US3666638A - Process for anodizing aluminum materials - Google Patents
Process for anodizing aluminum materials Download PDFInfo
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- US3666638A US3666638A US30405A US3666638DA US3666638A US 3666638 A US3666638 A US 3666638A US 30405 A US30405 A US 30405A US 3666638D A US3666638D A US 3666638DA US 3666638 A US3666638 A US 3666638A
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- aluminum
- anodizing
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- anodic coating
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 50
- 239000000463 material Substances 0.000 title abstract description 28
- 238000007743 anodising Methods 0.000 title abstract description 26
- 238000000034 method Methods 0.000 title description 33
- 239000011248 coating agent Substances 0.000 abstract description 28
- 238000000576 coating method Methods 0.000 abstract description 28
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 17
- 239000000956 alloy Substances 0.000 abstract description 16
- 229910045601 alloy Inorganic materials 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 14
- 238000005299 abrasion Methods 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 210000002445 nipple Anatomy 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- -1 e.g. Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000839309 Thesea Species 0.000 description 1
- 208000012886 Vertigo Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- UOCIZHQMWNPGEN-UHFFFAOYSA-N dialuminum;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[O-2].[Al+3].[Al+3] UOCIZHQMWNPGEN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- C25D11/12—Anodising more than once, e.g. in different baths
Definitions
- This invention relates to a process for producing a hard, corrosion resistant surface on aluminum and alloys thereof.
- hard-anodized aluminum is precluded in many applications where extremely corrosive environments exist because of the crack system which extends from the coating surface to the base metal. This crack system originates because of differences between the coefficients of thermal expansion of the metal and the hardanodic coating.
- Another disadvantage of hard-anodized aluminum is the lack of sufficient coverage at sharp edges such as corners and threaded areas.
- the materials which may be beneficially treated utilizing the present method comprises aluminum and aluminum based alloys including alloying elements copper, zinc, magnesium and zinc. These alloys include the structural and nonstructural alloys.
- An example of nonstructural alloys is aluminum 6061 composed of aluminum and magnesium.
- Examples of structural alloys, i.e., having the ability to withstand stress and strain, are aluminum 7075 and 2024 composed of aluminum and zinc, and aluminum and copper, respectively.
- Examples of items composed of structural alloys are automobile pistons.
- the treatment of aluminum utilizing a hard anodizing process produces a dense, hard-anodic coating on the treated materials having microscopic discontinuities extend to the metal and therefore are the means whereby corrosive materials come in contact with the metal and thereby cause the corrosion thereof.
- the hard-anodized material is subjected to a sulfuric acid anodizing process which results in the development of a corrosive resistant oxide lm beneath the first coat, i.e., between the hard coat and the base aluminum.
- the second anodic coating is able to permeate the first or outer coating of aluminum oxide due to the porous nature thereof.
- the material containing the resultant composite coating is subsequently immersed in boiling water to effect sealing, thereby resulting in a coating which is completely continuous. This results in a surface which is both corrosion and abrasion resistant.
- It is a further object of this invention to provide and disclose an improved process for anodizing aluminum materials comprising the subjection of aluminum materials to two distinct acid baths in selected order to produce a composite coating which is completely continuous and then sealing.
- FIG. 1 shows an illustration of the system utilized in the anodizing process.
- FIG. 2 shows a sectional view through 2-2 of FIG. l.
- FIG. 3 shows a ow chart of the steps of the anodizing process.
- the system comprises tank 10.
- the exterior of the tank may be constructed of any suitable material, e.g., plastic.
- the interior of tank 10 is lined with lead 13, as illustrated in FIG. 2, which also serves as the cathode.
- the tank may be of any suitable dimensions depending upon the size of the aluminum materials to be treated.
- a suitable mineral acid electrolyte eg., sulfuric acid 15, is contained within lead lined tank 10.
- Aluminum material 17 is immersed into the electrolyte.
- Said material may be supported by any suitable means, eg., traverse-beam 19.
- Said beam may be constructed of aluminum or titanium.
- Aluminum is more economical and has higher electrical conductivity, but is anodized along with the parts being processed, and therefore requires stripping before reracking.
- Titanium is not anodized, but is much more costly initially and has much lower current-carrying capacity.
- Conduit means 21 are provided near the bottom of tank for the 'admittance of compressed air for agitation and cooling.
- Source 23 supplies the necessary electrical power to decompose the electrolyte.
