US2018388A - Treating aluminum and aluminum alloy surfaces - Google Patents

Treating aluminum and aluminum alloy surfaces Download PDF

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Publication number
US2018388A
US2018388A US474665A US47466530A US2018388A US 2018388 A US2018388 A US 2018388A US 474665 A US474665 A US 474665A US 47466530 A US47466530 A US 47466530A US 2018388 A US2018388 A US 2018388A
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US
United States
Prior art keywords
aluminum
solution
coating
oxide
metal
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.)
Expired - Lifetime
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US474665A
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English (en)
Inventor
Tosterud Martin
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.)
ALUMINUM COLORS Inc
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ALUMINUM COLORS Inc
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Filing date
Publication date
Application filed by ALUMINUM COLORS Inc filed Critical ALUMINUM COLORS Inc
Priority to US474665A priority Critical patent/US2018388A/en
Priority to FR731997D priority patent/FR731997A/fr
Priority to GB35008/31A priority patent/GB391903A/en
Application granted granted Critical
Publication of US2018388A publication Critical patent/US2018388A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • 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
    • C23C22/82—After-treatment
    • C23C22/84—Dyeing

Definitions

  • vIt is an object of this invention to provide a process by which aluminum and .its alloys may have afiixed upon their surfaces colors of substantially any hue which are uniform and of a permanent nature.
  • Another object of the invention is the provision of an aluminum or aluminum alloy article, the surfaces of which are covered with a chemically produced coating in which is deposited an insoluble, inorganic compound.
  • the aluminum or aluminum alloy article is treated to produce upon its surface an oxide coating which is hard and dense and which has sufficient adsorbent qualities to retain, 5 when immersed in a liquid, an appreciable quantity of such liquid within and upon it.
  • oxide coating is a well known designation of the art which describes a layer of aluminum 0 oxide artificially produced on the aluminum or aluminum alloy surfaces by treatment of the metal surfaces with acids, such as sulfuric, chromic, etc., or alkalies, such as sodium carbonate or the alkali sulfates and acid sulfates such as sodium sulfate or sodium acid sulfate, etc., all with or without the addition of other substances and with or without the use of externally-applied electrical energy.
  • oxide coating does not include the very thin film of 20 aluminum oxide which is naturally formed upon that metal or its alloys by reason of contact with the air.
  • my invention employs novel methods of my invention to deposit in the oxide coating an insoluble, inorganic compound.
  • My novel methods comprise .in part, the placing of an oxide-coated aluminum or aluminum alloy in contact with a solution, preferably but not necessarily aqueous, of a soluble compound, the inorganic anion or cation of which will, when combined with the inorganic cation or anion of another soluble compound, produce an inorganic compound of a characteristic color and/or of corrosion-inhibitive properties.
  • the inorganic compound so precipitated in the oxide coating has a characteristic color, that color or some hue thereof is imparted to the oxide coating with the result that by the use of the method of my invention there may be produced aluminum or aluminum alloy articles having uniformly and permanently colored surfaces of substantially any desired shade. Also. if the insoluble, inorganic compound so precipitated is of a corrosion-inhibitive nature, the oxide coating containing it aifords substantially greater protection to the coated aluminum or aluminum alloy article. It will now be apparent that by use of my invention an aluminum or aluminum alloy article may be provided with a coating which may at once serve both as a colored surface and as a" means of protection against corrodon; or, onthe other hand, the coating may not be colored but yet may protect the metal against corrosive influences.
  • the aluminum or aluminum alloy which is to be treated is first provided with an oxide coating of certain characteristics.
  • the coating In order that the coating will not later separate from the metal surface,-it is necessary that it be hard, dense, and adherent. Of great importance, however, is the adsorbent nature of the coating.
  • the oxide coating In order to obtain the most satisfactory results the oxide coating should be adapted to adsorb a substantial amount of the solution with which, as above mentioned, it later comes in contact.
