US3331710A - Method for coating aluminum - Google Patents
Method for coating aluminum Download PDFInfo
- Publication number
- US3331710A US3331710A US304219A US30421963A US3331710A US 3331710 A US3331710 A US 3331710A US 304219 A US304219 A US 304219A US 30421963 A US30421963 A US 30421963A US 3331710 A US3331710 A US 3331710A
- Authority
- US
- United States
- Prior art keywords
- solution
- aluminum
- ion
- phosphate
- cleaning
- 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
Links
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
- C23C22/78—Pretreatment of the material to be coated
-
- 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 an improved method for coating aluminum and more particularly relates to a continuous 4step process which employs an improved aqueous acidic cleaner as its first stage for conditioning the surface of the aluminum to receive an integral chemical conversion coating.
- a S-stage or 6-stage process includes an alkali cleaner stage, a water rinse, a de-smutter stage followed by a water rinse, a chemical conversion coating stage and a final rinse.
- the final rinse may be either Water or dilute chromic acid and when chromic acid is used, it is sometimes preceded by an intermediate water rinse following the conversion coating stage.
- the 4 stages prior to the chemical conversion coating stage can be satisfactorily replaced by two stages when the cleaning is accomplished by an aqueous acidic solution, rather than an alkaline cleaning solution.
- the aqueous acidic cleaning solution is one which is capable of etching the contaminated aluminum surface sufliciently to make it receptive to the chemical conversion coating, and simultaneously is capable of forming a protective coating on the surfaces of a mild steel tank to enable continuous processing of aluminum therethrough.
- the improved process of this invention comprises the steps of contacting the aluminum surface to be coated with an aqueous acidic cleaning solution, rinsing, forming on the cleaned and rinsed surface the desired chemical conversion coating and thereafter rinsing the chemical conversion coated surface, with water or dilute chromic acid solution or the like.
- aqueous acidic phosphate solution containing controlled quantities of the fluoride ion and the hydrogen ion.
- the controlled quantities of fluoride and hydrogen ion function jointly to maintain the ability of the cleaning solution to etch the aluminum surface at a controllable and substantially constant rate and concurrently permit the use of a mild steel tank surface.
- the aqueous acidic solutions of this invention appropriately may be characterized as buffered solutions, which buffering resists change in acidity of the solution during its continuous use.
- the preferred solution is one which contains the phosphate of zinc, iron Patented July 18, 1967 or manganese, and preferably is zinc phosphate, the solution having a pH within the range of about 1.8 to about 3.2. It has been found in the use of such zinc phosphate solutions that the steel tank lining receives an adherent phosphate coating which becomes sufiiciently continuous to substantially stop any further reaction between the steel lining and the aqueous acidic cleaning composition and thus enables the continuous use of the cleaning solution for aluminum surface cleaning without destroying the tank lining or losing its necessary hydrogen ion concentration to enable satisfactory aluminum surface cleaning.
- the pH should be maintained in the same range as that above stated, namely about 1.8 to about 3.2, but in this case, it is necessary to employ a stainless steel tank for the alkali metal cleaning solution.
- the cleaning solution is buffered by the simultaneous presence of a mixture of alkali metal phosphates and phos phoric acid.
- the fluoride ion should be present in the aqueous acidic cleaning solutions of this invention in an amount suflicient to form AlF where x equals at least about 1.1-1.2, and preferably is present in an amount of at least about 0.02% in excess of AIF (l.l1.2).
- x equals at least about 1.1-1.2
- AIF l.l1.2
- the cleaning solution achieves an ability to attack the tank lining and in the case of a mild steel tank quantites of fluoride in excess of AlF (Ll-1.2) in amounts above about 0.05 %0.1% cause difliculty, whereas with stainless steel tank linings concentrations of active fluoride in in excess of AIF (l.1-l.2) of about 0.2%0.3% are similarly undesirable.
