US3909371A - Process for producing a protective film on an aluminum surface - Google Patents
Process for producing a protective film on an aluminum surface Download PDFInfo
- Publication number
- US3909371A US3909371A US300159A US30015972A US3909371A US 3909371 A US3909371 A US 3909371A US 300159 A US300159 A US 300159A US 30015972 A US30015972 A US 30015972A US 3909371 A US3909371 A US 3909371A
- Authority
- US
- United States
- Prior art keywords
- aluminum
- water
- percent
- soluble
- coating
- 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
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000001681 protective effect Effects 0.000 title description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- 150000003141 primary amines Chemical class 0.000 claims 2
- 150000003335 secondary amines Chemical class 0.000 claims 2
- -1 aliphatic primary amines Chemical class 0.000 abstract description 18
- 238000002048 anodisation reaction Methods 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 235000010210 aluminium Nutrition 0.000 description 40
- 239000000758 substrate Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 1
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
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
Definitions
- a process for producing a firmly adhered, corrosion resistant film on an aluminum or aluminum alloy surface by means of anodization using an electrolyte containing at least one of the compounds selected from the group consisting of, aliphatic primary amines and aliphatic secondary amines which compounds act upon a coating to cause the same to adhere intimately to the aluminum surface on one hand and impart corrosion resistance to the latter on the other.
- the formation of the aluminum oxide layer and resinous coating may be carried out in one step or in two steps.
- This invention relates to a process of producing on an aluminum or aluminum alloy surface a protective, ornamental and corrosion resistant film. More specifically, the present invention is concerned with the process in which an aluminum substrate is coated by immersion deposit with a continuous, smooth and firmly adhered resinous film. Yet more specifically, the invention is further concerned with the aluminum surface treatment in which an aluminum surface is provided with an anodized under-coat and a resinous over-coat simultaneously.
- a number of processes have been hitherto been proposed for treating and finishing aluminum-bearing substrates so that product aluminum articles are resistant to environmental attack, i.e. corrosion by acidic or alkaline atmosphere and will present a continuous, smooth, level surface appearance.
- a protective coating and/or an ornamental dye Prior to the application of a protective coating and/or an ornamental dye, the aluminum surface is subjected to an undercoat treatment such as by anodization and chemical conversion which has important bearing upon the properties of a protective film formed over the under-coat. Therefore, a variety of processes have also been proposed for forming an under-coat on an aluminum substrate. For example, there is known a process wherein a film is formed by chemical conversion on an aluminum surface, followed by application of a protective outer coating.
- the protective resinous film is securely adhered to the under-coated film but the coated aluminum surface is not satisfactorily corrosionresistant.
- a process wherein the aluminum surface is anodized prior to the application of a protective coating is well resistant to corrosion and superior in many respects chemically converted aluminum surface. But, the anodization employed therefor is extremely costly.
- an advanced process in which anodization is combined with chemical conversion but such combined process is rather complicated and economically infeasible.
- a desired corrosionresistant oxide film can be produced'on an aluminum or aluminum alloy surface by means of anodization employing an electrolyte which contains at least one of the compounds selected from the group consisting of aliphatic primary amines and aliphatic secondary amines.
- an electrolyte which contains at least one of the compounds selected from the group consisting of aliphatic primary amines and aliphatic secondary amines.
- the oxide film greatly enhances adhesion of the coating composition to the aluminum surface.
- the oxide film according to the invention is substantially transparent, hence a variety of colors may be chosen for an over-coat to be applied to the aluminum product.
- greasing, cleaning and water-rinsing the surface etching the waterwashed surface with an alkaline solution; neutralizing and water-washing the etched surface; and anodizing the surface in an electrolyte containing 1.0-15.0 weight percent of at least one member selected from the group consisting of aliphatic primary amines and aliphatic secondary amines which is soluble under the experimental conditions in the aqueous solution.
- Another aspect of the invention resides in the provision of a process which comprises:' degreasing, cleaning and water-rinsing the surface; etching the waterrinsed surface with an alkaline solution; neutralizing and water-washing the etched surface; and anodizing the surface in an electrolyte containing 1.0-15.0 weight percent of at least one member selected from the group consisting of aliphatic primary amines and aliphatic secondary amines which is soluble under the experimental conditions in the aqueous solution and 20.0-50.0 weight percent of a water-soluble thermosetting resin; allowing the thus anodized surface to set; and drying and hardening the surface at a temperature of l50200c over a period of 15-30 minutes.
- the electrolyte may' also contain an ETHODUOMEEN which is the trade name for ethylene oxide adducts with a fatty acid diamine:
- ETHODUOMEEN is the trade name for ethylene oxide adducts with a fatty acid diamine:
- the term aliphatic primary amines includes ehtylenediamine and the like.
