Coloring Titanium and Related Metals by Electrochemical Oxidation

Emily Gaul Department of Science and Mathematics, Columbia College, 600 South Michigan Ave, Chicago 11 60605-1996

The idea of coloring metals through "electrocution" intrigues my visual arts students. Anodizing titanium and the related metallic elements niobium and tantalum is a novel means of illustrating electrochemical principles as well as demonstratine the o ~ t i c a lheno omen on of thinlayer interference (iridescence).Using a common dc power BUDD~V with current-limiting ca~abilities.a conductive aqkobs electrolyte and tita&m-metal, one can obtain a wide range of iridescent oxide colors on the surface of the metal by simply varying the applied voltage. For example, titanium metal is colored purple at 15 V and bronze at 50 V. Similar effects can be obtained by substituting niobium or tantalum for titanium. Anodizing is a useful companion experiment to electroplating. Both are electrolytic and require an applied voltage, but whereas in electroplating a metal ion in the electrolyte is reduced onto the surface of the cathode made of the same or different metal, in anodizing the metal anode forms an oxide first on the exposed surface and then oxidizes inward. Previous articles in this Journal, have dealt with anodizing aluminum (1,2). Sulfuric acid electrolyte and air provide the oxygen, which reacts with the aluminum to form its oxide, alumina (AI20J. The electrolytically formed alumina gives a porous, spongy surface on the aluminum

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metal, which, when rinsed of the sulfuric acid, will readily absorb organic dye. Besides providing a means to color the metal, anodizing is important in industrial applications in providing a more corrosion-resistant coating for aluminum. In titanium anodizing, a much thinner transparent oxide layer of the metal is formed and colors result, not from the oxide layer absorbing added dyes as with aluminum, but rather from the effect of the thin oxide layer interfering with wavelengths (correspondingto various colors) of the incident light. In titanium anodizing the voltage is varied to obtain a variety of colors useful for the artist. The voltage range is higher and the applied current lower than in aluminum anodizing (3,4). Titanium, niobium, and tantalum have been used by metalworkers in the arts for their iridescent coloring when electrochemically or thermally anodized. The electrochemical reactions are as follows:
Cathode:
Anode:

4 p + 4K +2H2 (reduction) 2~0-to2+4H++4e!Ti

+ 0 + TiO, ,

(osdatim)

f y Figure 1. (above)Thin-layerinterference o light waves. Based on an illustration b Stuart Hamill. Figure 2. (rigM)Atitanium vessel spun from flatsheet at high heat; the finish is the oxides that formedduring the process (see Table 1 for color-temperature relationships. Vase and photo by Bill Seeley, Reactive Metals Studio. 176 Journal o Chemical Education f

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Oxveen. which is eenerated at the titanium anode bv the oxldstke breakdown of water, subsequently combinekth the metal to form titamurn dioxide no, As shown in Table 1,the thickness of the oxide formed is &rectly to the applied voltage (3,4).
Thin-Layer Interference Colorine titanium electrochemicallv is a vivid wav to illustrate-thin-film interference. Irid&cence due to thinlaver interference is also exhibited bv o ~ a l soil slicks. soaD , bkbbles, ancient buried glass, rainbow bout, Ymood rkgsG, mother of pearl, and pigeon and peacock feathers. Unlike colorants such as dyes and pigments, which operate by selective absorption of certain wavelengths of light, in iridescent coloring selective wavelengths of light are interfered with by the thin oxide f h ,and the color obsenred will vary with the angle of viewing (5). The colors result fmm interference of reflectedlieht fmm thin transparent oxides, as shown in Figure 1, w 6 r e part of the light of anv eiven waveleneth of color is reflected bv the fir; outer &&ace and of the light throwh the outer surface and reflects off the inner metal surfa& If two reflections of a particular color are a half. wavelength out of ~ h a s with each other (light wave crests e from one d a c e meet wave troughs fmm ;he other), they interfere with each other. When opposite phases meet, the light interference is called "destructive" and the color obsemed will be white light minus that color giving its complementary color. Converselv. if two waves of the same color or waveleneth are retlectei'.om the inner and outer surfaces where ihe crest of one maichea the crest of the other, the waves are in step or "in phase" and they will constructively interfere or reinforce each other and as a result the dolor will appear -brighter. Thus the red coloring in a rainbow tmut or red anodized titanium is due to the thin layer destructive interference of
Table 1. Titanium Heat Oxidation a d Anodized Spectrum (4) Showing the Relation of Film Thickness and Color to Voltage and Temperature of Oxidation

flgure 3. An anodized niobium sample showing the range of colors with varying voltage. Photo by Bill Seeley, Reactive Metals Studio.
Table 2. Comparison of Colors Produced at Given Voltages on Titantlum, Niobium, and Tantalum

Color Yellow Brass Purple Violet-blue Purple-blue Light blue Gray D e l U Pale aqua Green blue Pale bronze Pale green Purple Green Rose gold Red purple Bronze Gold purple Rose Dark green Gray

Voltage (dc)

Temperature
('C) 371 385 398 412 426 440 454 468 482 496 510 523 537 551 565 579 593 607 621 635

Film Thickness

(w))

0.03 0.035 0.04 0.046 0.053 0.06 0.063 0.066 0.07 0.08 0.95 0.H 0.12 0.13 0.14 0.15 0.16 0.17 0.18 0.19

Voltage (dc) Titanium Color 5 Yellow 10 Brass 15 Purple 20 V~olet-blue 25 Purple blue 30 Ught Mue 35 Gray Mue 40 Pale aqua 45 Green blue W Pale bronze 55 Pale green 60 Purple 65 Green 70 Rose gold 75 Red purple 80 Bronze 85 Gold purple 90 ~ose 95 Daric green 100 Gray 105 Gray
110 120 125 130 135 140 145 150