- tank 10 may lbe provided with iron pipe coils (not shown) for heating and cooling purposes.
- the aluminum panel acts as the anode in the anodizing process. Utilizing a H2504 bath, the following reaction is considered to take place at the cathode thereby liberating H2: 4H3O++4E 1 4H2O+2H2. The following reaction is considered to take place at the anode thereby liberating O2: 40H -"2H20i02
- the 02 combines with metallic aluminum to form aluminum oxide.
- the aluminum materials are lirst subjected to a cleaning process as indicated in FIG. 3.
- the proper cleaning cycle and cleaning material will depend on several factors, e.g., the type of final finish desired, the amount of soil and the kind of soil. If it is necessary to remove unusual accumulation of soil, auxiliary cleaning, i.e., vapor degreasing or spray washing should be performed prior to the first anodizing operation.
- a conventional hard anodize coating is first applied to an aluminum alloy, e.g., ⁇ 6061, material.
- An electrolyte consisting of a by Weight H2504 aqueous solution was utilized. Prior to use, the solution was saturated with carbon dioxide.
- the operating conditions utilized were:
- the process was carried out for a period of 160 minutes. Vigorous agitation utilizing compressed air was applied in order to prevent local overheating. An oxide coating of approximately 0.001 to 0.002" was obtained. An acid range of 12-25 by weight and a temperature range of 20-50 F. has been found operable. In addition to sulfuric acid, oxalic acid, alone or in combination with the sulfuric acid, may be utilized.
- the hard anodized aluminum 6061 is rinsed and then subjected to a second anodizing bath.
- An electrolyte consisting of 15% by weight of a H2504 aqueous solution was used. The operating conditions utilized were:
- Operable conditions include, e.g., temperature 60-80 F., current density 10-15 amp/ft.2 and voltage 14-19 volts.
- the anodizing process was continued for a period of 40-50 minutes.
- a reaction period of e.g., 15-50 minutes may be utilized.
- a resultant maximum coating of up to 0.0008" is desired.
- An acid range of 15-25% by Weight has been found operable.
- sulfuric acid oxalic, alone or in combination with sulfuric, chromic, boric, phosphoric and sul-famic may be utilized.
- the above treated aluminum 6061 is then subjected to a post-anodic treatment in order to provide enhanced corrosion resistance.
- sealing is used in the trade to describe various post-anodic treatments.
- the usual method of sealing comprises the immersion of the anodic coating in a hot or boiling-water bath in order to provide hydration of the anodically formed oxide.
- the sealing process is carried out at an approximate neutral pl-l and at a temperature above C., the formation of the tmonohydrate is favored. However, at temperatures below 80 C., the formation of the trihydrate is favored.
- the monohydrate is preferred from a protective standpoint due to its lower solubility in various corrosive environments.
- the 6061 aluminum alloy material containing the composite coating was sealed by the immersion thereof in boiling water having an approximate neutral pH for a period of 15 minutes, thereby forming the monohydrate.
- Combination #3 was treated in accordance with both the abrasion resistant sulfuric acid anodizing bath and the corrosion resistant sulfuric acid anodizing baths and sealed. The treated combinations were then placed in a 5% salt fog chamber for a period of 150 hours. The metal materials were then removed, allowed to dry, and examined. Substantial corrosion was evident on combination #l and #2. sIn addition, the aluminum fittings were frozen to the stainless steel threaded nipple. Combination #3 showed slight evidence of corrosion. In addition, the tting could be readily removed from the threaded nipple.
- a process for anodizing aluminum and alloys thereof comprising the steps of: (l) treatment of an aluminum material in a rst aqueous hard anodizing acid bath under operating conditions of:
- hard anodizing acid bath is selected from the group consisting of sulfuric acid, oxalic acid, and a mixture thereof.
- a process in accordance with claim 1 wherein the corrosion anodizing acid bath is selected from the group consisting of sulfuric, oxalic, chromic, boric, phosphoric, sulfamic, and a mixture of sulfuric and oxalic acids.
- the treated material is an aluminum based alloy containing alloy elements selected from the group consisting of copper, zinc, magnesium, manganese and silicon.