  • a further desirable quality of the oxide coating is its thickness, a comparatively thick coating being preferable. How- 'ever, the thickness of the coating is not a controlling factor, and some comparatively thin coatings, artificially produced, will give good results. Being adsorbent, the coating is necessarily porous. 4
  • adsorbent oxide coatings of a nature suitable to the purpose of my invention, I have used a large number of solutions, among which are included solutions of sulfuric acid, chromic acid, sodium carbonate and potassium dichromate, phosphoric acid and the salts thereof, ammonium citrate or lactate, citric acid and the salts there- I of, and sodium carbonate.
  • the treatment of the aluminum or aluminum alloy with these solutions to produce the desired oxide coating may consist in either immersing the metal in the solution and allowing the coating to be formed by the action of the solution, or by supplementing the action of the solution by making the metal to be coated the anode of a cell in which the solution serves as the electrolyte, and then impressing external electrical energy upon the electrodes of the cell.
  • chromic acid When chromic acid is used as the oxide coating solution, the conditions named in the case 20 oi sulfuric acid may be followed substantially. In my preferred practice, I have found a three per cent solution of chromic acid to give excellent results. The solution, during the coating process, should be heated to about 40. C..-
  • a solution containing about 0.5 to 6 per cent of sodium carbonate and about 0.1 to 1 per cent of potassium dichromate will give good results. but as a specific solution, I prefer one containing about 2 per cent of sodium carbonate and 0.5 per cent of potassium dichromate.
  • inorganic compound includes, in addition to those compounds which are strictly inorganic, the metallic ferri-cyanides and ferro cyanides.
  • insoluble inorganic compound refers to a compoimd of the defined nature which is substantially insoluble in water. The method of introducing these insoluble inorganic compounds into the preformed oxide coating consists of two steps.
  • the first step consists in placing the oxide-coated metal surface in contact with or immersing it in a solution containing either the anion or the cation of the insoluble inorganic compound which it is desired to deposit in the oxide coating.
  • the oxide-coated metal is held in contact with or immersed in the solution for a sufllcient time to allow the solution to be adsorbed in or on the oxide coating.
  • the 00 second step consists in bringing the oxide-coated metal, which now, as the result of the first step, has adsorbed in or on its oxide coating the solution used in the first step, in contact with a second solution, containing the cation or union which, by combining with the anion or cation present in the first and adsorbed solution, will produce the insoluble, inorganic compound desired.
  • the oxidecoated metal with the solution adsorbed from the first step in its oxide coating now adsorbs part chi).
  • inorganic compound so deposited is in cifect intc- 76 gral with 'or permanently aflixed in the oxide coating.
  • my invention concerns the coloring of aluminum or aluminum alloy articles which are to be used in various applications where certain colors are desirable.
  • the following may be cited as specific examples of the exact manner in which my invention may be practiced to obtain a number of different colors and shades thereof.
  • the oxide coating may be formed on the aluminum or aluminum alloy by any of the methods heretofore mentioned but it is preferred to use solutions of sulfuric acid or solutions of chromic acid or solutions of sodium carbonate and potassium dichromate.
  • Example 1 Brown colors may be obtained thus: For a light brown, the oxide-coated metal is first immersed in a solution of potassium bichromate (K2C1'2O'z) and is thereafter immersed in a solution of silver nitrate (AgNOa).
  • K2C1'2O'z potassium bichromate
  • AgNOa silver nitrate
  • the oxide-coated metal is immersed in a solution of a soluble copper salt such as copper sulfate (CuS04) and is thereafter immersed in a solution of potassium ferro cyanide (KlFelcNls)
  • a solution of lead acetate Pb[C2H3O2]2
  • a solution of ammonium sulfide [NH412S]
  • a red color may be obtained on aluminum and aluminum alloys by immersing the oxide-coated metal in a solution of uranyl acetate and thereafter immersing the oxide-coated metal in a solution of potassium ferro cyanide
  • a yellow color may be obtained upon aluminum and aluminum alloys by immersing the oxidecoated metal in cadmium acetate (Cd[C2HaO2]2), cadmium nitrate (Cd[NO3]2), or cadmium chloride (Cd[C2HaO2]2), cadmium nitrate (Cd[NO3]2)
  • Yellow colors may also be obtained by immersing the oxide-coated aluminum or aluminum alloys in a solution of lead acetate (PbECzHaOzh) and thereafter immersing the metal in potassium dichromate (KZCI'ZO'! or potassium chromate (KZCIOl). Yellow colors may also be obtained by the use of zinc acetate (Zn[C2H3O2]2) as an initial solution and potassium dichromate (KzCl'aOl) or a similar alkaline dichromate or chromate as a second solution.
