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Optics & Laser Technology 38 (2006) 440444 www.elsevier.com/locate/optlastec

An unusual phenomenon observed when anodising CP titanium to produce coloured surfaces for jewellery and other decorative uses
Lynne Bartlett
Central Saint Martins College of Art and Design, Southampton Row, London,UK Available online 21 July 2005

Abstract The unpredictability of the evenness of colour developed on titanium surfaces for use in jewellery has led to a research project at Central Saint Martins College of Art and Design (CSM) to investigate the detailed structure of the thin oxide lms that produce the interference colours. In the course of some initial investigations an unusual phenomenon was observed when a specic material was anodised. Examination of the anodised surface by scanning electron microscopy (SEM) showed a profusion of ower-like oxide growths developed in random orientations from about 30 V with increasing density up to 110 V. In honour of the late Professor Harvey Flower these features are currently referred to as Flower oxides or owers. Further work is continuing to clarify the nature of these growth features and their structure and composition. r 2005 Elsevier Ltd. All rights reserved.
Keywords: Titanium jewellery anodising

1. Introduction Titanium, coloured by either heat or anodising, has been used to create interesting and unusual jewellery for over 35 years. Fig. 1 shows examples of pieces using different techniques. The unpredictability of the evenness of the interference colour produced by the thin oxide lm on the surface of the metal has been the reason for the current investigation. In general, the studies on oxide formation on titanium have been in the context of the corrosion resistance of the metal. Thus anodisation has been undertaken in innumerable electrolytes: acidic, basic and neutral, organic and inorganic and at a range of temperatures and voltages [1]. Few papers have attempted to correlate the colour and the thickness of oxide layer needed to produce it. It is generally accepted that a thin layer in the range 10500 nm is required to show interference colours [2].
E-mail address: l.bartlett1@csm.arts.ac.uk. 0030-3992/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.optlastec.2005.06.026

In 1963 Sibert [3] in the course of a study on the factors inuencing lm formation concluded that in a phosphate electrolyte lm formation was at a rate of 20 A (2 nm) /V up to 200 V. This agrees with values published in 1967 by Cotton and Hayeld [4]. A correlation between oxide thickness, colour and oxide formation rates was published by Flower and Swann [5] in 1974 and the 1980 paper by Fukuzawa et al. [6] included a graph of lm thickness against oxidation time at different temperatures with an indication of the colour range observed. All these observations were based on calculated methods for determining the oxide thickness. Direct measurement of the thickness of the oxide layer was undertaken in 2003 by Gueneau de Mussy et al. [7] using transmission electron microscopy (TEM). In their experiments titanium was anodised in sulphuric acid to 120 V. Measurement of the total thickness of the oxide layer is not quoted but from the published diagrams it can be deduced that it is approximately 1300 nm overall. No mention is made of colour.

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solution of ammonium sulphate at room temperature [9]. The same solution was used for all the experiments. The surfaces of the oxidised samples were examined at Imperial College using a JEOL T200 scanning electron microscope (SEM). Anodising to 2123 V develops a royal blue colour. According to Sibert this should be produced by an oxide layer 4246 nm thick. A gold colour develops at 5561 V or 110122 nm. Thus in order of magnitude the thickness of a gold oxide is over twice the thickness of a royal blue one. 2.1. Phase one Initial experiments set out to compare the oxide layers developed on CP titanium by heating and anodising to produce two different, easily distinguishable colours, blue and gold. Two different surfaces were used: assupplied and hand-polished. Each sample coupon was scored across the middle and one half was polished with 1000 grade wet and dry paper and the other half was left untouched. During the polishing the unpolished half of each coupon was protected by wrapping it with Scotch tape. All samples were washed with a mixture of ammonia and washing-up liquid, dried and swabbed with acetone both before and after any mechanical polishing. Table 1 lists the samples, colouring methods and colours produced. A total of eight sample coupons were prepared. The coloured samples were then examined by SEM at magnications of 350 and 2000. For samples 1A, 2A, 1B, 2B, 1C, 2C and 2D the oxide surfaces showed a mirroring of the underlying metal structure whether as-supplied or polished. Little difference was seen between the heated and anodised samples. Sample 1D, where in order to get a gold colour on the polished surface, the unpolished surface had been anodised to pink, showed some unusual features in the form of owers or rings of oxide randomly distributed across the surface. In order to establish whether this interesting phenomenon was due to oxide thickness, samples of both materials were oxidised, by heat and anodising, to a thickness that gave a pink colour and to a thicker layer that produced blue/green. 2.2. Phase two A further eight sample coupons were prepared as for the previous experiment. Because of the differential oxidising rate, especially during anodising, in order to get a pink colour on the polished part of the scrap titanium the unpolished section became green. Table 2 gives details of the samples, colouring methods and resulting colours.