- the term aliphatic secondary amines includes dimethyl amine, N-methyl ethanolamine and the like.
- thermosetting resins as used herein includes acrylic resins, alkyd resins, acrylalkyd resins, urea resins, aminoalkyd resins, melamine resins and phenolic resins. These resins mentioned as above when used in amounts of less than 20.0 percent or more 50.0 percent will fail to form a satisfactory resinous film on an aluminum surface.
- the aluminum surface in the above second mentioned process is advantageously anodized for 5-30 minutes with DC 40-60 volts and a current density of 0.01-1 A/dm at a bath temperature of 50-90C. More advantageously, the surface can be anodized initially with a relatively low voltage i.e. DC 10-20 volts for 5-15 minutes, thereby forming thereon an oxide film and then with a relatively high voltage i.e. DC 30-60 volts for l-15 minutes thereby electrically depositing thereon a resinous film.
- EXAMPLE I An aluminum workpiece was subjected to the pretreatment in which it was degreased and cleaned by dipping for 30 seconds in 8 percent NaOH solution maintained at C, washed with water, neutralized by dipping for 15 seconds in a 15 percent I-INO solution at room temperature, and washed again with water.
- the pretreated substrate was subjected to anodization using an electrolyte containing 3 weight percent of ETHODUOMEEN (trade name for ethylene oxide adduct of fatty acid diamine) operated with DC 55 volts Table I Coating compositions (parts by weight) Adhesion (kg/cm”) Coat Ethylene No.
- EXAMPLE VI source and a current density of 1 A/dm at a bath temperature of about 30c.
- the substrate was thus anodized for 15 minutes, whereupon there was obtained a transparent oxide film deposited on the aluminum workpiece.
- EXAMPLE II An aluminum-bearing substrate was pretreated in the manner described in EXAMPLE I.
- the pretreated substrate was subjected to anodization using an electrolyte containing 10 weight percent of ethylenediamine operated with DC 30 volts and a current dinsity of 0.5 A/dm at a bath temperature of about 18C.
- the substrate was thus anodized for 30 minutes, whereupon a transparent oxide film was produced on the aluminum workpiece.
- EXAMPLE III-V Aluminum workpieces were subjected to the pretreatment in which they were degreased and cleaned by dipping for 30 seconds in 8 percent NaOH solution maintained at 80C, washed with water, neutralized by dipping for 20 seconds in a percent NI-IO solution at room temperature, and washed again with water.
- the thus pretreated substrates were subjected to anodization using electrolytes containing 1.0, 3.0 and 5.0 weight percent respectively of N-methyl ethanolamine operated with DC 50-100 volts and a current density of 0.15-0.55 A/dm at a bath temperature of about 11C.
- the substrate was thus anodized for 15 minutes whereupon a transparent oxide film was produced on each aluminum substrate.
- COMPARATIVE EXAMPLE An aluminum substrate was pretreated in the manner described in EXAMPLE I.
- the pretreated substrate was subjected to anodization using a 15 percent H 80 electrolyte operated with DC 15 volts and a current density of l A/dm at a bath temperature of about C.
- the substrate was thus anodized for 15 minutes, then washed and dried thereby providing a comparative test piece.
- This test piece together with the alumi num piece obtained according to EXAMPLE I and EX- AMPLE II were immersed for 1 minute in an immersion bath containing the coating compositions shown in Table 1.
- Electrolyte Composition (weight percent) Titanium oxide Acrylic resin Melamine resin ETHODUOMEEN Glycol Ethylalcohol Water Surfactant every-Pa OOOOOONN EXAMPLE VII
- An aluminum substrate was pretreated in the manner described in EXAMPLE I.
- the pretreated substrate was subjected to anodization using an electrolyte of the composition shown in Table III operated with DC 40 volts and a current density of 0.5 A/dm at a bath temperature of C.
- the substrate was thus anodized for 15 minutes, and then pulled out, drained for 8 minutes, allowed to set for 7 minutes and thereafter heated at C for 30 minutes to harden the coating, whereupon there was produced a continuous, uniform, firmly adhered film on the aluminum workpiece.
- EXAMPLE VIII An aluminum substrate was pretreated in the manner described in EXAMPLES III-V.
