STEFAN KUPPER Coloring of Anodized Aluminium Abridged version of a paper presented atthe “5. Diskussions- tagung Anorganisch-technische Chemie" of DECHEMA in Franifurt from 13th to 4th February, 1996 The annual world production of aluminium, one of the four most important commercial metals, is now in excess of 20 million t. This demand is substantiated by such material properties as high mechanical strength of its alloys, low specific density and excellent forming behaviour. Other aspects of aluminium are its aesthetically attrac- tive silvery shine and, most importantly, its resist- ance to corrosion. Accordingly, preferred applica- tions are aircraft construction, the automotive industry and exterior architecture. ‘Surprisingly, the high corrosion resistance of aluminium is attributable to its ready oxidizabili- ty. In the presence of moisture and atmospheric oxygen, a firmly adhering oxide film is formed on bright aluminium surfaces, counteracting further corrosion by passivating the base metal [1]. How- ever, this 1-3 nm thick natural oxide layer is not sufficient for technical corrosion control so that processes were developed which increase the natural corrosion resistance several times to the industrially desirable level. 1, CORROSION CONTROL BY CONVERSION There are several surface treatment processes, so-called conversion processes, in which alumini- um is passivated by chromating or by application of solutions containing complex titanium and zir- onium compounds [2]. However, these pracess- es are only the first step before painting. Unfortu- nately, the metallic shine of aluminium, one of its key features, is inevitably lost as a result. 2. CORROSION CONTROL BY ANODIZATION ‘An equally effective technology is the Eloxal “elec- trolyticaly oxidized aluminium") process (3]. This process is characterized by the anodic formation of a passivating oxide layer which not only is Henkel-Referate 33/1997Henkel Referate 33/1997 St. Kupper Coloring of Anodized Aluminium Figure 1 Layer composition of the oxide film on anodized aluminium [4] 2 400m = b 12mm c Sam highly corrosion-resistant, but also keeps the metallic sheen intact for long periods through its transparency. This is important above all when, besides resistance, appearance is also an impor- tant factor. The porosity of the freshly produced alumini- um oxide layer enables it to be colored so that, in addition to the silvery tone, many other colors of metallic appearance can be produced. In three preliminary process stages, the alu- rminium profile to be anodized is first cleaned and then pickled to create a uniform surface. The Figure 2 Example of the dip coloring of anodized aluminium AlizarinRot SO «OH OH cone, oO ' + 4 pickling treatment acts on the degree of bright- ness from dull to very bright. Finally, in the third step, descaling, alloy components which were exposed but not removed by pickling are re- moved. In the architectural field, these alloy com- ponents are mainly silicon and manganese. During anodization by the direct-current sul- furic acid process, the workpiece is coated in one hour with an approximately 20 ym thick, mainly oxidic glass-like layer. The porosity of this layer with 800 pores per jim? makes it suitable for the coloring step which is followed by sealing. During sealing with hot water, the predominantly amor- phous oxide layer is hydrated to boehmite which closes the pores with an increase in volume and firmly locks in the coloring substances. It is only this attertreatment that achieves defined layerand quality properties which are specified by the “Qualanod Giitegemeinschaft” and which are es- sential to long-term corrosion control. Figure 1 shows the composition of the oxide layer [4]. itis a double layer which consists of a nonporous base layer or barrier layer on the metal side. On the electrolyte side, it is permeated by pores in the middle of hexagonal cells. The direct- current sulfuric acid process produces pores about 12nmin diameter which almost reach down to the base metal. 3. MULTISTAGE COLORING PROCESSES All the multistage coloring processes, including dip, electrolytic metal salt and interference color- ing, require a sufficiently thick, porous and seala- ble oxide layer. In dip coloring, the anodized profiles are submersed in aqueous solutions of organic dyes which penetrate into the pores and are adsorbed conto their inner walls (Figure 2). The concentra- tion of dye in the pore decreases from the electro: Iyte side to the metal side, but can be influenced by the dye concentration and residence time in the coloring bath. Organic dyes provide for a broad range of colors such as can also be found, for example, in colored paints. The dyes which, previously, often lacked light stability were replaced by lightfast dyes. Bleeding, i.e. the desorption of soluble dyes dur: ing sealing, and the resulting risk of contamina- tion to this bath and other baths demand a careful choice of the coloring parameters. In all dip coloring processes, a separate bath has to be available for each shade of color. The installation of such coloring lines involves high capital outlay and maintenance costs. Figure 3 Example of the electrolytic metal salt coloring of anodized aluminium with tin(t) salts uh ADs N [XS XN Fa 30 100 150 200 250 Time rin} Depth profile of Sn black coloring by Auger electron spectroscopy In electrolytic metal salt coloring, the first step is again anodization in the usual way. Figure 2 shows that, in the subsequent coloring step, finely divided elemental metal is deposited at the bottom of the pore, i.e. in the immediate vicinity of the cathode, from a metal salt solution during the cathodic phase of an alternating current cycle lasting several minutes [5]. The deposited metal acts through light scattering and absorption and not through its own color. The visible color tone depends on how much of the incident light is reflected. Metals which can be electrochemically de- posited from aqueous solution are suitable for metal salt coloring. However, only tin, nickel, cobalt and, to some extent, copper are of practi- cal relevance. The colors obtainable cover a nar- Henkel-Referate 33/1997St. Kipoer Coloring of Anodized Aluminium to bath impurities, high light stability and corro- sion resistance, tin-based electrolytic coloring is prevalent in Europe for bronze and black tones. In interference coloring, the intial anodizing step is followed by another two electrochemical process stages. To produce interference colors, a second anodization is carried out in a bath Figure 4 Interference coloring of anodized