Fig. 1. Titanium jewellery

It is observed that different colours i.e. rates of oxidation can be produced under the same conditions depending on the nature of the surface of the titanium metal prior to oxidation. In 1952 Hass observed that the rate of oxidation when heating at 400450 1C depended on the surface quality of the metal substrate [8]. He noted that abrasively polished titanium oxidised faster than evaporated lms which have mirror-nish surfaces.

2. Programme of experiments and results The experiments were carried out in three phases. For each phase the same materials, sample preparation procedure and analysis were used. Coupons of commercial purity (CP) titanium from two sources were prepared. One was a scrap material of unknown origin, 0.5 mm thick, designated 1, which analysis showed to be CP grade. The sample size was 3 cm 1 cm. The other material, 2, was sheet from a commercial source, 0.406 mm thick that was supplied with a lightly acid-etched surface. A different sample size, 2.3 cm 1 cm was used so that the two materials could be quickly identied. Two methods of colouring were used: heating in a kiln at 700 1C and anodising in a 10% by weight aqueous

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442 L. Bartlett / Optics & Laser Technology 38 (2006) 440444 Table 1 Summary of initial colouring procedures and results Sample code 1A 1A 2A 2A 1B 1B 2B 2B 1C 1C 2C 2C 1D 1D 2D 2D
a

Metal sourcea/type Scrap Scrap RMS RMS Scrap Scrap RMS RMS Scrap Scrap RMS RMS Scrap Scrap RMS RMS

Mechanical nish Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished

Colouring process Heat Heat Heat Heat Heat Heat Heat Heat Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised

Voltage (V) or temp.1C 3 min/700 1C 3 min/700 1C 2 min/700 1C 2 min/700 1C 4 min/700 1C 4 min/700 1C 7 min/700 1C 7 min/700 1C 21 V 21 V 23 V 23 V 55 V 55 V 61 V 61 V

Colour Royal Royal Royal Royal Gold Gold Pink Gold Royal Royal Royal Royal Pink Gold Gold Gold blue blue blue blue

blue blue blue blue

CP titanium sheet either scrap of unknown origin or from Reactive Metal Studios(RMS)/USA.

Table 2 Summary of colouring procedures and results for second experimental phase Sample code 1F 1F 2F 2F 1G 1G 2G 2G 1H 1H 2H 2H 1I 1I 2I 2I
a

Metal sourcea/type Scrap Scrap RMS RMS Scrap Scrap RMS RMS Scrap Scrap RMS RMS Scrap Scrap RMS RMS

Mechanical nish Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Unpolished Polished Polished Unpolished Unpolished Polished Unpolished Polished

Colouring process Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised Heat Heat Heat Heat Heat Heat Heat Heat

Voltage (V) or temp.1C 87 V 87 V 89 V 89 V 110 V 110 V 112 V 112 V 10 min/700 1C 10 min/700 1C 12 min/700 1C 12 min/700 1C 15 min/700 1C 15 min/700 1C 16 min/700 1C 16 min/700 1C

Colour Green Pink Pink Pink Purple/pink Blue/green Turquoise Blue/green Pink/green Pinkish Turquoise Yellow/green Brownish/green Brownish/green Gold Greenish

CP titanium sheet either scrap of unknown origin or from Reactive Metal Studios(RMS)/USA.

Fig. 2 shows samples AF. Samples 1F, 2F, 1G, 2G, 1H and 2H were examined by SEM. Contrary to expectations, the samples anodised to pink, 2F and the polished part of 1F did not exhibit rings of oxide but only ne nodules. However, the unpolished part of 1F which had been anodised to a bright green showed owers scattered all over the surface with a three-dimensional structure. A comparison of the SEM images at 2000 for 1D, 2D, 1F and 2F is given in Fig. 3. More rings of oxide of differing sizes, perhaps indicating various stages of formation were observed

Fig. 2. Samples of CP Ti coloured by heat or anodised.

on the unpolished part of sample 1G which had been anodised to 110 V. The polished part of this sample showed coral-like colonies of oxide. The heat-coloured samples 1H and 2H did not show any particular features

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that indicated anything other than a fairly uniform oxide layer across the surface. Sample 2G, anodised to a blue/green colour at 112 V, has a few ne nodules of oxide but mostly shows the underlying metal surface structure. Thus it was established that the owers were only produced on the unpolished scrap titanium when the material was anodised.