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A METHOD FOR PRODUCING AN ABRASION RESISTANT ANODIC COATING WITH A DESIRED CORROSION RESISTANT CHARACTERISTIC ON THE SURFACE OF ALUMINUM AND ALLOYS THEREOF COMPRISING THE STEPS OF: (1) INITIALLY ANODIZING THE ALUMINUM MATERIAL IN AN ACID BATH AT CERTAIN CONDITIONS OF TEMPERATURE, CURRENT DENSITY, VOLTAGE ETC., IN ORDER TO PRODUCE A DENSE, HARD ANODIC COATING; (2) SUBJECT THE MATERIAL TO ANOTHER ACID ANODIZING BATH AT CERTAIN TEMPERATURES, CURRENT DENSITY VOLTAGE, ETC., IN ORDER TO DEVELOP A CORROSION RESISTANT ANODIC COATING BETWEEN THE HARD ANODIC COATING AND THE BASE ALUMINUM MATERIAL THEREBY MINIMIZING THE EFFECTS OF THE MICROSPOPIC DISCONTINUITIES, AND THEN (3) SEALING.
Description
May 30, 1972 F HARRlS EI'AL 3,666,638
PROCESS FOR ANODIZING ALUMINUM MATERIALS Filed April 21, 1970 INVENTORS,
mm w
ATTORNEYL,
United States Patent O 3,666,638 PROCESS FOR ANODIZYING ALUMINUM MATERIALS Frank L. Harris, 3803 Massachusetts Ave. SE., Washington, D.C. 20019, and Sidney Levine, 8505 Buckhannon Drive, Potomac, Md. 20854 Filed Apr. 21, 1970, Ser. No. 30,405 Int. Cl. C23f 7/06 U.S. Cl. 204-35 N 6 Claims ABSTRACT OF THE DISCLOSURE A method for producing an abrasion resistant anodic coating with a desired corrosion resistant characteristic on the surfaces of aluminum and alloys thereof comprising the steps of:
(l) initially anodizing the aluminum material in an acid -bath at certain conditions of temperature, current density, voltage etc., in order to produce a dense, hard anodic coating;
(2) subject the material to another acid anodizing bath at certain temperatures, current density, voltage, etc., in order to develop a corrosion resistant anodic coating between the hard anodic coating andthe base aluminum material thereby minimizing the effects of the microscopic discontinuities, and then (3) sealing.
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalty thereon.
This invention relates to a process for producing a hard, corrosion resistant surface on aluminum and alloys thereof.
In the field of illumination, aluminum has long been recognized for its ability to reflect White light. However, the use of aluminum as a reflector was. curtailed by the loss of reflectivity over an extended period of time due to industrial atmospheric influences and yweathering and to the susceptibility of the reflector surface to scratching, when cleaned.
In the early l930s the sulfuric acid anodic oxidation process made its commercial debut in the United States, thereby permitting the formation of a protective coating of aluminum oxide on the aluminum surface. This development overcame the loss of light output due to corrosive influences and resistance to surface abrasion.
The application of the anodic coating accomplished the desired results. However, other problems were introduced. For example, the initial reflection factor of the aluminum was lowered. However, new chemical and electrochemical brightening procedures were developed. With the introduction of theseA processes, considerable interest in brightf'inished and anodically treated aluminum developed in areas outside the eld of illumination, eg., automotive and appliance trim, refrigerator shelves, architectural applications, and continuously processed coiled stock for subsequent fabrication. The aluminum industry responded by the introduction of alloys receptive to the brightening and anodic processing technique for stamping, extrusion, spinnings, machined parts, forgin gs, etc.
The use of hard-anodized aluminum is precluded in many applications where extremely corrosive environments exist because of the crack system which extends from the coating surface to the base metal. This crack system originates because of differences between the coefficients of thermal expansion of the metal and the hardanodic coating. Another disadvantage of hard-anodized aluminum is the lack of sufficient coverage at sharp edges such as corners and threaded areas.
ice
It was considered that the corrosion resistance of hardanodized aluminum or alloys thereof could be significantly increased by plugging the microscopic discontinuities so that there would be no free pathways to the base metal. It was deemed practical to close the crack system by de- -velopment of an anodic coating between the metal and' the hard coat after development of the hard coat. This composite coating provides an effective barrier at points where the cracks are open to the base metal.