  • Yellow colors may also be obtained by using barium nitrate (Ba[NO3]z) or barium acetate (BalCzHaOzh) as the initial solution and an alkaline dichromate or chromate as the subsequent solution.
  • barium nitrate Ba[NO3]z
  • barium acetate BalCzHaOzh
  • Example 4 The surfaces of aluminum or aluminum alloys may be whitened by immersing the oxide-coated metal into an initial solution of lead acetate (PbwzHao-zla) and thereafter immersing the metal in a solution of sodiumvsulfate (NaSO i).
  • PbwzHao-zla lead acetate
  • NaSO i sodiumvsulfate
  • Aluminum and its alloys may also be whitened by immersing the oxide-coated metal in an initial solution of lead acetate (PblCzHaOzla) and thereafter immersing the metal in a solution of sodium arsenate (Na3AsO4)
  • Example 5 Blue colors, for example the deep color known as Prussian blue may be produced upon aluminum or its alloys by initially immersing the oxidecoated metal in a solution of potassium ferro cyanide (K4Fe[CN]s) and thereafter immersing the metal in a solution of ferric sulfate (FGZESO-ih) or ferric chloride (FeCla).
  • the color is produced in each case by the precipitation in the oxide coating of the oxide-coated aluminum or aluminum alloy of an insoluble, inorganic compound.
  • silver bichromate' (AgzCrzOv) copper ferro cyanide (CuzFeiCNk), or lead sulfide (PbS) is precipitated in the oxide coating, according to the reagents used.
  • uranium ferro cyanide is precipitated to form a red colored coating.
  • a precipitate of cadmium sulfide, lead chromate, zinc chromate, or barium chromate, respectively, is deposited in the oxide coating to form various shades of yellow.
  • Example 4 lead sulfate and lead arsenite respectively are precipitated in the oxide coating with the result that a white color is produced.
  • Example 5 cobalt sulfide and nickel sulfide are respectively deposited in the oxide coating to produce a black surface on the aluminum and its alloys.
  • Example 6 ferric ferrocyanide and ferro-ferri cyanide are respectively 6 aluminum alloy article in accordance with my invention, the depth and intensity of the color produced may be increased by repeating the treatment with various soluble compounds.
  • the light green color which is imparted to the oxide-coated aluminum or aluminum alloy by first immersing the metal in copper sulfate and then immersing it in sodium arsenite, may be increased in depth and intensity by again immersing the colored, oxidecoated metal in copper sulfate followed by an immersion in sodium arsenite.
  • I claim- 1 Method of providing the surface of aluminum and aluminum-alloy articles with color of uniform and permanent characteristics by forming on the surface of the aluminum or aluminum alloy adsorbent oxide coating and adsorbing in said coating inorganic compounds separately from solutions thereof, said compounds being adapted to react to precipitate an insoluble inorganic compound of characteristic color.
  • the method comprising forming on the sur- 5 face of an aluminum or aluminum-alloy article a porous adsorbent oxide coating, and thereafter by metathetical reaction depositing in the pores of the coating an insoluble inorganic precipitate of permanent color.
  • An aluminum or aluminum-alloy article having an adsorbent oxide coating containing an insoluble colored inorganic compound precipitated therein.
  • An aluminum or aluminum-alloy article having an adsorbent oxide coating containing a yellow lead-chromium compound such as is precipitated by the reaction of a soluble lead compound and a soluble salt of chromic acid adsorbed by the coating.
  • An aluminum or aluminum-alloy article having an adsorbent oxide coating containing a black sulphide such as is precipitated by the reaction of a soluble cobalt or equivalent nickel compound and soluble ammonium sulphide adsorbed by the coating.
  • An article of aluminum or aluminuml-alloy having on its surface an adsorbent anodic oxide 15 coating containing in its pores an insoluble incoating containing in its pores a precipitate of organic precipitate of permanent color. lead chromate.
  • An article of aluminum or aluminum alloy 17.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
US474665A 1930-08-11 1930-08-11 Treating aluminum and aluminum alloy surfaces Expired - Lifetime US2018388A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US474665A US2018388A (en) 1930-08-11 1930-08-11 Treating aluminum and aluminum alloy surfaces
FR731997D FR731997A (fr) 1930-08-11 1931-12-16 Perfectionnements au traitement superficiel de l'aluminium ou de ses alliages
GB35008/31A GB391903A (en) 1930-08-11 1931-12-17 Improvements in or relating to the surface treatment of aluminium or aluminium alloys