- the pretreated sub- Table IV Electrolyte composition (weight percent) Acrylic resin 2 Melamine resin N-methyl ethanolamine Glycol Ethylalcohol Water Surfactant What is claimed is:
- a process for forming a coating on an aluminum or aluminum alloy surface which comprises: degreasing, cleaning and water-rinsing the surface; etching the water-rinsed surface with an alkaline solution; neutralizing and water-washing the etched surface; and treating the surface as the anode to form an aluminum oxide layer thereon in an aqueous electrolyte containing 1.0 15.0 weight percent of at least one compound which is soluble in the aqueous solution under the experimental conditions selected from the group consisting of, aliphatic primary amines and aliphatic secondary amines; immersing the treated surface in a coating composition comprising 20-50 percent of at least one water-soluble thermosetting resin and 01-10 percent of at least one compound soluble in the aqueous solution under the experimental conditions, which compound is selected from the group consisting of, aliphatic primary amines and aliphatic secondary amines and allowing the thus coated aluminum surface to set, dry and harden at 200C. over a period of 15-30 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Electrochemical Coating By Surface Reaction (AREA)
- Chemical Treatment Of Metals (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/556,975 US3988217A (en) | 1971-10-22 | 1975-03-10 | Process for producing a protective film on an aluminum surface |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP46083340A JPS5214214B2 (enrdf_load_stackoverflow) | 1971-10-22 | 1971-10-22 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/556,975 Division US3988217A (en) | 1971-10-22 | 1975-03-10 | Process for producing a protective film on an aluminum surface |
Publications (1)
Publication Number | Publication Date |
---|---|
US3909371A true US3909371A (en) | 1975-09-30 |
Family
ID=13799694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US300159A Expired - Lifetime US3909371A (en) | 1971-10-22 | 1972-10-24 | Process for producing a protective film on an aluminum surface |
Country Status (2)
Country | Link |
---|---|
US (1) | US3909371A (enrdf_load_stackoverflow) |
JP (1) | JPS5214214B2 (enrdf_load_stackoverflow) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000053A (en) * | 1972-10-28 | 1976-12-28 | Nippon Paint Co., Ltd. | Method for treatment of aluminum substrate |
WO2005014894A1 (en) * | 2003-08-06 | 2005-02-17 | Decoma International Inc. | Protective coating for automotive trim pieces and method of making the same |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0832966B2 (ja) * | 1990-02-01 | 1996-03-29 | スカイアルミニウム株式会社 | 缶蓋用アルミニウム合金塗装用板及びその製造方法 |
JPH03274296A (ja) * | 1990-03-22 | 1991-12-05 | Sky Alum Co Ltd | 深絞り用アルミニウム合金塗装用材及びその製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855351A (en) * | 1954-09-20 | 1958-10-07 | Sanford Process Co Inc | Process for electrolytically producing oxide coating on aluminum and aluminum alloys |
US3455805A (en) * | 1966-02-01 | 1969-07-15 | Shell Oil Co | Process for coating surfaces by electrodeposition |
US3632486A (en) * | 1967-10-17 | 1972-01-04 | Metalloxyd Gmbh | Method and arrangement for continuous etching and anodizing of aluminum |
US3681224A (en) * | 1970-05-08 | 1972-08-01 | Textron Inc | Electrophoretic coating method |
US3726783A (en) * | 1968-02-03 | 1973-04-10 | Metalloxyd Gmbh | Apparatus for producing an aluminum foil or band with an electrically insulating or decorative coating thereon |
US3775266A (en) * | 1971-06-29 | 1973-11-27 | Kuboko Paint Co | Process for forming resinous films on anodized aluminum substrates |
-
1971
- 1971-10-22 JP JP46083340A patent/JPS5214214B2/ja not_active Expired
-
1972
- 1972-10-24 US US300159A patent/US3909371A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2855351A (en) * | 1954-09-20 | 1958-10-07 | Sanford Process Co Inc | Process for electrolytically producing oxide coating on aluminum and aluminum alloys |
US3455805A (en) * | 1966-02-01 | 1969-07-15 | Shell Oil Co | Process for coating surfaces by electrodeposition |
US3632486A (en) * | 1967-10-17 | 1972-01-04 | Metalloxyd Gmbh | Method and arrangement for continuous etching and anodizing of aluminum |
US3726783A (en) * | 1968-02-03 | 1973-04-10 | Metalloxyd Gmbh | Apparatus for producing an aluminum foil or band with an electrically insulating or decorative coating thereon |
US3681224A (en) * | 1970-05-08 | 1972-08-01 | Textron Inc | Electrophoretic coating method |
US3775266A (en) * | 1971-06-29 | 1973-11-27 | Kuboko Paint Co | Process for forming resinous films on anodized aluminum substrates |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000053A (en) * | 1972-10-28 | 1976-12-28 | Nippon Paint Co., Ltd. | Method for treatment of aluminum substrate |
WO2005014894A1 (en) * | 2003-08-06 | 2005-02-17 | Decoma International Inc. | Protective coating for automotive trim pieces and method of making the same |
Also Published As
Publication number | Publication date |
---|---|
JPS4847448A (enrdf_load_stackoverflow) | 1973-07-05 |
JPS5214214B2 (enrdf_load_stackoverflow) | 1977-04-20 |
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