Mechanism of Electrolytic Coloring Of Anodized Aluminum By Toshihiko Sato Gel layer formation of aluminum hydroxide oceurs in the pores of anodized aluminum during electrolytic cotoring of the oxide film. This coloring mechanism can explain several phenomena of coloring observed in anodizing. odie oxide film on aluminum 1s colored in a solution containing metal 1ons when constant ‘cathodic voltage or constant AC voltage 1s, applied to the oxide film, This colonng occurs. because of deposition of metal in the pores of the anodized aluminum Cathodic current of AG or DC electrolysis decreases during electrolysis Cathodic polarization of the oxide film was studied to determine the reason for the decrease in current Following this, cathodic polarization of the oxide {film in @ coloring bath containing nickel sulfate and boric, acid was studied to increase understanding of the coloring mechanism Experimental Procedure Aluminum plates of 99.5 percent punty were used as specimens. The anodic oxide film was formed in 15 weight percent sulfune acid with 18 VOC applied Film thickness was 10 um The film was polanzed in sulfunc acid (pH2 0) oF 1n a coloring bath (pH 3 §) containing 20 g/L of nickel sulfate (NiSO, 6:0) and 30 g/L of bone acid (H,B0,) at a Results and Discussion Figure 1 shows change of cathodic potential vs. elec- trolyzingtime Portion 1 of the curve savertical step of 15 which appeared at the beginning of cathodic electrolysis and is caused by the resistance of the barner layer of the ‘oxide film and the resistance of the electrolyte in the pores. of the film The cathodic voltage was nearly constant for ‘two se¢ (portion 2), then rose to 40 V (portion 3) dunng the next iveseconds One of the following four hypotheses wil ‘account for the increase in potential. (1) Goncentration of hydrogen rons decreases in the pores of the film by cathodic polanzation and concentration over-potential Increases (2) Hydrogen tons decrease in the pores and resistance of the solution in the pores increases (3) Hydrogen gas bubbles exist in the pores because of cathodic reduction of hydrogen ions, making resistance of the solution increase (4) Electncally resistive matenal 1s deposited in the pores ‘The experiment shown in Fig 2 was performed to verity these hypotheses The oxide film was cathodically eloc~ trolyzed and cathodic polarization was stopped when the cathodic potential reached the level -V3, The oxide film 1s. allowed to stand in the electrolyzing bath for five min, then ‘cathodic polarization ss resumed fon concentration in the pores should have recovered during the pause Then fthe vertical rise in potential is to -V; at the resumption, one of the first three hypotheses 1s correct If the vertical nse in Potential is to -V,, hypothesis (4) 1s correct n 4 L o 5 10 15 Electrolyzing time, sec Constant current density of 1 0 A/dm* - Fig 1—Cathode potential change of de mn suture acid Bath. m-3 5 min j Electrotyzing time, sec Fig 2 Schematic ew of expermenttoventyhypotneses PLATING AND SURFACE FINISHING0 5 10 15 Electrotyzing time, sec 8 ig, 3— Cala srctare ods) of anadiaed Homo By May “The oxide film was electrolyzed In H:SO, (pH 20) and when cathodic voltage reached ~30V, electrolysis was stopped for five min Upon resumption, the potential was -80V Therefore, hypothesis (4) 1s correct, meaning that electrically resistive material is deposited in the pores of anodic oxide film Murphy and Michelson reported! that a colloidal sol” fayer of aluminum hydroxide exists at the bottomot the pores of oxide film, as shown in Fig 3 The pH. ‘of the sol layer changes to neutral or basie when the oxide Im 1s cathodically polarized Then the sol layer changes into a gel layer This gel layer 1s the cause of the rise in cathodic potential yer and Almitt reported’ the formation of aluminum hydroxide film nan etched layer of aluminum when etched with alternating current in the manufacture of aluminum electrodes for electrolytic capacitors They attnbuted the formation of aluminum hydroxide to the mcrease in focal pH caused by the cathodic halt-cycle ‘The