C-5541C test for neutral salt spray specifications.
  • the MIL-C-5541C specification and test methods are incorporated herein by reference.
  • a cleaner solution concentrate was prepared by blending 100 ml of 96% sulfuric acid and 416 ml of 75% phosphoric acid and diluting to one liter.
  • a cleaner solution was prepared by mixing 140 ml of cleaner solution and 70 ml of hydrofluoric acid solution concentrate as prepared in Example 1 and diluting to 7 liters.
  • the deoxidizer solution used in this example was identical to that used in Example 1.
  • Panels of aluminum alloy, 2024-T3 were immersed in the above cleaning solution at a temperature of 48,8°C (120°F) for a period of 10 minutes. Thereafter the panels were removed, rinsed with water and immersed in the deoxidizer solution at ambient temperatures for a period of 15 minutes. Thereafter, the panels were rinsed and chromated. These panels passed the MIL-C-5541C neutral salt spray specifications.
  • a cleaner concentrate solution was prepared by blending 256 ml of 96% sulfuric acid, 90 grams of Mirawet® B (amphoteric surfactant), 90 grams of Surfonic® LF-17 (ethoxylated alcohol) and diluting to one liter with water.
  • 40 milliliters of the hydrofluoric concentrate were added.
  • 21 milliliters of the hydrofluoric concentrate were added, and in respect to the 0.009%, 2 milliliters of the hydrofluoric acid concentrate were added.
  • a 4 liter deoxidizer bath was prepared in a manner similar to that of Examples 1 above.
  • the ingredients employed in the deoxidizer baths are set forth in Tables I and II below.
  • cleaning solution contains 0.3% by volume sulfuric acid (96%), 0.17% by volume hydrofluoric acid (70%), and up to 0.2% by volume sodium 2-ethyl hexyl sulfate surfactant for a strong etch cleaner.
  • This cleaner should be used for 5-10 minutes at temperatures of from about 43,3°C (110°F) to about 54,4°C (130°F).
  • the aluminum panels prefferably to a deoxidiziang step for about 10-15 minutes by immersion in a deoxidizing bath of preferrably 8% by volume hydrogen peroxide (35%), 3% by volume (42°Bé) nitric acid and up to 0.5% of a stabilizer for the peroxide (preferrably MIRATAINE® CBS (cocoamidopropyl hydroxy sultaine).
  • a deoxidizing bath of preferrably 8% by volume hydrogen peroxide (35%), 3% by volume (42°Bé) nitric acid and up to 0.5% of a stabilizer for the peroxide (preferrably MIRATAINE® CBS (cocoamidopropyl hydroxy sultaine).
  • a cleaning solution of 0.5% by volume sulfuric acid (96%), 1.7% phosphoric acid by volume (75%), and up to 0.2% of a surfactant combination which is a mixture of Triton® N-100 and Surfonic® LF-17. This is used at a temperature of from about 24,1°C (110°F) to about 60°C (140°F) for 5 to 10 minutes followed by the same deoxidizer step as established above for from about 5 to 15 minutes.
  • a cleaner-etching-deoxidizer bath was prepared containing 8% H2O2, 2.5% HNO3, 1.5% phosphoric acid and 2 ml/liter of Triton® X-102 surfactant (octylphenoxy polyethoxy ethanol).
  • Aluminum panels were immersed in the cleaning-etching deoxidizer solution for 10 minutes at 48,8°C (120°F). The panels were rinsed and then chromated in an Alodine® 1200S chromating solution according to manufacturer's recommendations. The chromated panels were then tested in neutral salt spray for 336 hours. There was no pitting or corrosion of the aluminum panels.
  • a cleaner-etching-deoxidizer bath was prepared containing 8% H2O2, 2.5% HNO3, 1 ml/liter of 79% HBF4 and 2 ml/liter Triton® X-102 surfactant.
  • Aluminum panels were immersed in the cleaner-etching-deoxidizer solution for 10 minutes at 48,8°C (120°F). The panels were rinsed and then chromated in an Alodine® 1200S solution according to manufacturer's recommendations. The chromated panels were then tested in neutral salt spray for 336 hours. There was no pitting or corrosion of the aluminum panels.
  • the combining of the acid cleaning-etch step with the deoxidizer step into one treating step is an advance in the art.
  • the combining of two steps into a single step reduces the equipment necessary to provide a commercial process and in addition reduces the processing time for each aluminum piece.

