US3915813A - Method for electrolytically coloring aluminum articles - Google Patents
Method for electrolytically coloring aluminum articles Download PDFInfo
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- US3915813A US3915813A US416809A US41680973A US3915813A US 3915813 A US3915813 A US 3915813A US 416809 A US416809 A US 416809A US 41680973 A US41680973 A US 41680973A US 3915813 A US3915813 A US 3915813A
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 34
- 238000004040 coloring Methods 0.000 title claims description 21
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000007743 anodising Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 10
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 7
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 7
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 6
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000003086 colorant Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000553 6063 aluminium alloy Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019646 color tone Nutrition 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical class [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 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
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
- C25D11/22—Electrolytic after-treatment for colouring layers
Definitions
- An aluminum article is colored by forming an oxidized coating thereon by usual anodizing treatment and sub- [301 Foreign Apphcatlon Pnonty Data sequently subjecting the treated article to electrolysis Nov. 21, 1972 Japan 47-1175 61 in a metal salt containing electrolytic h with rent having a discontinuous distorted wave.
- the present invention relates to a method for coloring aluminum articles, more particularly to a method for coloring aluminum articles uniformly.
- aluminum refers to pure aluminum, commercial aluminum containing small amounts of impurities and aluminum alloys predominantly composed of aluminum.
- the conventional process has the drawback of being poor in throwing power. More specifically, when treated with the known process, a plate material will be colored deep at its periphery whilst the center portion thereof will exhibit a pale color. With a shaped extrusion, the process fails to produce a satisfactory coloring effect especially on a recessed portion. It is further noted that when a plurality of articles are suspended from the same hanger for electrolytic treatment, there arises a color difference between articles positioned in vertical arrangement or between those arranged on the same level. Moreover, it is difficult to color articles in different colors using the same electrolytic bath.
- This invention provides a method for electrolytically coloring aluminum articles free of the foregoing drawbacks.
- the present method comprises a first step of forming an oxidized coating on an aluminum article by usual anodizing treatment and a second step of subjecting the treated article to electrolysis in a metal salt-containing electrolytic bath using discontinuous distorted wave current.
- the current has alternating positive current portions and negative current portions, at least the negative portion having a conduction angle controlled by a thyristor, the positive current portions being thereby rendered larger than the negative current portions so as to assure excellent throwing power and to thereby make it possible for the second step to give coatings in different color tones using the same electrolytic bath.
- acids conventionally used to form anodic coatings are all employable, examples thereof being sulfuric acid, oxalic acid, chromic acid, etc., among which sulfuric acid is generally used.
- the acid concentration is suitably 100 to 200 g/l.
- the electrolysis is preferably conducted with direct current having a current density of 1.0 to 1.5 A/dm
- the electrolytic bath for the second step contains as a main ingredient a mineral acid or organic acid useful for the formation of anodic coating like the electrolytic bath of the first step and at least one metal salt added to the acid ingredient.
- sulfuric acid and boric acid are usable as the mineral acid, and oxalic acid and sulfosalicylic acid as the organic acid, among which sulfuric acid is preferable. It is advantageous to use in the second step an acid such as given above which is capable of forming an anodic coating because the positive current portions of the discontinuous distorted wave current will participate in anodizing the aluminum article.
- the metal salt are watersoluble salts of tin, silver copper, selenium, cobalt, nickel and the like.
- the electrolytic bath may contain 10 to 300 g/l of sulfuric acid and l to 50 g/l of stannous sulfate.
- the bath When subjected to electrolysis in the bath thus prepared, aluminum articles are colored in tones widely ranging from gold to dark amber.
- the bath may contain 10 to 300 g/l of sulfuric acid and 0.5 to 5.0 g/l of silver sulfate.
- the electrolysis of aluminum in such bath gives a wide variety of colors ranging from gold to dark bronze. If the amount of metal salt is below the lower limit, the electrolytic bath will have a poor coloring ability.
- the discontinuous distorted wave current is supplied from a single-phase power source or threephase power source. Polyphase power sources in excess of three in phase number involve problems in design and are practically infeasible.