- the fluoride ion may be provided in the aqueous acidic cleaning solutions of this invention as HF, fluoboric acid, or fluosilicic acid and since equal quantities of fluoboric and fluosilicic acids provide less fluoride ion activity in the solution than HF supplies, the concentration of fluoboric and fluosilic may be substantially greater than that given above for HF, e.g. fluoboric may be present in concentrations of 2-3 times that of HF, while fluosilicic may be present in concentrations of 2-2/: times that of HF.
- the phosphate ion may be provided at least partially as phosphoric acid and partially as the salt of one of the metal ions zinc, iron or manganese, or one of the alkali metal ions, sodium, potassium or ammonium.
- the P0 ion concentration may satisfactorily extend upwardly from about 0.10% as a minimum. There is nothing critical about the upper concentration to which the P0 ion may extend, but for practical purposes concentrations in excess of 2%3% P0 provide no additional benefit.
- the concentration of the selected metal ion, or the metallic phosphate salt is preferably such as to provide sufficient metallic ion to form a phosphate salt with all of the P0 ion which is present, to thus produce a solution having a pH within the above stated range.
- the zinc, iron or manganese ions may be used in any installation which employs a mild steel tank for the aqueous acidic cleaning solution and in this case zinc is the preferred metal ion for this purpose.
- the rate of cleaning is improved, in certain instances, and that in other instances diflicult to remove surface coatings on the aluminum to be cleaned are more effectively removed when the cleaning solution includes an oxidizing agent.
- the nitrate ion represents the preferred oxidizing agent, but it is satisfactory to employ other conventional oxidizing agents such as chlorate, bromate, peroxide, sulfite and the like.
- quantities of oxidizing agents in the 7 range of about 0.01% to 1% nitrate, or its equivalent is satisfactory. It is understood that the cleaning solutions stitute a preferred form of this invention which have been found to be particularly advantageous for use with certain aluminum alloys such as 6061, 6062, etc.
- suitable surface active agents include the non-ionic types such as polyethylene or polypropylene glycols, polyether alcohols, and substituted poly-glycol esters, and the anionic types such as sulfonated hydrocarbons and fatty alcohol sul- "fates.
- the preferred wetting agents for this purpose are the substituted polyglycol esters and derivatives of polyethylene glycols and polyether alcohols sold under the trade name of Igepal (Allied Chemical and -Dye Cor poration), particularly Igepal CA 630 or Igepal CA 630 and those sold under the trade name Triton (Rohm & Haas Co.) and particularly Triton X-l00.
- Cleaning solutions of this invention may be applied to the aluminum surface to be cleaned by spraying or dipping the aluminum part into the tank containing the cleaning solution.
- the cleaning solution may be suitably maintained at a temperature in the range of about 90 F. to the boiling point of the solution in the absence of a surface active agent in the solution.
- the temperature of the solution should be slightly above the cloud point temperature for the particular surface active agent which is present.
- the chemical conversion coating which'may be formed on the aluminum surface cleaned with the above described aqueous acidic cleaning solution isany of the conversion coatings which are now'conventional and well understood by those skilled in this art.
- Such conversion coatings include those which result from the application of hexavalent chromium-containing aqueous solutions which may include a reducing agent in the solution as I applied or function to reduce the hexavalent chromium compound in situ on the surface, chromate phosphate solutions, chromate-fluoride, chromate-film forming resin solutions and the like.
- suitable solutions for the formation of such conversion coatings are disclosed in Bell US. Patent 2,902,390, issued-Sept. 1, 1959, Schuster et al. U.S.
- Patents 2,768,103 and 2,768,104 issued Oct. 23, 1956, .and Schuster US. Patents 2,911,332, issued Nov..3, 1959, and 3,094,435, issued June 18, 1963.
- Such conversion coating forming solutions are typically applied by spraying or dipping the part to be coated in the solu- V 7 tion .at room to elevated temperatures as high as about 180 'F., preferably room to 130 'F.
- the applied solution may be dried on the surface with air or the application of heat in the form of infrared rays, hot air or the like, and the coating is then in condition for rinsing in.