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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)
  • Detergent Compositions (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photoreceptors In Electrophotography (AREA)

Claims (21)

  1. Procédé pour le traitement d'un article en aluminium qui comprend les étapes consistant à : nettoyer, désoxyder et revêtir par conversion l'article en aluminium, caractérisé par le fait de désoxyder l'article en aluminium par mise en contact de celui-ci avec une solution de peroxyde d'hydrogène acide stabilisée, une solution d'acide vanadique hétéropolaire acide ou une solution de sel d'acide vanadique hétéropolaire acide.
  2. Procédé selon la revendication 1, dans lequel la valeur de pH de la solution de peroxyde d'hydrogène stabilisée acide est inférieure à 3.
  3. Procédé selon la revendication 1, dans lequel l'article en aluminium est nettoyé par mise en contact avec une solution de nettoyage alcaline.
  4. Procédé selon la revendication 3, dans lequel la solution de nettoyage est à une température allant de 32°C (90°F) jusqu'à 80°C (175°F).
  5. Procédé selon la revendication 3, dans lequel la solution désoxydante est une solution de peroxyde d'hydrogène stabilisée à une température allant de la température ambiante jusqu'à 65°C (150°F) et à une valeur de pH inférieure à 3.
  6. Procédé selon la revendication 5, dans lequel la valeur de pH est inférieure à 0,5.
  7. Procédé selon la revendication 1, dans lequel l'article en aluminium est nettoyé par mise en contact avec une solution acide aqueuse à une valeur de pH inférieure à 2.
  8. Procédé selon la revendication 7, dans lequel l'article en aluminium, après mise en contact avec la solution de nettoyage acide, est mis en contact avec une solution de peroxyde d'hydrogène stabilisée à une valeur de pH inférieure à 1,5.
  9. Procédé selon la revendication 8, dans lequel la valeur de pH de la solution désoxydante de peroxyde d'hydrogène stabilisée est inférieure à 0,5.
  10. Procédé selon la revendication 7, qui comprend les étapes consistant à :
    a. mettre en contact un article en aluminium avec une solution acide à une température allant de 32°C (90°F) jusqu'à 80°C (175°F) à une valeur de pH inférieure à 2 pendant 1 à 15 minutes pour nettoyer l'article en aluminium ; et
    b. mettre en contact l'article en aluminium nettoyé avec une solution de peroxyde d'hydrogène stabilisée acide à une température allant d'environ la température ambiante jusqu'à 65°C (150°F) pendant 1 à 25 minutes pour désoxyder l'article en aluminium.
  11. Procédé en deux étapes selon la revendication 1, dans lequel l'étape combinée de nettoyage et de désoxydation comprend : la mise en contact d'un article en aluminium avec une solution de peroxyde d'hydrogène stabilisée acide nettoyante-décapante-désoxydante à une température allant de 32°C (90°F) jusqu'à 80°C (175°F) pendant de 2 à 25 minutes, dans lequel la valeur de pH de la solution est inférieure à 2.
  12. Procédé selon la revendication 11, dans lequel la valeur du pH est inférieure à 0,5.
  13. Procédé selon la revendication 11, dans lequel la solution nettoyante-décapante-désoxydante comprend :
    a) du peroxyde d'hydrogène dans une quantité de 0,03 à 30 % en poids
    b) 0,1 à 5 g/l de stabilisant pour le peroxyde d'hydrogène
    c) de l'acide nitrique dans une quantité de 0,5 à 10 % en poids de 42° Baumé
    d) une source d'ions fluorure donnant 0,009 jusqu'à 0,17 % en poids de HF.
  14. Procédé selon la revendication 11, dans lequel la solution nettoyante-décapante-désoxydante comprend :
    a) du peroxyde d'hydrogène dans une quantité de 0,003 jusqu'à 30 % en poids
    b) 0,1 à 5 g/l de stabilisant pour le peroxyde d'hydrogène
    c) de l'acide phosphorique
    d) de l'acide nitrique dans une quantité de 0,5 à 10 % en poids de 42° Baumé.
  15. Procédé selon la revendication 11, dans lequel l'article désoxydé est revêtu par conversion par mise en contact avec un chromate contenant une composition de revêtement par conversion.
  16. Procédé selon la revendication 1, dans lequel l'aluminium est nettoyé par mise en contact avec une solution nettoyante comprenant 0,3 % d'acide sulfurique (96 %), 0,17 % d'acide fluorhydrique (70 %) et 0,2 % de 2-éthyl hexylsulfate de sodium et dans lequel le substrat d'aluminium est nettoyé dans cette solution pendant une durée de 5 à 10 minutes à une température allant de 43°C (110°F) jusqu'à 54°C (130°F).
  17. Procédé selon la revendication 1, dans lequel la solution désoxydante comprend 8 % en volume de peroxyde d'hydrogène (35 %), 3 % en volume d'acide nitrique 42° Baumé et dans lequel l'aluminium est immergé dans la solution désoxydante pendant une durée allant de 10 à 15 minutes à température ambiante.
  18. Procédé selon la revendication 1, dans lequel l'aluminium est nettoyé par mise en contact avec une solution de nettoyage qui comprend environ 0,5 % d'acide sulfurique (96 %), 1,7 % d'acide phosphorique (75 %) et jusqu'à 0,2 % d'un agent tensioactif et l'aluminium est traité dans cette solution pendant une durée allant de 5 à 10 minutes à une température de 43°C (110°F) jusqu'à 60°C (140°F).
  19. Procédé selon la revendication 1, dans lequel l'article en aluminium est nettoyé par mise en contact avec une solution de nettoyage acide contenant jusqu'à 10 % en poids d'au moins un acide et de 0 à 5 % en poids d'un agent tensioactif dans lequel la valeur de pH de la solution nettoyante acide est inférieure à 2.
  20. Procédé selon la revendication 1, dans lequel la solution de peroxyde d'hydrogène stabilisée contient de 0,03 à 30 % en poids de peroxyde d'hydrogène et la valeur de pH n'est pas supérieure à 1,5.
  21. Procédé selon la revendication 1, dans lequel l'étape de revêtement par conversion comprend la mise en contact avec un chromate contenant une composition de revêtement par conversion.
EP89113143A 1988-07-19 1989-07-18 Système de nettoyage/désoxydation sans chrome Expired - Lifetime EP0351771B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US22106588A 1988-07-19 1988-07-19
US221065 1988-07-19
US37499289A 1989-07-07 1989-07-07
US374992 1989-07-07