aluminium Direct-current sulfuric acid ‘anodization Additional phosphoric acid anodization Electrolytical coloring VV Vi - row range from light bronze to black. Only copper produces reddish tones when used on its own. The depth of color is largely independent of the thickness of the oxide layer and is determined solely by the quantity of metal deposited. A bath for electrolytic coloring with tin con- tains, for example, 10 g of till) salts, 20 g of sulfuric acid and antioxidants which counteract oxidation to Sn(lV). Other additives are organic. throw improvers. They provide for a uniform color of the anodized aluminium parts which are locat- ed at different distances from the counterelec- trode. The process is carried out with a constant voltage at room temperature. The required color is achieved by varying the electrolysis times. A coloring time of 15 seconds is sufficient for light bronze while black takes 15 minutes to achieve. For black tones in a 20 ym thick anodizing layer, the pores have to be about halfilled. By virtue of its favorable throwing power, low costs, tolerance Henkel Reterate 33/1997 whose electrolyte has a lower dissolving capacity for the oxide layer than sulfuric acid. Since the pore size is dependent on the electrolyte, an oxide layer with a different pore size, for example 33 nm, is formed with phosphoric acid below the old oxide film (2]. The pores are enlarged to 30 ‘nm in 4 to 10 minutes on the base metal side whereas, on the electrolyte size, they taper down to the starting diameter of 12 nm (Figure 4). As in metal salt coloring, elemental metal particles are deposited at the bottom of these enlarged pores, but in a more uniform distribu-Table 1 ‘Comparison of coloring processes for anodized aluminium Combination coloring | Subdued color tones| Interference coloring | Grey, bronze, gold with various color tones Integral coloring Bronze, grey, brown, gold Wider range of colors than in metal salt coloring, higher light stability than in dip coloring Wider range of colors than in metal salt coloring, good performance Properties Single-bath process, high light stability, easy to carry out Process Colors Advantages Disadvantages Dip coloring Al bright tones Wide range of colors, Many separate baths and black easy to carry out, low energy consumption Electrolstical Champagne-colored | Inexpensive, high light Narrow range of colors, metal salt coloring | bronze to black stability, good mechanical no bright tones (particularly Sn) properties Multipath process, hence complicated and expensive Very complicated and expensive process, many process steps, expensive due to the number of baths High energy consumption, cooling necessary, narrow range of colors, ‘no bright tones tion. Incident light is reflected both at the base metal interface and at the surfaces of the depos- ited metal columns. If a suitable interval is estab- lished between these planes through the anodiz- ing conditions, interferences visible as colors occur. Together with the light-scattering effect, diverse visually attractive colors from gray through bronze and gold to brown can be produced in various shades. However, this diversity of colors coupled with high resistance to light and corro- sion requires a complicated and expensive pro- cess involving several process steps. 4, ONE-STAGE COLORING PROCESSES The coloring process can also be carried out in a single step together with anodization. This princi- ple is known as integral coloring. In integral coloring and the associated ano- ization, the conditions are less uniform than in the direct-current sulfuric acid process. There are more than 30 integral coloring processes which produce colored aluminium during anodization. In all these processes, electrolytes such as suffuric or phosphoric acid have largely been replaced by multifunctional carboxylic or sulfonic acids which have a far lower dissolving capacity for the oxide layer and lower conductivity. Because of this, higher bath voltages and current densities, for example 50-250 V at 20-30°C, have to be used so that the bath has to be intensively cooled throughout [1]. Without the addition of other metallic elec- trolytes, gray, yellow and deep bronze to black Henkel Referate 33/1997St. Kipper Coloring of Anodized Aluminium colors can be produced on high-purity aluminium with the electrolytes present in the solution or emanating from alloy components of the alumini- um. This limited range of colors is indicative of mechanisms similar to those encountered in met- al salt coloring. Today, itis known that the color is formed by small quantities of elemental alumini- um. However, the metal particles are incorporat- ed in the oxide layer itself and not in the pores. However, the color impression is formed by the same physical principle: the metal particles act as scattering and absorption sites for the incident light and the reflected component determines the color impression. The aluminium particles are presumably formed under the influence of large local field strengths: aluminium previously dis- solved near the anode is reduced again and then incorporated in the oxide film. The color tones can be varied to a limited extent by adding metal salts to the electrolyte solution. Such variation is possible through alloy constituents alone, such as iron, silicon, manga- nese or copper, so that reproducible colors can only be obtained by careful monitoring of the bath and alloy. Because of this, integral coloring has largely been replaced by electrolytic metal salt coloring since about 1970. 5 OUTLOOK Despite the impressive range of colors obtainable in the coloring of aluminium, above all by the dip and metal salt coloring processes, the develop- ment of new coloring processes is nat yet com- plete (Table 1). This is reflected in interference Henkel Referate 33/1997 coloring which, today, covers a broad spectrum of colors. The aluminium coloring industry is in competition with paint and plastics manufactur- ers and stil has to take on the major “color” challenge of producing white panels by anodize tion Literature 1. Greenwood, N. N.; Earnshaw, A.: Chemistry of the Ele- ments, Pergamon Press Ltd. 1988 2. Kresse, J.: Aluminium-Oberflachenbehandiung, DFO-Be- richtsband Nr. 27, 1995 3. Wernick, $.; Pinner, R.; Sheasby, P. G.: The Surface ‘Treatment and Finishing of Aluminium and its Alloys, Sth Ed., Finishing Publications Ltd 4, Keller, F.; Hunter, M. 8; Robinson, D. L.: J, Electrochem, Soc. 100 (1953) 411 5. Gohausen, HJ; Puderbach, H.: Aluminium §9 (1983) 769 Correspondence author: Dr, Stefan Kipper, Henkel KGaA, Disseldort