- a silicon controlled rectifier hereinafter referred to as SCR
- SCR silicon controlled rectifier
- FIG. 1 is a diagram showing an electric circuit for electrolytically coloring aluminum articles according to this invention in which a single-phase power source is used, a coloring electrolytic cell being shown in horizontal section;
- FIG. 2 is a fragmentary diagram showing an electric circuit including a modification of the single-phase power source of FIG. 1;
- FIG. 3 is a fragmentary diagram showing an electric circuit including a three-phase power source connected to the electrolytic cell of FIG. 1;
- FIG. 4 shows the waveshape of current obtained using the single-phase power source of FIG. 1;
- FIG. 5 shows the waveshape of current obtained using the three-phase power source of FIG. 3;
- FIG. 6 is a diagram showing an electric circuit used for testing throwing power achieved with the singlephase power source, the diagram showing an electrolytic cell in horizontal section;
- FIG. 7 is a graph showing the test results of throwing power as determined using the single-phase power source of FIG. 6;
- FIG. 8 is a graph showing the test results of throwing power as determined using the three-phase power source of FIG. 3 in place of the single-phase power source of FIG. 6;
- FIG. 9 is a side elevation showing a number of extruded aluminum shapes as arranged in two rows and suspended in the electrolytic cell of FIG. 1;
- FIG. 10 is a side elevation on an enlarged scale showing a modification of extruded aluminum shape to be colored electrolytically.
- FIG. 1 there is shown a coloring electrolytic cell 1 containing an electrolytic bath for the second step and accommodating two aluminum articles 2.
- Each of the aluminum articles 2 opposes a carbon electrode 3 serving as a counter-electrode.
- the aluminum articles 2 and carbon electrodes 3 are connected to a single-phase power source 4 for electrolysis to form an electric circuit.
- SR silicon rectifier
- SCR 6 which are arranged in parallel and oriented in opposite directions to each other.
- Indicated at 7 is the secondary winding of a transformer.
- Positive current i flows from the aluminum articles to the carbon electrodes 3, and negative current i flows from the carbon electrodes 3 to the aluminum articles 2.
- the portion of positive current i rectified by the SR 5 has a constant conduction angle a of 180
- the portion of negative current i rectified by SCR 6 has a conduction angle B which is variably controlled by the SCR 6.
- the portion of positive current i may preferably have a greater conduction angle, but the parallel arrangement of the SR 5 and SCR 6 may possibly involve a trouble in the electric installation.
- an SCR 8 is substituted for the SR 5 in a modified electric circuit of single-phase power source 9 as partly shown in FIG. 2.
- the conduction angle a of portion of the positive current i is preferably greater than the conduction angle [3 of portion of negative current
- FIG. 3 shows a three-phase power source 10 as used for the power source of electrolytic circuit seen in FIG. 1.
- One phase of the power source 10 incorporates an SCR 11 and the remaining two phases include SCRs 12 and 13 in parallel.
- Indicated at 14 is the secondary winding of transformer.
- the conduction angle -y of portion of positive current i is greater than the conduction angle 5 of portion of negative current i and the conduction angle 6 of portion of negative current 1' It will be readily understood from FIGS. 4 and 5 that by virtue of control of SCR the waveshape of current is changed to a discontinuous distorted wave. Varying the porportion of the conduction angle of negative current portion to the conduction angle of positive current portion gives various shapes of discontinuous distorted waves. The proportion between the conduction angle of positive current portion and the conduction angle of negative current portion corresponds to the proportion between the anodizing current and the current depositing metal ions into the anodic coating on the aluminum article.
- the aluminum article can be colored to the desired lightness by suitably determining the conduction angle of the negative current portion.
- the greater the conduction angle of negative current portion the darker will be the resulting color, whereas the smaller the angle, the lighter the color obtained.
- FIG. 6 shows an electrolytic electric circuit for testing the throwing power.
- the drawing shows a coloring electrolytic cell 15 measuring 300 mm in length, 100 mm in width and 150 mm in height.