Publications (2)

Publication Number Publication Date
EP0351771A1 EP0351771A1 (fr) 1990-01-24
EP0351771B1 true EP0351771B1 (fr) 1995-08-30

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EP (1) EP0351771B1 (fr)
JP (1) JPH0277581A (fr)
AT (1) ATE127167T1 (fr)
AU (1) AU616776B2 (fr)
BR (1) BR8903578A (fr)
CA (1) CA1319591C (fr)
DE (1) DE68924012T2 (fr)
MX (1) MX170063B (fr)
TR (1) TR28132A (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209816A (en) * 1992-06-04 1993-05-11 Micron Technology, Inc. Method of chemical mechanical polishing aluminum containing metal layers and slurry for chemical mechanical polishing
US5637252A (en) * 1996-01-29 1997-06-10 Henkel Corporation Inhibitor for aqueous liquid deoxidizing composition and process for aluminum, with reduced etching of titanium
US7846349B2 (en) 2004-12-22 2010-12-07 Applied Materials, Inc. Solution for the selective removal of metal from aluminum substrates
US8398779B2 (en) 2009-03-02 2013-03-19 Applied Materials, Inc. Non destructive selective deposition removal of non-metallic deposits from aluminum containing substrates

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4451304A (en) * 1981-05-04 1984-05-29 Walter Batiuk Method of improving the corrosion resistance of chemical conversion coated aluminum
AT377539B (de) * 1981-06-24 1985-03-25 Badische Corp Monofiler, aus zwei komponenten bestehender, elektrisch leitender textilfaden
JPS58197277A (ja) * 1982-05-08 1983-11-16 Mitsubishi Gas Chem Co Inc 金属の化学的溶解処理液
CA1273861A (fr) * 1986-01-21 1990-09-11 Thomas H. Fick Methode de nettoyage de l'aluminium

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DE68924012T2 (de) 1996-05-02
JPH0277581A (ja) 1990-03-16
MX170063B (es) 1993-08-05
AU3823089A (en) 1990-01-25
BR8903578A (pt) 1990-04-17
DE68924012D1 (de) 1995-10-05
ATE127167T1 (de) 1995-09-15
AU616776B2 (en) 1991-11-07
CA1319591C (fr) 1993-06-29
EP0351771A1 (fr) 1990-01-24
TR28132A (tr) 1996-03-01

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