2.3. Phase three The rst observation of the phenomenon had been at about 55 V and there had been no indications at 21 V. In order to determine at what voltage the owers rst appeared, a series of 12 coupons of the scrap titanium were anodised at intervals of 5 V from 25 to 80 V. Table 3 lists the voltages and the colours produced. Fig. 4 shows the coloured samples and illustrates the variability of the colouring especially at the higher voltages. All the SEM examinations were carried out at 10,000. Fig. 5 shows the developing owers at various voltages. The 40 and 55 V samples were examined rst. Both showed the presence of owers but at 40 V there were fewer of them. Examination of the samples at 25 and 35 V followed. These showed that there was nothing but the underlying metal surface structure to be seen at 25 V. Some incipient owers and a few small but denite examples were visible at 35 V. As it was possible to place two samples in the chamber of the electron microscope at the same time, the nal examination included the 30 and 75 V samples. As expected there was a profusion of owers at all stages of development visible on the 75 V sample. The 30 V sample showed just one or two very small owers.

Fig. 3. SEM images of anodised samples.

Fig. 4. Anodised samples of unpolished scrap CP Ti.

Table 3 Anodising of scrap titanium at 5 V intervals Sample code 1J 1J 1J 1J 1J 1J 1J 1J 1J 1J 1J 1J

a

Metal sourcea/type Scrap Scrap Scrap Scrap Scrap Scrap Scrap Scrap Scrap Scrap Scrap Scrap

Mechanical nish Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished Unpolished

Colouring process Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised Anodised

Voltage (V) 25 30 35 40 45 50 55 60 65 70 75 80

Colour Cyan blue Pale turquoise Silver Pale gold Yellow Gold Orange gold Pink Mauve Blue/gold patches Turquoise Green

CP titanium sheet of unknown origin.

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Fig. 5. Scrap CP Ti, unpolished, anodized at various voltages. SEM images at 10,000.

the fact that titanium from a known source does not exhibit this behaviour under similar conditions. It has been established that the Flower oxides that are observed when the unpolished scrap metal is anodised commence growth at close to 30 V and continue to increase in density with increasing voltage. The differing appearance of the owers seems to indicate a dynamic process of growth and disintegration as the overall oxide layer thickens but no suggestions have been advanced for such a process. It has so far not proved possible to discover what processes the scrap sheet may have undergone to produce the somewhat cellular appearance seen under magnication by SEM. The surface analysis of the scrap indicates only that the material is CP grade titanium. Simple washing and degreasing of the metal does not remove the unknown attribute but mechanical polishing does. There are no obvious visual differences between the samples which show owers and those which do not but the oxide growth is appreciably faster on the surfaces that exhibit the Flower oxides. This unexpected and curious feature has not been previously documented and further work is planned to investigate the nature of the owers in terms of structure, precise composition and initiation. An experimental programme is in hand to examine the cross section of the oxide layer attached to the titanium surface. This preliminary work was undertaken with the help of the late Professor Harvey Flower at Imperial College, London and this paper is produced in his honour.

3. Conclusions References In the majority of cases the thin oxide layer developed on the surface of polished or unpolished CP grade titanium that exhibits interference colours is uniform in appearance and follows the topographical structure of the underlying metal surface. This applies whether the oxide has been created by heat or anodising. The unusual growth features that are observed when scrap CP titanium is anodised must be caused by some, as yet, unidentied attribute of the surface of this material which acts as a growth site, under electrochemical conditions, for what is most likely to be some form of crystalline titanium oxide. This is conrmed by
[1] [2] [3] [4] [5] [6] Aladjem A. J Mater Sci 1973;8:688. Nassau K. Sci Am 1980;243(4):124. Sibert ME. J Electrochem Soc 1963;110:65. Cotton JB, Hayeld PCS. Trans Inst Met Finish 1967;45:48. Flower HF, Swann PR. Acta Metall 1974;22:1339. Fukuzawa et al. In: Kimura H, Izumi O, editors. Fourth international conference on titanium 1980, Kyoto, AIME, New York, 1980. p. 2783. . [7] Gueneau de Mussy J- P, et al. Scrip Mater 2003;48:23. [8] Hass G. Vacuum 1952;2:331. [9] Ward James Brent, The colouring and working of refractory metals, Worshipful Company of Goldsmiths Project Report No. 35/1, London; January 1982.