hydrocarbon may not be the best explanation of the two surface technology involved in the working of jewellery alloys.
energy states of a gold surface. References
Recent studies of the surface of solids show that a gold surface 1 A.W. Adamson, 'Physical Chemistry of Surfaces', 3rd Edition, Wiley, 1976
may exist either with its bulk atomic properties (unreconstructed 2 D. Maugis, 'Le Vide' 186, 1977, pp. 1-19, and in 'Microscopic Aspects of Adhesion
and Lubrication, edited byJ.M. Georges, Elsevier, 1982
surface) or with shorter (reconstructed) atom bond lengths at the 3 F.M. Fowkes, in `Treatise on Adhesion and Adhesives, Vol. 1, edited byR.L. Patrick,
surface. This could be the reason for the apparent experimental M. Dekker, 1966
4 A.A. Griffith, Phil. Trans, Roy. Soc., 1920, A221, 163-198
duality which exists, with the unreconstructed surfaces behaving 5 E.H. Andrews, Org. Coat. Appl. Polym. Sct Proc., 1982, 47, 328-331
in a hydrophylic manner while the reconstructed surfaces show 6 D. Maugis and M. Barquins, J. Phys. D. Appl. Phys., 1978, 77, 1989-2023
7 J. Schultz and A.N. Gent, J. Chem. Phys., 1973, 70, 708
hydrophobic behaviour. 8 A. Gent, Rubber Technol., 1947, 47, 202
The question of whether gold is hydrophobic or hydrophilic has 9 F.M. Fowkes, Adv. Chem, Ser., 1964, 43, 99
10 D.H. Kaelble, 'Physical Chemistry of Adhesion', Wiley, 1971
engineering consequences. One of these is the dropwise 11 EM. Rwkes, in 'Microscopic Aspects of Adhesion and Lubrication', edited byJ.M.
condensation of water vapour in heat exchanges. Georges, Elsevier, 1982
12 'Handbook of Chemistry and Physics', 60th Edition, CRC, 1979
Electrodeposited or evaporated gold surfaces of thickness greater 13 A.H. Cottrell, 'The Mechanical Properties of Matter; J. Wiley, 1964
than 200 nm, unlike those of steel or copper, show dropwise 14 A.A.V. Grosse,J. lnorg. Nucl. Chem., 1964, 26, 1349
15 H. Schonhorn,]. Phy.r, Chen., 1967, 71,4578
condensation. J.W. Westwater reviewed the state of the art in this 16 R.A. Erb, J. Phys. Chem,, 1965, 69, 1307
journal (21), and commented in the following terms: 'dropwise 17 J. Cognard and C. Boichard, in 'Adhesion', Vol. 8, edited by K.W. Allen, Elsevier
Applied Science, pp. 169-193, 1983
condensation will have commercial application as soon as the 18 K.W. Bewig and W.A. Zisman, J Phys. Chem., 1964, 68, 1804
troublesome problem of how to maintain it for a long time period 19 E. Thelen, J. Phys. Chem., 1967, 71, 1946-1948
20 F.M. Fowkes, Ind. Eng. Chem., 1964, 56, 40
is solved. Gold may offer the solution or indicate how to obtain the 21 J.W. Westwater, GoldBu!!., 1981, 14, (3), 95-101
solution'. 22 K.W. Bewig and W.A. Zisman, J Phys. Chem., 1965, 69, 4238
23 G. Valette,J Electroanal. Chem., 1983, 139, 285-302
Either gold has a unique behaviour towards organic 24 J. Clavillierand C. NeuyenvanHuong,J. Electroanal. Chem., 1973,41, 193. (In
contaminants or gold surfaces exist in two energetic states. Further the original work it was stated that gold was the most hydrophobic metal. In a
recent discussion with J. Clavillier he advised it to be expressed as the 'less
workshould aim towards obtaining experimental evidence for one hydrophilic metal')
or the other explanation found in the current literature. 25 M.L. White,]. Phys. Chem., 1964, 68, 3083-3085
26 T. Smith,]. Co!!. Ins Sei., 1980, 75, 51-55
Besides the above application it is of great interest to the jewellery 27 G.L. GainesJr., J. Coll. Int. Sci., 1981, 79, 295
industry that reliable adhesive joints to gold be developed, and 28 M. Schneegans and E. Meneel, J Coll. Int. Sei., 1982, 88, 97-99
29 R. Feders, Surf. Sei,, 1977, 68, 229-235
achieving this goal may change much of the present art and 30 M.A. Van Hove, Surf. Sei., 1979, 81, 1-7
Electropolishing of Gold
One of the aspects of gold working which has always been open to at the electrode surface and the redissolution of this oxide by the chloride
improvement, in particular with regard to the large jewellery ions present in the solution. Such behaviour, if controlled, might lead
manufacturing industry, is that of surface finishing of the gold piece. to useful polishing of the gold surface and Verlinden et al. have found
Mechanical finishing (polishing) is time consuming and requires skilled that modifying the electrolyte by the addition of glycerol reduced the
personnel. Electrolytic polishing in which gold is removed anodically gold dissolution rate to the extent that this could be achieved.
in a solution in a controlled manner to give a bright finish has been used Pure gold deposits with different morphologies were formed from
but is susceptible to a number of obstacles, chief of which is the difficulty additive-free cyanide gold plating solutions by varying the cathodic
of achieving a consistent finish on alloys of different caratage and current densities. Anodic polarization runs with these specimens in
containing different alloying elements. Most electropolishing which is hydrochloric acid-glycerol (25 : 75 weight per cent) solutions at room
carried out on gold alloys is effected in toxic cyanide solutions, which temperature revealed a passivation potential, due to the formation of
means that special precautions are needed to ensure safety. an Au(III)oxide film, which was independent of the structure and
Recent work reported by J. Verlinden, J.P. Celis and J.R. Roos morphology of the gold surface. At potentials close to that of passivation
('Passivity of Metals and Semiconductors, edited by M. Froment, periodic oscillations of current occurred similar to those previously
Elsevier Science Publishers, Amsterdam, 1984) on the passivation- obtained with unmodified hydrochloric acid solutions, and high quality
depassivation behaviour of gold in a hydrochloric acid-glycerol solution electropolishing of the gold surface was obtained. The quality of the
for the purpose of thinning electrodeposited gold samples for TEM surface finish appeared to be virtually independent of the initial
examination, extends our understanding of the subject and, if specimen topography and structure.
applicable to gold alloys, might well have significant practical Further improved control of the thinning process was achieved by
applications in other areas. applying a cyclic potential sweep between the active and passive ranges,
Previous work on the anodic behaviour of gold in hydrochloric acid so controlling the frequency of current oscillations and the times for
solutions had shown that when the gold electrode was held in a certain which the surface was in the active and passive regions.
potential range the current oscillated periodically and this was thought It will be interesting to see whether these potentially useful results
to be due to two competing processes viz, the formation of Au(III) oxide can be extended and applied to practical gold alloys. C.L.
GoldBull, 1984, 17, (4) 139