The materials which may be beneficially treated utilizing the present method comprises aluminum and aluminum based alloys including alloying elements copper, zinc, magnesium and zinc. These alloys include the structural and nonstructural alloys. An example of nonstructural alloys is aluminum 6061 composed of aluminum and magnesium. Examples of structural alloys, i.e., having the ability to withstand stress and strain, are aluminum 7075 and 2024 composed of aluminum and zinc, and aluminum and copper, respectively. Examples of items composed of structural alloys are automobile pistons. Thus, it is apparent that many objects composed of aluminum and its alloys must have the ability to withstand both the effects of corrosion and abrasion.
The treatment of aluminum utilizing a hard anodizing process produces a dense, hard-anodic coating on the treated materials having microscopic discontinuities extend to the metal and therefore are the means whereby corrosive materials come in contact with the metal and thereby cause the corrosion thereof. To counteract the corrosive effect, the hard-anodized material is subjected to a sulfuric acid anodizing process which results in the development of a corrosive resistant oxide lm beneath the first coat, i.e., between the hard coat and the base aluminum. The second anodic coating is able to permeate the first or outer coating of aluminum oxide due to the porous nature thereof. The material containing the resultant composite coating is subsequently immersed in boiling water to effect sealing, thereby resulting in a coating which is completely continuous. This results in a surface which is both corrosion and abrasion resistant.
It is an object of this invention to provide and disclose an improved process for anodizing aluminum.
It is a further object of this invention to provide and disclose an improved process for anodizing aluminum alloys.
It is a further object of this invention to provide and disclose an improved process for anodizing aluminum materials comprising the subjection of aluminum materials to two distinct acid baths in selected order to produce a composite coating which is completely continuous and then sealing.
Other objects and a fuller understanding of this invention may be ascertained by referring to the following description and claims taken in conjunction with the accompanying drawing in which:
FIG. 1 shows an illustration of the system utilized in the anodizing process.
FIG. 2 shows a sectional view through 2-2 of FIG. l.
FIG. 3 shows a ow chart of the steps of the anodizing process.
Referring now to FIG. l, the system comprises tank 10. The exterior of the tank may be constructed of any suitable material, e.g., plastic. The interior of tank 10 is lined with lead 13, as illustrated in FIG. 2, which also serves as the cathode. The tank may be of any suitable dimensions depending upon the size of the aluminum materials to be treated. A suitable mineral acid electrolyte, eg., sulfuric acid 15, is contained within lead lined tank 10. Aluminum material 17 is immersed into the electrolyte. Said material may be supported by any suitable means, eg., traverse-beam 19. Said beam may be constructed of aluminum or titanium. Aluminum is more economical and has higher electrical conductivity, but is anodized along with the parts being processed, and therefore requires stripping before reracking. Titanium is not anodized, but is much more costly initially and has much lower current-carrying capacity. Conduit means 21 are provided near the bottom of tank for the 'admittance of compressed air for agitation and cooling. Source 23 supplies the necessary electrical power to decompose the electrolyte. In addition tank 10 may lbe provided with iron pipe coils (not shown) for heating and cooling purposes.
The aluminum panel acts as the anode in the anodizing process. Utilizing a H2504 bath, the following reaction is considered to take place at the cathode thereby liberating H2: 4H3O++4E 1 4H2O+2H2. The following reaction is considered to take place at the anode thereby liberating O2: 40H -"2H20i02|-4E. The 02 combines with metallic aluminum to form aluminum oxide.
In operation, the aluminum materials are lirst subjected to a cleaning process as indicated in FIG. 3. The proper cleaning cycle and cleaning material will depend on several factors, e.g., the type of final finish desired, the amount of soil and the kind of soil. If it is necessary to remove unusual accumulation of soil, auxiliary cleaning, i.e., vapor degreasing or spray washing should be performed prior to the first anodizing operation.
In the present invention, a conventional hard anodize coating is first applied to an aluminum alloy, e.g.,` 6061, material. An electrolyte consisting of a by Weight H2504 aqueous solution was utilized. Prior to use, the solution was saturated with carbon dioxide. The operating conditions utilized were:
Temperature: 25-32 F. Current density: 25 amp/ft.2 Voltage: Up to 75 volts.
The process was carried out for a period of 160 minutes. Vigorous agitation utilizing compressed air was applied in order to prevent local overheating. An oxide coating of approximately 0.001 to 0.002" was obtained. An acid range of 12-25 by weight and a temperature range of 20-50 F. has been found operable. In addition to sulfuric acid, oxalic acid, alone or in combination with the sulfuric acid, may be utilized.