- a partition 16 which is centrally formed with a hole 17 having a diameter of 6 mm.
- two aluminum plates 18 and 19 are suspended which are made of AA 1 100 aluminum alloy and each of which measures 50 mm X 100 mm X 1.2 mm.
- the aluminum plate 18 is positioned at an approximate midportion between the partition 16 and one side wall of the electrolytic cell 15.
- the other aluminum plate 19 is disposed close to the 4 other side wall of the cell 15.
- the aluminum plate 18 only is provided with a counter-electrode, i.e. a carbon electrode 20 measuring 50 mm X 50 mm X 10 mm and positioned beside the side wall.
- the same single-phase power source 4 as in FIG. 1 is used for electrolysis.
- the plates 18 and 19 have already been anodized by the first step of electrolytic treatment conducted in a 15% sulfuric acid bath at a bath temperature of 20C with direct current having a current density of 1.5 A/dm for 20 minutes, the plates 18 and 19 therefore having anodic coatings of 911..
- the second step of treatment was conducted for 3 minutes to color the plates 18 and 19, using the electric circuit of FIG. 6 and an electrolytic bath containing g/l of sulfuric acid and 20 g/l of stannous sulfate and having a temperature of 25C, the secondary voltage of transformer being 15 V.
- FIG. 7 shows the lightnesses of plates 18 and 19 and color differences therebetween.
- the above-mentioned second step was carried out varying the conduction angle of negative current i to observe changes in the lightness of color L of plate 18 and color L of plate 19 as well as the changes in color difference.
- L values and AE are plotted as ordinate, and the conduction angle as abscissa. The lower the L value, the darker is the color. The higher the AE, the greater is the color difference. At about 0.5, the color difference is indetectable. It is seen from the graph that hardly any coloring takes place if the conduction angle is less than 30, whereas in excess of 150, a marked color difference arises. Accordingly, in the case where a singlephase power source is used, the conduction angle of portion of negative current i should be varied within the range of 30 to 150.
- FIG. 8 is a graph corresponding to FIG. 7 and obtained using a three-phase power source in place of the single-phase power source of FIG. 6. The graph indicates that when the three-phase power source is used, the conduction angles of negative currents i and 1' should be determined within the range of 30 to respectively.
- EXAMPLE 1 Ten extruded shapes of AA 6063 aluminum alloy were prepared which had sectional forms shown in FIG. 9 and measuring 60 mm in the dimension of a portion, 30 mm in the dimension of b portion and 1,000 mm in length. For pretreatment, the shapes were etched with a 5 percent caustic soda washing solution at 46C for 8 minutes. The shapes were then subjected to two steps of electrolytic treatment as described below. The ten shapes were suspended by hangers in two rows, five shapes in each row, and arranged in an anodizing cell as illustrated in FIG. 9.
- the uppermost shapes 15A and 15F were spaced apart by a distance 0 which was 80 mm, and the lowermost shapes 15E and 15,] were spaced apart by a distance d that was 40 mm, with each two vertically adjacent shapes spaced apart by a distance e that was 50 mm.
- the carbon electrodes 21 were located at a distance f of 250 mm from a plane 22 at the middle of the space between the two rows of opposing shapes.
- the shapes were subjected to electrolysis in a 15% sulfuric solution bath at a bath temperature of 20C with direct current of 1.5
- the shapes were subjected to electrolytic treatment at a constant voltage for 3 minutes in a bath containing 80 g/l of sulfuric acid and 22 g/l of stannous sulfate and having a temperature of 26C, using the single-phase power source shown in FIG. 1.
- the secondary voltage of transformer was V and the conduction angle of negative current portion was controlled to 65.
- Gold color was obtained.
- the shapes were washed with water, dried and then sealed in pure water for minutes.
- the colors of surface A facing the counter-electrode, recessed portion B and rear surface C, on the opposite side of surface A, of each shape thus treated were measured by I-Iunters 6 treatment was conducted in the same manner as in Example l. Gold color was obtained.
- the second step was followed with alternating current, using the same shape 16 as above obtained by the first step of electrolytic treatment.