- EXAMPLE I A solution was prepared containing 0.02% zinc, 0.28% P0 and 0.02% fluoride as HF. This solution gave a free acid based on 10 ml. sample titrated against 0.1 normal sodium hydroxide of 0.6 point, using bromcresol green as the indicator, and a total acid of 4.6 points, using phenolphthalein as the indicator. The pH was 2.90.
- the aluminum extrusions Prior to cleaning the aluminum extrusions, they had a grayish to irridescent film containing fingerprints and spaced grease spots thereover and subsequent to the cleaning were changed to a normal appearing uniform gray aluminum surface color. After the chromate conversion coating and subsequent rinsing step, the extrusions had a light brown film of substantial uniformity over their entiresurface. The coated extrusions were then dried in an oven at a temperatureof about 225 F. for about one minute and withdrawn, at which time the coatings had changed to a darker brown color.
- a process for coating aluminum which consists essentially of the steps of contacting a surface of aluminum with an aqueous acidic cleaning solution consisting essentially of the phosphate ion, the fluoride ion and a metal ion selected from the group consisting of zinc, manganese, and iron, said solution having a pH in the range of about 1.8 to about 3.2, the phosphate ions being present in an amount of at least 0.1% by weight, the metal ion being present in an amount at least suflicient to form the phosphate salt with the phosphate ions present and the fluoride ions being equivalent to an amount, which when added as HF is from about 0.02 to 0.3% by Weight in excess of that required to form AlF where x is- 1.1 to 1.2, with the aluminum introduced into the solution by the Work being treated, maintaining said solution in contact with the aluminum surface for a time sufficient to effect cleaning thereof, water rinsing the surface, thereafter forming a chromate chemical conversion coating on said rinsed surface.
- the cleaning solution also contains an oxidizing agent and wherein after the formation of the chromate chemical conversion coating on the water-rinsed surface, the coated surface is rinsed With a solution selected from the group consisting of water and dilute aqueous hexavalent chromium-containing solutions.
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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)
- Chemical Treatment Of Metals (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US304219A US3331710A (en) | 1963-08-23 | 1963-08-23 | Method for coating aluminum |
FR983285A FR1409489A (fr) | 1963-08-23 | 1964-07-28 | Procédé de revêtement de l'aluminium |
BE651584D BE651584A (de) | 1963-08-23 | 1964-08-07 | |
GB34310/64A GB1073754A (en) | 1963-08-23 | 1964-08-21 | Improvements relating to the coating of aluminium |
DEM62180A DE1285830B (de) | 1963-08-23 | 1964-08-21 | Verfahren zum Aufbringen von UEberzuegen auf Aluminium und dessen Legierungen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US304219A US3331710A (en) | 1963-08-23 | 1963-08-23 | Method for coating aluminum |
Publications (1)
Publication Number | Publication Date |
---|---|
US3331710A true US3331710A (en) | 1967-07-18 |
Family
ID=23175577
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US304219A Expired - Lifetime US3331710A (en) | 1963-08-23 | 1963-08-23 | Method for coating aluminum |
Country Status (4)
Country | Link |
---|---|
US (1) | US3331710A (de) |
BE (1) | BE651584A (de) |
DE (1) | DE1285830B (de) |
GB (1) | GB1073754A (de) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3420715A (en) * | 1965-06-04 | 1969-01-07 | Cons Foods Corp | Additive for phosphate coating solution |
US3468766A (en) * | 1965-08-27 | 1969-09-23 | Mc Donnell Douglas Corp | Treatment of aluminum |
US3549540A (en) * | 1966-10-31 | 1970-12-22 | Amchem Prod | Method and compositions for treating aluminum surfaces |