The hard anodized aluminum 6061 is rinsed and then subjected to a second anodizing bath. An electrolyte consisting of 15% by weight of a H2504 aqueous solution was used. The operating conditions utilized were:
Temperature: 70 F. 1 Current density: 15 amp/ft.z Voltage: 19 volts.
It should be understood that the specific values cited above are not restrictive, but are determined by coating requirements in each instance. Operable conditions include, e.g., temperature 60-80 F., current density 10-15 amp/ft.2 and voltage 14-19 volts.
The anodizing process was continued for a period of 40-50 minutes. A reaction period of e.g., 15-50 minutes may be utilized. A resultant maximum coating of up to 0.0008" is desired. An acid range of 15-25% by Weight has been found operable. In addition to sulfuric acid, oxalic, alone or in combination with sulfuric, chromic, boric, phosphoric and sul-famic may be utilized.
It is pointed out that both of the acid bath steps and the sealing step of this new method are separately disclosed'in the prior art, i.e., Metal Finishing 1969 Guidebook Directory. Therefore no novelty is claimed in the separate steps of the method. The patentable novelty is considered to reside in the combination of the steps in a selected consecutive order in the treatment of an aluminum material to obtain a hard anodized finish with greatly improved corrosion resistance and unirnpaired abrasion resistant. Furthermore, the invention is not limited to the above disclosed specific acid baths.
The above treated aluminum 6061 is then subjected to a post-anodic treatment in order to provide enhanced corrosion resistance. The term sealing is used in the trade to describe various post-anodic treatments. The usual method of sealing comprises the immersion of the anodic coating in a hot or boiling-water bath in order to provide hydration of the anodically formed oxide.
The following reactions are considered to take place during sealing, (1) the formation of the aluminum oxide monohydrate, which is illustrated -by the following equation:
A1203 H209 A1203 and (2) the formation of aluminum oxide trihydrate, which is illustrated by the following equation:
Generally, it has been discovered that if the sealing process is carried out at an approximate neutral pl-l and at a temperature above C., the formation of the tmonohydrate is favored. However, at temperatures below 80 C., the formation of the trihydrate is favored. The monohydrate is preferred from a protective standpoint due to its lower solubility in various corrosive environments.
The 6061 aluminum alloy material containing the composite coating was sealed by the immersion thereof in boiling water having an approximate neutral pH for a period of 15 minutes, thereby forming the monohydrate.
Experimentation was conducted in order to show the benecial eiects resulting from the utilization of the aluminum materials which have been treated in accordance with the present process. Three metal objects, each consisting of the combination of a stainless steel threaded nipple and an aluminum fitting (6061) therefor, were selected. The stainless steel and aluminum combination was selected because of its propensity to corrode under adverse condition. Combination #l was treated in accordance with the heretofore described abrasion resistant sulfuric acid anodizing process and sealed. Combination #2 was treated in accordance with the heretofore described corrosion resistant sulfuric acid anodizing process and sealed. Combination #3 was treated in accordance with both the abrasion resistant sulfuric acid anodizing bath and the corrosion resistant sulfuric acid anodizing baths and sealed. The treated combinations were then placed in a 5% salt fog chamber for a period of 150 hours. The metal materials were then removed, allowed to dry, and examined. Substantial corrosion was evident on combination #l and #2. sIn addition, the aluminum fittings were frozen to the stainless steel threaded nipple. Combination #3 showed slight evidence of corrosion. In addition, the tting could be readily removed from the threaded nipple.
Although we have described our invention with a certain degree of particularity, we wish it to be understood that We do not desire to be limited to the exact details shown and described, for obvious modification will occur to a person skilled in the art.
Having described our invention, -we claim:
1. A process for anodizing aluminum and alloys thereof comprising the steps of: (l) treatment of an aluminum material in a rst aqueous hard anodizing acid bath under operating conditions of:
Temperature: 20-50 F.
Current density: 25 amp/ft.2
,Voltagez up to 75 volts for a period of 20-160 minutes in order to produce an abrasion resistant anodic surface, rinsing, treatment of said aluminum material in a second aqueous'corrosion resistant anodizing acid bath under operating conditions of:
Temperature: 60-80 F.
Current density: 10-25 amp/ft.2
Voltage: 14-18 volts for a period of 15-50 minutes such that a continuous anodic coating develops beneath the abrasion resistant anodic coating, and sealing.