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US474665A US2018388A (en) 1930-08-11 1930-08-11 Treating aluminum and aluminum alloy surfaces
FR731997T 1931-12-16
GB35008/31A GB391903A (en) 1930-08-11 1931-12-17 Improvements in or relating to the surface treatment of aluminium or aluminium alloys

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2458073A (en) * 1944-01-06 1949-01-04 Parker Appliance Co Coating magnesium and magnesium alloys
US2522474A (en) * 1942-07-02 1950-09-12 Battelle Memorial Institute Treatment of zinc surfaces
US2538317A (en) * 1945-12-28 1951-01-16 Reynolds Metals Co Treatment of aluminum sheets
US2553064A (en) * 1951-05-15 Surfacing and cleaning aluminum
US2584400A (en) * 1944-10-20 1952-02-05 Sonnino Carlo Process for anodic oxidation of aluminum and its alloys
US2769265A (en) * 1947-06-18 1956-11-06 Boeing Co Metal foil appliques and method of making same
US2785098A (en) * 1955-01-26 1957-03-12 Horizons Inc Treating of aluminum and aluminum alloy surfaces
US2987417A (en) * 1958-06-23 1961-06-06 Aluminum Co Of America Pigmenting aluminum oxide coating
US2995459A (en) * 1957-11-26 1961-08-08 Faberge Inc Method for coloring nacreous materials and products and compositions provided thereby
US3032435A (en) * 1958-07-17 1962-05-01 Knapsack Greisheim Ag Process for improving the corrosion resistance of pieces of light metals and light metal alloys
US3053719A (en) * 1958-12-08 1962-09-11 Purex Corp Ltd Composition and process for etching magnesium
US3096571A (en) * 1958-12-29 1963-07-09 Morris Kurtzon Inc Method and apparatus for making a screen or grille
US3152970A (en) * 1961-10-03 1964-10-13 Darwin P Jensen Application of pigment to anodized aluminum
US3418219A (en) * 1966-03-29 1968-12-24 Martin Marietta Corp Coloring anodized aluminum
US3546028A (en) * 1966-07-11 1970-12-08 Cominco Ltd Process of improving corrosion resistance of colored oxide coatings on titanium-rich zinc alloys and resulting product
US3549540A (en) * 1966-10-31 1970-12-22 Amchem Prod Method and compositions for treating aluminum surfaces
US5296285A (en) * 1992-05-26 1994-03-22 Mcdonnell Douglas Corporation High emittance low absorptance coatings
WO1996015296A1 (fr) * 1994-11-14 1996-05-23 The Secretary Of State For Defence Traitement de l'aluminium ou d'alliages d'aluminium
US20030236016A1 (en) * 2002-06-20 2003-12-25 The Furukawa Electric Co., Ltd. Tubular bus bar, insulating coating method therefor, and insulating coating structure therefor
CN110923777A (zh) * 2019-09-10 2020-03-27 西北稀有金属材料研究院宁夏有限公司 一种铍铝合金表面导电氧化的方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2868702A (en) * 1952-11-04 1959-01-13 Helen E Brennan Method of forming a dielectric oxide film on a metal strip
US3278958A (en) * 1955-03-31 1966-10-18 Dick Co Ab Method of imaging a photolithographic plate and elements for use in the preparation of same
US4526671A (en) * 1982-09-24 1985-07-02 Pilot Man-Nen-Hitsu Kabushiki Kaisha Surface treatment of aluminum or aluminum alloys
JPS6021397A (ja) * 1983-07-15 1985-02-02 Pilot Pen Co Ltd:The アルミニウム又はアルミニウム合金の表面処理方法
JPH0747836B2 (ja) * 1990-03-02 1995-05-24 ワイケイケイ株式会社 アルミニウム又はアルミニウム合金材の着色法