- shape 16 was treated for 5 minutes in an electrolytic bath containing g/l of nickelous sulfate, g/l of ammonium sulfate and 30 g/l of orthoboric acid and having a temperature of 25C with alternating current having a current density of 0.3 A/dm and voltage of 15 V.
- Table 2 shows the results of coloring treatments achieved in Example 2 and the above-described comparison example, in terms of color difference AE between surfaces D and E illustrated in FIG. 10.
- Table 2 Color-Difference Meter The results are listed in Table 1 below. Note Table l Shapes A B C Measured values Measured values Measured values L a b L a b L a b ISA 45.5 0.4 9.1 47.0 0.4 9.3 46.6 0.4 9.2
- the present method assures very excellent throwing power.
- the shape was colored uniformly even in its recessed portion as well as on the rear surface which did not face the counterelectrode.
- the second step of treatment was further conducted with varying conduction angles of 30 to 150,whereby it was ascertained that the angle range of 30 to 100 produced gold color, whilst angles ranging from 100 to 150 yielded light amber color.
- EXAMPLE 2 An extruded shape 16 of AA 6063 aluminum alloy having a sectional form of FIG. 10- and measuring 25 mm in the dimension of g portion, 30 mm in the dimension of h portion and 1,000 mm in length was subjected to the first step of electrolytic treatment as in Example I to form a anodic coating of 8 to 9p..
- the shape 16 was subjected for 3 minutes to electrolytic treatment at a constant voltage in an electrolytic bath containing 80 g/l of sulfuric acid and 10 g/l of stannous sulfate and having a temperature of 25C, using the single-phase power source of FIG. 2 supplying a secondary voltage of 15 V, with the conduction angle of positive current portion controlled to 160 and the conduction angle of negative current portion controlled to 100.
- the method of this invention assures higher throwing power than the comparison example wherein alternating current was used.
- EXAMPLE 3 In exactly the same manner as in Example 1, the same shapes as used therein were subjected to the first step of electrolytic treatment and then to the second step of electrolytic treatment at a constant voltage for 3 minutes in a bath containing g/l of sulfuric acid and 22 g/l of stannous sulfate and having a temperature of 26C, using the three-phase power source shown in FIG. 3, each secondary voltage of transformer being 20 V. The conduction angle of positive current portion was controlled to and that of each negative current portion, to 93. An after-treatment was conducted in the same manner as in Example 1. The colors of surface A facing the counter-electrode, recessed portion B and rear surface C, on the opposite side of surface A, of each shape thus treated was measured by I-Iunters Color-Difference Meter with the results listed in Table 3.
- Table 3 indicates that the use of three-phase power source also entailed hardly any varistions in color between the surface A, recessed portion B and rear sur Table 4 shows the resulting colors in Example 4 and comparison example as determined by Hunters Color- Difference Meter.
- the second step of treatment was further conducted with varying conduction angles of negative current por tion of 30 to 1 10 to find that the angle range of 30 to 60 produced gold color, angles ranging from 60 to 90 resulted in light amber color and amber color was obtained with angles ranging from 90 to 1 10.
- EXAMPLE 4 A bus bar made of AA 6063 aluminum and measuring 50 mm in width, 100 mm in length and 3 mm in thickness was subjected to the first step of electrolytic treatment in the same manner as in Example 1 to form an anodic coating of 8 to 9a.
- the anodized bus bar was then subjected to the second step of electrolytic treatment for 2 minutes in a bath of 20 g/l of silver sulfate and 0.5 g/l of silver sulfate with the three-phase power source shown in FIG. 3.
- the secondary voltage of transformer was 100 V, and the conduction angle of positive current portion was controlled to 93 and the conduction angle of each negative current portion to 45.
- An aftertreatment was conducted in the same manner as in Example 1. The same procedure as above was followed except that the second treatment was carried out for minutes.
- the same bus bars as above obtained by the first step of electrolytic treatment were subjected to electrolytic treatment for 3 minutes and 10 minutes, respectively, in the same electrolytic bath with alternating current having a current density of 0.3 A/dm and voltage of V.