2. A process in accordance With claim 1 wherein the hard anodizing acid bath is selected from the group consisting of sulfuric acid, oxalic acid, and a mixture thereof.
3. A process in accordance with claim 1 wherein the corrosion anodizing acid bath is selected from the group consisting of sulfuric, oxalic, chromic, boric, phosphoric, sulfamic, and a mixture of sulfuric and oxalic acids.
4. A process in accordance with claim 1 wherein the treated material is aluminum.
5. A process in accordance with claim 1 wherein the treated material is an aluminum based alloy containing alloy elements selected from the group consisting of copper, zinc, magnesium, manganese and silicon.
6. A process in accordance with claim 1 wherein the resultant composite coating is sealed by the immersion thereof in boiling water for a period of 15 minutes.
References Cited UNITED STATES PATENTS I OHN H. MACK, Primary Examiner W. I. SOLOMON, Assistant Examiner U.S. C1. X.R. 204-42
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US3040570A | 1970-04-21 | 1970-04-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3666638A true US3666638A (en) | 1972-05-30 |
Family
ID=21854048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US30405A Expired - Lifetime US3666638A (en) | 1970-04-21 | 1970-04-21 | Process for anodizing aluminum materials |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3666638A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875026A (en) * | 1974-05-22 | 1975-04-01 | Rca Corp | Method for producing aluminum holographic masters |
| US3962049A (en) * | 1971-05-13 | 1976-06-08 | Kabushiki Kaisha Aiden | Process for coloring aluminum anodic oxide film |
| US4554216A (en) * | 1982-02-23 | 1985-11-19 | Hoechst Aktiengesellschaft | Process for manufacturing support materials for offset printing plates |
| US4554057A (en) * | 1982-02-23 | 1985-11-19 | Hoechst Aktiengesellschaft | Process for manufacturing support materials for offset printing plates |
| US4606796A (en) * | 1983-01-24 | 1986-08-19 | Asahi Malleable Iron Co., Ltd. | Colored, anodized aluminum-base article and method of preparing same |
| US5158663A (en) * | 1991-08-12 | 1992-10-27 | Joseph Yahalom | Protective coatings for metal parts to be used at high temperatures |
| US5382347A (en) * | 1991-08-18 | 1995-01-17 | Yahalom; Joseph | Protective coatings for metal parts to be used at high temperatures |
| US20050150771A1 (en) * | 2003-12-23 | 2005-07-14 | Erich Kock | Method for anodizing aluminum materials |
| US20080035486A1 (en) * | 2004-05-04 | 2008-02-14 | Anton Albrecht | Method for Production of a Coating and Anode Used in Such a Method |
| US20080265218A1 (en) * | 2007-04-24 | 2008-10-30 | Lifchits Alexandre D | Composite layer and method of forming same |
| US20140008236A1 (en) * | 2012-07-04 | 2014-01-09 | Universite De Lorraine | Anodization treatment method for aluminum alloys containing cooper |
| CN105350051A (en) * | 2015-11-13 | 2016-02-24 | 哈尔滨东安发动机(集团)有限公司 | Method for avoiding Sn-Bi alloy pollution on surface of aluminum part |
| CN105401201A (en) * | 2015-12-22 | 2016-03-16 | 上海申和热磁电子有限公司 | Anodic oxidation technology used for aluminum alloy base material of TFT liquid crystal glass panel |
| US20160102417A1 (en) * | 2014-10-13 | 2016-04-14 | United Technologies Corporation | Hierarchically structured duplex anodized aluminum alloy |
| US20160138179A1 (en) * | 2014-03-27 | 2016-05-19 | Suzuki Motor Corporation | Anodizing treatment method and structure of internal combustion engine |
| CN107245748A (en) * | 2017-04-24 | 2017-10-13 | 南京邮电大学 | A kind of two-step anodization technique of aluminium alloy |
| CN109208055A (en) * | 2017-06-30 | 2019-01-15 | 比亚迪股份有限公司 | A kind of aluminium alloy and preparation method thereof and handset shell |
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| US11149334B2 (en) * | 2018-08-14 | 2021-10-19 | Johnson Brass & Machine Foundry, Inc. | Methods for forming clean aluminum alloys |