US3819424A (en) * | 1971-06-17 | 1974-06-25 | Oxy Metal Finishing Corp | Method and composition for treating metal surfaces |
US3857739A (en) * | 1972-08-31 | 1974-12-31 | Dominion Foundries & Steel | Compositions and processes for producing chromium conversion coatings on surfaces of zinc or cadmium |
US3864147A (en) * | 1972-09-25 | 1975-02-04 | Macdermid Inc | Method of improving the bonding capability of polymer surfaces for subsequently applied coatings, and products thereof |
US3932130A (en) * | 1974-07-03 | 1976-01-13 | Texaco Inc. | Inhibition of aluminum corrosion by sulfuric acid solutions |
US4111722A (en) * | 1976-02-09 | 1978-09-05 | Oxy Metal Industries Corporation | Tannin treatment of aluminum with a fluoride cleaner |
US4256602A (en) * | 1978-12-01 | 1981-03-17 | Pennwalt Corporation | Fluoroborate complex composition and method for cleaning aluminum at low temperatures |
US4427458A (en) | 1980-12-01 | 1984-01-24 | Yoshida Kogyo K. K. | Method for forming protective surface film on aluminum shaped articles |
US20070066503A1 (en) * | 2005-08-19 | 2007-03-22 | Mores Basaly | Methods and compositions for acid treatment of a metal surface |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3705633A1 (de) * | 1987-02-21 | 1988-09-01 | Metallgesellschaft Ag | Verfahren zur vorbereitung von werkstuecken aus aluminium oder dessen legierungen fuer die lackierung |
DE4317217A1 (de) * | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chromfreie Konversionsbehandlung von Aluminium |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2234206A (en) * | 1935-06-03 | 1941-03-11 | Metal Finishing Res Corp | Coated aluminum |
US2257960A (en) * | 1939-01-12 | 1941-10-07 | William M Humphrey | Cleaning aluminum surfaces |
US2312855A (en) * | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
US2316220A (en) * | 1939-04-22 | 1943-04-13 | Aluminum Co Of America | Composition for cleaning aluminum |
US2477841A (en) * | 1945-09-10 | 1949-08-02 | Parker Rust Proof Co | Method of coating metal surfaces comprising aluminum |
US2500673A (en) * | 1947-05-22 | 1950-03-14 | Parker Rust Proof Co | Process of producing a phosphate coating on metals high in aluminum |
US2593449A (en) * | 1950-10-26 | 1952-04-22 | Kaiser Aluminium Chem Corp | Method and composition for treating aluminum and aluminum alloys |
US2901821A (en) * | 1955-11-18 | 1959-09-01 | Detrex Chem Ind | Aluminum coated with aluminum benzoate, and method and composition for making same |
US2909455A (en) * | 1958-09-24 | 1959-10-20 | Amchem Prod | Method of coating a succession of aluminum surfaces |
US3007817A (en) * | 1957-11-29 | 1961-11-07 | Parker Rust Proof Co | Cold cleaning and cold phosphate coating process |
US3106499A (en) * | 1959-05-11 | 1963-10-08 | Rohr Corp | Process and composition for cleaning and polishing aluminum and its alloys |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1149965B (de) * | 1957-06-07 | 1963-06-06 | Ver Leichtmetallwerke Gmbh | Verfahren zur Verbesserung der Haftfestigkeit von organischen Stoffen auf Aluminium oder Aluminiumlegierungen |
-
1963
- 1963-08-23 US US304219A patent/US3331710A/en not_active Expired - Lifetime
-
1964
- 1964-08-07 BE BE651584D patent/BE651584A/xx unknown
- 1964-08-21 GB GB34310/64A patent/GB1073754A/en not_active Expired
- 1964-08-21 DE DEM62180A patent/DE1285830B/de active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2234206A (en) * | 1935-06-03 | 1941-03-11 | Metal Finishing Res Corp | Coated aluminum |
US2257960A (en) * | 1939-01-12 | 1941-10-07 | William M Humphrey | Cleaning aluminum surfaces |
US2316220A (en) * | 1939-04-22 | 1943-04-13 | Aluminum Co Of America | Composition for cleaning aluminum |
US2312855A (en) * | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
US2477841A (en) * | 1945-09-10 | 1949-08-02 | Parker Rust Proof Co | Method of coating metal surfaces comprising aluminum |
