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

• 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 equeous solution of sodium or potassium nitrite.
• 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, zinc and the like.
• 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 about 50% by weight, and preferably from about .2 to about 8% by weight and more preferably from about 0.4% to about 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 about 2% and most preferably up to about 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 and the like, 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 about ambient to about 170 o F and preferably from about 90 o F to about 150 o F.
• the pH of the solution is preferably below about 3 and more preferably below about 1.5 and most preferably below about 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 about 90 o F to about 175 o F and most preferably from about 100 o F to about 150 o 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 about 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 about ambient to about 150 o 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 about 1 to about 25 minutes.
• the contact time is generally shorter at higher temperatures.
• Stabilizers for peroxides are well known and are exemplified in U.S. Patent 4,509,678. This patent is incorporated herein by reference.
• 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.
• 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 contaminatin of the chromating composition with the components of the deoxidizing treatment composition.
• a cleaning solution was prepared as follows:
• a deoxidizer solution was prepared as follows: A concentrate was first prepared by blending 3800 mls of 35% hydrogen peroxide and 200 mls of Dowfax® 241 (sodium dodecyl diphenyl oxide disulfonate).
• Panels of aluminum alloy 2024-T3 were immersed in the cleaning solution at a temperature of 120 o 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 incorprated herein by reference.
• a cleaner solution concentrate was prepared by blending 100 mls of 96% sulfuric acid and 416 mls of 75% phosphoric acid and diluting to one liter.
• a cleaner solution was prepared by mixing 140 mls of cleaner solution and 70 mls of hydrfluoric 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 120 o 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 mls 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 110 o F to about 130 o 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 o 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 o Bé) nitric acid and up to 0.5% of a stabilizer for the peroxide (preferrably MIRATAINE® CBS (cocoamidopropyl hydroxy sultaine).
• etching cleaner When it is desired to have an etching cleaner with lower etching properties, it is preferred to employ 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 110 o F to about 140 o F for 5 to 10 minutes followed by the same deoxidizer step as established above for from about 5 to 15 minutes.
• a cleaning solution 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 110 o F to about 140 o 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 120 o 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 120 o 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 commerical 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)
• Treatment Of Water By Oxidation Or Reduction (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Processing Of Solid Wastes (AREA)
• Photoreceptors In Electrophotography (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (4)

• 1989
  • 1989-07-18 CA CA000605932A patent/CA1319591C/en not_active Expired - Fee Related
  • 1989-07-18 EP EP89113143A patent/EP0351771B1/de not_active Expired - Lifetime
  • 1989-07-18 AT AT89113143T patent/ATE127167T1/de not_active IP Right Cessation
  • 1989-07-18 DE DE68924012T patent/DE68924012T2/de not_active Expired - Fee Related
  • 1989-07-19 MX MX016855A patent/MX170063B/es unknown
  • 1989-07-19 AU AU38230/89A patent/AU616776B2/en not_active Ceased
  • 1989-07-19 TR TR00788/89A patent/TR28132A/xx unknown
  • 1989-07-19 BR BR898903578A patent/BR8903578A/pt not_active IP Right Cessation
  • 1989-07-19 JP JP1187239A patent/JPH0277581A/ja active Pending

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