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1970
- 1970-04-21 US US30405A patent/US3666638A/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3962049A (en) * | 1971-05-13 | 1976-06-08 | Kabushiki Kaisha Aiden | Process for coloring aluminum anodic oxide film |
| US3875026A (en) * | 1974-05-22 | 1975-04-01 | Rca Corp | Method for producing aluminum holographic masters |
| US4554216A (en) * | 1982-02-23 | 1985-11-19 | Hoechst Aktiengesellschaft | Process for manufacturing support materials for offset printing plates |
| US4554057A (en) * | 1982-02-23 | 1985-11-19 | Hoechst Aktiengesellschaft | Process for manufacturing support materials for offset printing plates |
| US4606796A (en) * | 1983-01-24 | 1986-08-19 | Asahi Malleable Iron Co., Ltd. | Colored, anodized aluminum-base article and method of preparing same |
| US5158663A (en) * | 1991-08-12 | 1992-10-27 | Joseph Yahalom | Protective coatings for metal parts to be used at high temperatures |
| US5382347A (en) * | 1991-08-18 | 1995-01-17 | Yahalom; Joseph | Protective coatings for metal parts to be used at high temperatures |
| US20050150771A1 (en) * | 2003-12-23 | 2005-07-14 | Erich Kock | Method for anodizing aluminum materials |
| US20080035486A1 (en) * | 2004-05-04 | 2008-02-14 | Anton Albrecht | Method for Production of a Coating and Anode Used in Such a Method |
| US7771578B2 (en) | 2004-05-04 | 2010-08-10 | Mtu Aero Engines Gmbh | Method for producing of a galvanic coating |
| US20080265218A1 (en) * | 2007-04-24 | 2008-10-30 | Lifchits Alexandre D | Composite layer and method of forming same |
| US20140008236A1 (en) * | 2012-07-04 | 2014-01-09 | Universite De Lorraine | Anodization treatment method for aluminum alloys containing cooper |
| US10458034B2 (en) * | 2014-03-27 | 2019-10-29 | Suzuki Motor Corporation | Anodizing treatment method and structure of internal combustion engine |
| US10179956B2 (en) | 2014-03-27 | 2019-01-15 | Suzuki Motor Corporation | Anodic oxide coating, treatment method therefor, and piston for internal combustion engine |
| US20160138179A1 (en) * | 2014-03-27 | 2016-05-19 | Suzuki Motor Corporation | Anodizing treatment method and structure of internal combustion engine |
| US20160102417A1 (en) * | 2014-10-13 | 2016-04-14 | United Technologies Corporation | Hierarchically structured duplex anodized aluminum alloy |
| US11299815B2 (en) | 2014-10-13 | 2022-04-12 | Raytheon Technologies Corporation | Hierarchically structured duplex anodized aluminum alloy |
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| CN105350051A (en) * | 2015-11-13 | 2016-02-24 | 哈尔滨东安发动机(集团)有限公司 | Method for avoiding Sn-Bi alloy pollution on surface of aluminum part |
| CN105350051B (en) * | 2015-11-13 | 2017-08-08 | 哈尔滨东安发动机(集团)有限公司 | A kind of method for solving aluminum hardware surface Sn Bi alloy contaminations |
| CN105401201A (en) * | 2015-12-22 | 2016-03-16 | 上海申和热磁电子有限公司 | Anodic oxidation technology used for aluminum alloy base material of TFT liquid crystal glass panel |
| CN107245748A (en) * | 2017-04-24 | 2017-10-13 | 南京邮电大学 | A kind of two-step anodization technique of aluminium alloy |
| CN109208055A (en) * | 2017-06-30 | 2019-01-15 | 比亚迪股份有限公司 | A kind of aluminium alloy and preparation method thereof and handset shell |
| US11149334B2 (en) * | 2018-08-14 | 2021-10-19 | Johnson Brass & Machine Foundry, Inc. | Methods for forming clean aluminum alloys |
| US11149333B2 (en) * | 2018-08-14 | 2021-10-19 | Johnson Brass & Machine Foundry, Inc. | Clean aluminum alloys |
| US11597987B2 (en) * | 2018-08-14 | 2023-03-07 | Johnson Brass & Machine Foundry, Inc. | Clean aluminum alloys and methods for forming such alloys |
| US11613800B2 (en) * | 2018-08-14 | 2023-03-28 | Johnson Brass & Machine Foundry, Inc. | Clean aluminum alloys and methods for forming such alloys |
| US12134828B2 (en) | 2020-11-13 | 2024-11-05 | Rtx Corporation | Mixed acid anodization |
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