interval of flat potential (Step 2 1n Fig 1) 1s the relaxation time when acid pH rises to the pH of gelation of, aluminum hydroxide The rising potential of Step 315 the result of the change of the sol layer into a gel layer When the cathodic potential reaches maximum, it exhibits small amplitude variations because of spalling of the oxide film The barner layer 1s fractured and its electrical resistance drops, causing a decrease in cathodic potential (Step 4). ‘The effects of current density on cathodic polarzation were studied It was found that the higher the current density, the higher the rise n potential This result means. that a stronger gel layer 18 formed at higher current, densities When the oxide film was cathodteally polarizedin sulfuric acid solution containing 5 g/L of aluminum sulfate, the Step3 risen potential was higher than shownin Fig 1 Astronger gel layers formed under these conditions In another experiment, the oxide film was allowed to ‘stand in distilled water for three hr, then electrolyzed in sulfunicacid The curve of Steps 1 and 2 was the sameasin Fig 1, but the amphtude of Step was greater With distiled ‘Sol—a colo eystem resembing& que MaRicH 1901 Fig 4—Cathodio poteniat change of onde Tam Teoneaaed Bra? To cated cect, water, absorbed anions, such as sulfate, on the sol layer decrease Then a stronger gel layer is formed by cathodic polarzation The "DC/AC colonng process” 1s one of the moditied processes of electrolytic coloring The oxide film 1s re- ‘anodized before coloring, then AC voltage 1s applied in the coloring bath The re-anodizing takes place in a sulfunc acid bath of pH 20 at 30 V for two min, then cathodically polarized in the same bath al @ current density of -10 ‘A/dm*. The potential time curve ts shown in Fig 4 The vertical ning potential at the beginning of electrolysis 1s higher than that shown in Fig. 1 The oxide film was anodized at 30 V, so that the bamer layer is thicker than. usual, causing the higher vertical rise “The relaxation time (corresponding to Step 2) sthe same asinFig 1 because the length and diameter ofthe film were thesame as those of anormal film The increaseof the Step 3 cathodic potential, however, 1s less than that of Fig. 1 When the oxide film is anodized at a pH of 2, some depth of sol layer n the pores changes into barner layer Then the amount of soln the pores s smaller thanin normal film and the potential increase 1s correspondingly smaller ‘similar experiment wath 50 ml/L of phosphone acid and five min standing yielded the result of lower vertical rising potential with no rise n cathodic potential (not illustrated). Im this case, some depth of barner layer dissolved and became thinner Sol layer m the pores would be dissolved ‘away from the bottom of the pores by the chelating action of the phosphone acid The gel layer did not form in the pores, accounting for the lack of rise in cathodic potential Cathodic Electrolysis in the Coloring Bath Figure § shows the potential time curve for oxide film cathodically anodized in the coloring bath After polartza- tion, the film was colored dark brown Some spots of bare aluminum were observed because of spalling The vertical rising potential was -13 V and the interval of flat potential was one second The Step 3 area showed arise 10-16 V, ‘changes being smallerthan nFig 1 Itrsapparent that gel layer will normally be formed when an oxide film «5 cathodteally electrolyzed in a coloring bath, and that 11spees t0men 6) Etectroyzing time, 2e0 20) Fig 5—Catboce poleral change of onde fm nthe coloring Bath the cause of the decrease of current during colonng “The mechanism of colonng sillustrated schematically in| Fig 6 A sol layer of aluminum hydroxide exists at the bottom of the oxide film in the coloring bath (a) When cathodic current flows through the film, hydrogen sons and ‘metal 1ons are cathodically reduced The pH in the pores rises because of the reduction of hydrogen ions and the sol layer changes into a gel layer At the same time, reduced ‘metal ions deposit metal in the pores Cathodic current decreases because of the gel