Nmblum Color Yellow Bra% Plum Vmlet-blue Sky blue Blueish gray Light gray blue Green gold Orange gold Rose Blue purple Green blue Sea green Gold green Green Brass Dull gold Green Plum rose Magenta Blue masenta Greemse Green Greedpurple Greenlpurple erald Green Pale Green Silver Green Blue silver Silver

Tantalum Color

Brass Yellow Purple Blue violet Bluesiiver Sky blue Silver blue Silver Silver Silver Pale yellow Yellow Gold Copper Pale Orange OIange gokl Purple pink Purple Purple Blue Turquoise Turquoise Yellow green Pea Green Silver green Pale yellow Yellow Ti7

Volume 70 Number 3 March 1993

blue-green, or cyan, which is the complementary color of red. The color that will be observed will vary with the thickness of the oxide layer (Table 11,which varies directly with the voltage or temperature used to produce it (3, 4). The light reinforcement or interference differs with perspective; hence a person will see a peacock feather as bluegreen from one angle and as gold from another.
Thermal versus Anodic Coloring The thin oxide films can be generated on titanium by reaction of oxygen with metal by either of two methods: thermal or heat oxidation and electrolytic oxidation or anodizinn (3, 4). During thermal oxidation. the thickness of the with time and the temogdefilm varies~proportionately perature of the metal. Colors within the blue and gold range are obtained by heating titanium metal with a propane flame. Colors resulting from higher temperature are obtained by heating with an acetylene torch or placing in a kiln (see Fig. 2.) Oxidation by electrochemicalanodization has the advantage over thermal oxidation in that the voltage, hence the film thickness. can be more accuratelv controlled (Fie. 3). In addition niobium and tantalum aie less satisfackl'y colored bv heat but exhibit an even wider ranee of interference colo& than titanium when wlored elec&chemically as shown in Table 2. Procedure Titanium can be anodized in any wnducting electrolyte such as Dr. Pepper, Epsom salts, or ammonium sulfate. The best results were found using trisodium phosphate. Approximately 200 mL of 10% solution of trisodium phosphate (a detergent base available in most hardware stores) is added to a 250-mL Pyrex glass or plastic beaker. Deionized water is recommended to avoid reactions of the chlorides present in tap water, particularly at the higher voltages. Anodizing reactions should be run at room temperature. The cathode is a 6- x 2 314411. strip of 26-gauge titanium with an attached tab to conned to the external leads. The cathode. with a n extrndine tab. is wraDDed around the inside of the beaker, and coiered by a &ip of plastic mesh (such as used for needlework) to prevent its touching the anode. A2- x &in. strip of 26-gauge titanium or niobium or thinner tantalum foil is used as the working anode. The greater the purity of the metal and the cleaner the surface, the more brilliant the colors exhibited. If the metal is industrial grade it can be cleaned as follows:

Scrub with 320-gradefollowed by 400400 grade silicon earbide paper followed by steel wool and steel wool and detergent, then rinse with acetone to remove grease, oil, or salt residue. Titanium must be acid-etched to reach its greatest color ~otential. Niobium (which is s h i ~ ~ in d ~rotective l a s e a ~ tic) and tantalum need only be &&eased before use.'Any metal intended for use as jewelry should first be cut to shape with its edges well filed. It can he flattened with a rubber or rawhide mallet. A low current-limiting 0-200-V dc power supply'is connected in series with a voltmeter to the cathode (-) and anode (+I. Electroplating power supplies do not provide the higher voltages and lower currents required for titanium anodizing. Alligator connectors should be sc~pulously cleaned. The electrodes are then placed in the electrolyte except for the connecting tabs. To prevent a short circuit the electrolyte should not come into direct contact with the leads from the power supply, nor should the two electrodes come in contact with each other when the voltage is on. Rubber gloves must be worn at all times and work should never be done on a metal table. The voltage can be varied to produce a range of thin layer interference colors as shown in Table 1. Only the part of the metal that is in contact with the electrolyte.wil1be anodized. Colors are obtained almost immediately. Students may mask portions of the reactive metal with electrical insulating tape, and then unmask portions of the tape as they work from high to low voltages, thus creating an image. The final ~ r o d u c t should be rinsed in deionized water to remove tke trisodium phosphate. The thin layer. which is easily scratched, can be protected by spray acrylic.
Literature Cited 1. Doe1tz.A. E.;Tharaud,S.;Sheehan,W. F. J. Chem. Edue. 1988.60, 156157.
c 2. Blstt, R. G. J. c h e m ~ d u ism,66,268. 3. Seeley, W. A. MFAThesls,UniveraifyofKansas, 1982isvailablehmReactive Metals Studio, see fmtnote 1 . 1 4. Untca~ht, JemIry Conmpl~ 0. end lkchhalagy; Doubleday: Garden City. Nea York, 1982; rp 723.130. 5. Nassau, K The Physics and Chemistry ofColor; Wiley-Interscience: New York,1983, Chapter 12, p 2 N .

'React ve Meta s S l ~ 0. PO B x 870. Clarma e AZ 86324 s a a o (101 SoJrce lor tnese rnalerla s I tanurn nloo Lm, tanta8Jrn only,. and anodizing power supplies, as well as the thesis cited inref. 3.

178

Journal of Chemical Education

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