US2500673A (en) * | 1947-05-22 | 1950-03-14 | Parker Rust Proof Co | Process of producing a phosphate coating on metals high in aluminum |
US2593449A (en) * | 1950-10-26 | 1952-04-22 | Kaiser Aluminium Chem Corp | Method and composition for treating aluminum and aluminum alloys |
US2901821A (en) * | 1955-11-18 | 1959-09-01 | Detrex Chem Ind | Aluminum coated with aluminum benzoate, and method and composition for making same |
US3007817A (en) * | 1957-11-29 | 1961-11-07 | Parker Rust Proof Co | Cold cleaning and cold phosphate coating process |
US2909455A (en) * | 1958-09-24 | 1959-10-20 | Amchem Prod | Method of coating a succession of aluminum surfaces |
US3106499A (en) * | 1959-05-11 | 1963-10-08 | Rohr Corp | Process and composition for cleaning and polishing aluminum and its alloys |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3420715A (en) * | 1965-06-04 | 1969-01-07 | Cons Foods Corp | Additive for phosphate coating solution |
US3468766A (en) * | 1965-08-27 | 1969-09-23 | Mc Donnell Douglas Corp | Treatment of aluminum |
US3549540A (en) * | 1966-10-31 | 1970-12-22 | Amchem Prod | Method and compositions for treating aluminum surfaces |
US3819424A (en) * | 1971-06-17 | 1974-06-25 | Oxy Metal Finishing Corp | Method and composition for treating metal surfaces |
USRE29827E (en) * | 1972-08-31 | 1978-11-07 | Dominion Foundries And Steel, Limited | Compositions and processes for producing chromium conversion coatings on surfaces of zinc or cadmium |
US3857739A (en) * | 1972-08-31 | 1974-12-31 | Dominion Foundries & Steel | Compositions and processes for producing chromium conversion coatings on surfaces of zinc or cadmium |
US3864147A (en) * | 1972-09-25 | 1975-02-04 | Macdermid Inc | Method of improving the bonding capability of polymer surfaces for subsequently applied coatings, and products thereof |
US3932130A (en) * | 1974-07-03 | 1976-01-13 | Texaco Inc. | Inhibition of aluminum corrosion by sulfuric acid solutions |
US4111722A (en) * | 1976-02-09 | 1978-09-05 | Oxy Metal Industries Corporation | Tannin treatment of aluminum with a fluoride cleaner |
US4256602A (en) * | 1978-12-01 | 1981-03-17 | Pennwalt Corporation | Fluoroborate complex composition and method for cleaning aluminum at low temperatures |
US4427458A (en) | 1980-12-01 | 1984-01-24 | Yoshida Kogyo K. K. | Method for forming protective surface film on aluminum shaped articles |
US20070066503A1 (en) * | 2005-08-19 | 2007-03-22 | Mores Basaly | Methods and compositions for acid treatment of a metal surface |
US20090090635A1 (en) * | 2005-08-19 | 2009-04-09 | Houghton Metal Finishing Company | Methods and compositions for acid treatment of a metal surface |
AU2006283664B2 (en) * | 2005-08-19 | 2012-04-12 | Houghton Technical Corp. | Methods and compositions for acid treatment of a metal surface |
US8252195B2 (en) | 2005-08-19 | 2012-08-28 | Houghton Technical Corp. | Methods and compositions for acid treatment of a metal surface |
US8518286B2 (en) | 2005-08-19 | 2013-08-27 | Houghton Technical Corp. | Methods and compositons for acid treatment of a metal surface |
US9732428B2 (en) | 2005-08-19 | 2017-08-15 | Houghton Technical Corp. | Methods and compositions for acid treatment of a metal surface |
US10260153B2 (en) | 2005-08-19 | 2019-04-16 | Houghton Technical Corp. | Methods and compositions for acid treatment of a metal surface |
Also Published As
Publication number | Publication date |
---|---|
BE651584A (de) | 1964-12-01 |
DE1285830B (de) | 1968-12-19 |
GB1073754A (en) | 1967-06-28 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016 Effective date: 19810317 |
|
AS | Assignment |
Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
|
AS | Assignment |
Owner name: PARKER CHEMICAL COMPANY, 32100 STEPHENSON HWY., MA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004194/0047 Effective date: 19830928 |