- Example 4 The same procedure as in Example 4 was followed with the conduction angle of positive current portion of It was found that partial deposition of metal ions took place to produce an uneven color tone.
- a method for electrolytically coloring aluminum articles comprising a first step of forming an oxidized coating on an aluminum article by usual anodizing treatment and a second step of subjecting the treated article to electrolytic coloration in a metal salt-containing electrolytic bath with discontinuous wave current having alternating positive current portions and negative current portions, at least the negative current portion having a conduction angle controlled by a thyristor, the positive current portions being thereby rendered larger than the negative current portions, the said electrolytic bath used for the second step containing as a main ingredient an acid selected from the group consisting of mineral acids and organic acids and the said metal salt being a salt of metal selected from the group consisting of tin, silver, copper, selenium, cobalt and nickel.
- metal salt-containing electrolytic bath contains 10 to 300 g/l of sulfuric acid and l to 50 g/l of stannous sulfate added thereto.
- metal salt-containing electrolytic bath contains 10 to 300 g/l of sulfuric acid and 0.5 to 5.0 g/l of silver sulfate added thereto.
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP47117561A JPS5249408B2 (enrdf_load_stackoverflow) | 1972-11-21 | 1972-11-21 |
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US3915813A true US3915813A (en) | 1975-10-28 |
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US416809A Expired - Lifetime US3915813A (en) | 1972-11-21 | 1973-11-19 | Method for electrolytically coloring aluminum articles |
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US (1) | US3915813A (enrdf_load_stackoverflow) |
JP (1) | JPS5249408B2 (enrdf_load_stackoverflow) |
AU (1) | AU471462B2 (enrdf_load_stackoverflow) |
DE (1) | DE2358089A1 (enrdf_load_stackoverflow) |
GB (1) | GB1398231A (enrdf_load_stackoverflow) |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4147598A (en) * | 1975-08-27 | 1979-04-03 | Riken Keikinzoku Kogyo Kabushiki Kaisha | Method for producing colored anodic oxide films on aluminum based alloy materials |
WO1980000158A1 (en) * | 1978-06-28 | 1980-02-07 | Reynolds Metals Co | Coating system |
US4251330A (en) * | 1978-01-17 | 1981-02-17 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminium by means of optical interference effects |
US4310586A (en) * | 1978-01-17 | 1982-01-12 | Alcan Research And Development Limited | Aluminium articles having anodic oxide coatings and methods of coloring them by means of optical interference effects |
US4316780A (en) * | 1979-09-20 | 1982-02-23 | Nippon Light Metal Company Limited | Method of producing color-anodized aluminium articles |
US4632735A (en) * | 1979-07-04 | 1986-12-30 | Empresa Nacional Del Aluminio, S.A. | Process for the electrolytic coloring of aluminum or aluminum alloys |
US4917780A (en) * | 1988-07-19 | 1990-04-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for coloring anodized aluminum by AC electrolysis |
US4992155A (en) * | 1986-07-23 | 1991-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Circuitry for the electrolytic coloring of anodized aluminum surfaces |
US5963435A (en) * | 1997-03-25 | 1999-10-05 | Gianna Sweeney | Apparatus for coating metal with oxide |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5727953B2 (enrdf_load_stackoverflow) * | 1974-02-07 | 1982-06-14 | ||
ES437604A1 (es) * | 1975-05-12 | 1977-01-16 | Empresa Nacional Aluminio | Sistema de autocontrol y regulacion del valor medio de la tension aplicada en procesos de coloracion electrolitica de aluminio anodizado. |