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2553064A (en) * 1951-05-15 Surfacing and cleaning aluminum
US2522474A (en) * 1942-07-02 1950-09-12 Battelle Memorial Institute Treatment of zinc surfaces
US2458073A (en) * 1944-01-06 1949-01-04 Parker Appliance Co Coating magnesium and magnesium alloys
US2584400A (en) * 1944-10-20 1952-02-05 Sonnino Carlo Process for anodic oxidation of aluminum and its alloys
US2538317A (en) * 1945-12-28 1951-01-16 Reynolds Metals Co Treatment of aluminum sheets
US2769265A (en) * 1947-06-18 1956-11-06 Boeing Co Metal foil appliques and method of making same
US2785098A (en) * 1955-01-26 1957-03-12 Horizons Inc Treating of aluminum and aluminum alloy surfaces
US2995459A (en) * 1957-11-26 1961-08-08 Faberge Inc Method for coloring nacreous materials and products and compositions provided thereby
US2987417A (en) * 1958-06-23 1961-06-06 Aluminum Co Of America Pigmenting aluminum oxide coating
US3032435A (en) * 1958-07-17 1962-05-01 Knapsack Greisheim Ag Process for improving the corrosion resistance of pieces of light metals and light metal alloys
US3053719A (en) * 1958-12-08 1962-09-11 Purex Corp Ltd Composition and process for etching magnesium
US3096571A (en) * 1958-12-29 1963-07-09 Morris Kurtzon Inc Method and apparatus for making a screen or grille
US3152970A (en) * 1961-10-03 1964-10-13 Darwin P Jensen Application of pigment to anodized aluminum
US3418219A (en) * 1966-03-29 1968-12-24 Martin Marietta Corp Coloring anodized aluminum
US3546028A (en) * 1966-07-11 1970-12-08 Cominco Ltd Process of improving corrosion resistance of colored oxide coatings on titanium-rich zinc alloys and resulting product
US3549540A (en) * 1966-10-31 1970-12-22 Amchem Prod Method and compositions for treating aluminum surfaces
US5296285A (en) * 1992-05-26 1994-03-22 Mcdonnell Douglas Corporation High emittance low absorptance coatings
WO1996015296A1 (fr) * 1994-11-14 1996-05-23 The Secretary Of State For Defence Traitement de l'aluminium ou d'alliages d'aluminium
GB2308851A (en) * 1994-11-14 1997-07-09 Secr Defence Treatment of aluminium or aluminium alloys
US5954893A (en) * 1994-11-14 1999-09-21 The Secretary Of State For Defence Treatment of aluminium or aluminium alloys
CN1113985C (zh) * 1994-11-14 2003-07-09 秦内蒂克有限公司 铝或铝合金的处理
US20030236016A1 (en) * 2002-06-20 2003-12-25 The Furukawa Electric Co., Ltd. Tubular bus bar, insulating coating method therefor, and insulating coating structure therefor
CN110923777A (zh) * 2019-09-10 2020-03-27 西北稀有金属材料研究院宁夏有限公司 一种铍铝合金表面导电氧化的方法

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FR731997A (fr) 1932-09-10
GB391903A (en) 1933-05-11

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