layer (b) Continued elec- trolysis thicker gel layers are formed and more metal 1s, deposited in the pores (c) Eventually, metal deposition 1s halted, but the pores cannot be filled with metal This coloring mechanism 1s termed the Get Layer Model Coloring Phenomena Several coloring phenomena eccur during coloring opera- tions that can be explained by the mechanism of Fig. 6 (1) The oxide film has a lighter color at higher voltage Figute 7 shows the relationship between the AC coloring voltage and the hue of the colored film (L value), where the higher values of L mean lighter color The oxide films were colored for three rin in a NiSO,-Hi80; coloring bath, the darkest color for normal oxide film occursat 15 VAC (curve 1) When higher voltages are applied, athicker barnerlayer is formed on the bottom of the pores Aluminum oxide film 1s colored by direct current in some Japanese factories, where itis colored lighter at higher cathodic voltage (2) When much oxide tlm 1s treated in a colonng bath, AAI" (ons accumulate in the bath, resulting in lighter color lon content is therefore controlled, because an increase of tons generates more gel layer in the pores, preventing metal deposition (3) The shade of the colored film 1s largely affected by rinsing conditions, which must be controlled. The film 1s normally rinsed with DI water or tap water after anodizing When rinsing time is shor, sulfunc acid or Al” 1ons cannot be removed sufficiently When rinsing time 1s longer, the ‘amount of absorbed ions on the surface of sol 1s less and more gel layer 1s formed dunng coloring electrolysis. The resulting color is thus lighter ‘Fig €Sehemaie ww of cooing moshanion (4) Curve (2) of Fig 7 shows the relationship between AC voltage of the DC/AC colonng processand the shade of the colored fiim In this case, the film can be colored at voltages even higher than that of the AC coloring method There 1s less sol in the pores, so not much gel layer Is formed and the film has a darker color (6) The film can be colored blue by immersing wt in phosphor acid for five min before coloring This causes the sol in the pores to be chelated with phosphate ions It cannot then be gelated during AC colonng, metal can be deposited and the film colored even at 40 VAC. This 1s ilustrated by Curve (3) of Fig 7 ‘Special oxide film anodized in normal sulfuric acid and re-anodized in phosphonc acid can show an “interference color.” such as blue, green, red, etc , with AG coloring A special barrier layer ts formed on the normal barrier layer land the gel layer is not formed because of the presence of phosphate ons Then the height of deposited metal in the pores salmost equal, grving rise to the interference colors Coloring voltage, AC Fig 7~Aelalondap between anade of colonng(L vale) and he colonna olage (3) ode hms colored ip NISO.-H BOs both, 2) ante Hime ve Shodited tnd colored NGOLH.BO. wah DCIAC eolotng metho (3) ‘hie ama mrsersea im phospnone acd bath, then colored mNISO.-HBO» PLATING AND SURFACE FINISHINGConclusions Formation of agel layer in the pores of anodized aluminum Plays an important role m electrolytic coloring, making control of gel formation essential to obtaining the ame shade from batch to batch Such control 1s equatly necessary when developing novel color films References 1 JF Murphy and GE Michelson, Proc. Aluminum Development Assoe Cont. on Anodizing, Nottingham (England), 83 (1961) C.K Dyerand AS Alwnt,J Electrochem Soc , 128,300 (1981) About the Autho (Dr Toshihiko Sato fea professor in the Dept of Melaturgy, ‘Shibaura Technical University, 3-9 Stubaura, Minato-ku, TokYO, Jopan He holds 85, MS and PhD degrees in engineenng from ‘Tohoku University, He has been associated wih Shibeura Univeraty since 1086, Rrerusuc LEAD ANODES “sixty-eight years of proven quality” Whatever your lead anode needs be, let us, ‘with our 88 years of expertence, help you. Lot us prove our exclusive "Homogeneous Bonding” process, assuring positive ciec- trical contact between hood and anode, ‘throughout the life of the anode. 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