JPS5913095A (ja) * | 1982-07-13 | 1984-01-23 | Fujisash Co | アルミニウム又はアルミニウム合金の電解着色法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3708407A (en) * | 1968-09-09 | 1973-01-02 | Scionics Corp | Process for anodizing aluminum and its alloys |
US3769180A (en) * | 1971-12-29 | 1973-10-30 | O Gedde | Process for electrolytically coloring previously anodized aluminum using alternating current |
US3787295A (en) * | 1970-04-02 | 1974-01-22 | Alusuisse | Method of electrolytic coloring of oxide layers on aluminum and aluminum base alloys |
US3795590A (en) * | 1968-12-23 | 1974-03-05 | Cegedur Gp | Process for coloring aluminum and alloys of aluminum having an anodized surface |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1902983C3 (de) * | 1968-06-21 | 1978-06-22 | Keller, Eberhard, 7121 Freudental | Verfahren zum elektrolytischen Färben von anodischen Oxidschichten auf Aluminium oder Aluminiumlegierungen |
US3597339A (en) * | 1968-09-09 | 1971-08-03 | Scionics Of California Inc | Process for anodizing aluminum and its alloys |
-
1972
- 1972-11-21 JP JP47117561A patent/JPS5249408B2/ja not_active Expired
-
1973
- 1973-11-15 GB GB5299073A patent/GB1398231A/en not_active Expired
- 1973-11-19 US US416809A patent/US3915813A/en not_active Expired - Lifetime
- 1973-11-20 AU AU62707/73A patent/AU471462B2/en not_active Expired
- 1973-11-20 SE SE7315668A patent/SE409473B/sv unknown
- 1973-11-21 DE DE2358089A patent/DE2358089A1/de active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3708407A (en) * | 1968-09-09 | 1973-01-02 | Scionics Corp | Process for anodizing aluminum and its alloys |
US3795590A (en) * | 1968-12-23 | 1974-03-05 | Cegedur Gp | Process for coloring aluminum and alloys of aluminum having an anodized surface |
US3787295A (en) * | 1970-04-02 | 1974-01-22 | Alusuisse | Method of electrolytic coloring of oxide layers on aluminum and aluminum base alloys |
US3769180A (en) * | 1971-12-29 | 1973-10-30 | O Gedde | Process for electrolytically coloring previously anodized aluminum using alternating current |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4147598A (en) * | 1975-08-27 | 1979-04-03 | Riken Keikinzoku Kogyo Kabushiki Kaisha | Method for producing colored anodic oxide films on aluminum based alloy materials |
US4251330A (en) * | 1978-01-17 | 1981-02-17 | Alcan Research And Development Limited | Electrolytic coloring of anodized aluminium by means of optical interference effects |
US4310586A (en) * | 1978-01-17 | 1982-01-12 | Alcan Research And Development Limited | Aluminium articles having anodic oxide coatings and methods of coloring them by means of optical interference effects |
WO1980000158A1 (en) * | 1978-06-28 | 1980-02-07 | Reynolds Metals Co | Coating system |
US4632735A (en) * | 1979-07-04 | 1986-12-30 | Empresa Nacional Del Aluminio, S.A. | Process for the electrolytic coloring of aluminum or aluminum alloys |
US4316780A (en) * | 1979-09-20 | 1982-02-23 | Nippon Light Metal Company Limited | Method of producing color-anodized aluminium articles |
US4992155A (en) * | 1986-07-23 | 1991-02-12 | Henkel Kommanditgesellschaft Auf Aktien | Circuitry for the electrolytic coloring of anodized aluminum surfaces |
US4917780A (en) * | 1988-07-19 | 1990-04-17 | Henkel Kommanditgesellschaft Auf Aktien | Process for coloring anodized aluminum by AC electrolysis |
AU609320B2 (en) * | 1988-07-19 | 1991-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Colour anodizing of aluminium surfaces with p-toluenesulfonic acid |
US5963435A (en) * | 1997-03-25 | 1999-10-05 | Gianna Sweeney | Apparatus for coating metal with oxide |
Also Published As
Publication number | Publication date |
---|---|
DE2358089A1 (de) | 1974-05-30 |
JPS5249408B2 (enrdf_load_stackoverflow) | 1977-12-17 |
AU471462B2 (en) | 1976-04-29 |
AU6270773A (en) | 1975-05-22 |
SE409473B (sv) | 1979-08-20 |
JPS4975433A (enrdf_load_stackoverflow) | 1974-07-22 |
GB1398231A (en) | 1975-06-18 |
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