Depletion Gilding PDF
Depletion Gilding PDF
Introduction because the treatments described recipes for refining, testing, alloying
The techniques of surface enrichment have a relevance to some of the more and soldering of gold, for gilding
of jewellery and other artefacts made modern processes such as wet and silver and other metals, and for the
from alloys containing gold have dry colouring. preparation of base metal alloys. An
been practised for well over 2000 The fact that base metals and silver English translation of the text was
years. The techniques are known as can be removed by chemical means published in 1926 (4) and discussed
Depletion Gilding or Mise en Couleur from gold alloys is well known. For more recently by Hunt (5). Of
and, in essence, the process involves example, when gold is assayed by particular interest in the context of
the removal of base metals and silver cupellation (fire assay), “parting “ with depletion gilding is Recipe No. 25:
from the surface layers to leave them nitric acid is used to remove silver “For treating gold or for thoroughly
considerably enriched in gold. This is leaving behind a residue of fine gold. purifying it and rendering it
obviously radically different from Similarly, refining by “inquartation” is brilliant: misy 4 parts; alum 4 parts;
other gilding processes such as done by alloying gold scrap with salt 4 parts. Pulverize with water
electroplating, electroless plating and copper such that the gold content is (to make a paste) and having
the older techniques of water gilding not greater than about 25%. It can then coated the gold with it place in an
and fire gilding where gold is applied be treated with nitric acid to remove earthenware vessel put in a
from an external source onto a silver and the base metals to leave furnace and luted with clay (i.e.
substrate, usually of base metal or silver. gold. Many early cultures in different sealed with clay) and heat until
Similar changes in surface parts of the world used chemical above named substances have
composition to enhance the colour and means for the surface enrichment of become molten; then withdraw it
finish of carat gold jewellery are gold-containing alloys and even for (the gold) and scour carefully.”
achieved nowadays using processes gold refining before nitric acid was According to Pliny, misy is either
such as Wet and Dry Colouring, bright available. In Europe, for example, iron or copper pyrites or their
acid dipping and pickling and chemical nitric acid has only been in use since oxidation products, i.e. the sulphates.
‘bombing’ with cyanide/peroxide the twelfth century
mixtures although these do not Pre-Columbian Goldsmiths
necessarily all involve surface Mediterranean Cultures The pre-Columbian cultures of Central
enrichment of gold. The last named Analysis of fifth and fourth century BC and South America were highly skilled
process is particularly hazardous Greek “white gold” and electrum coins at metal working, and archaeologists
because of dangers of spillage and has shown the existence of a gold- have drawn attention to the methods
toxicity and there are other enriched surface layer with that were used to produce gold-
disadvantages as will be seen later. concentrations of over 70% gold being enriched surfaces on items made from
There appears to be very little found in places, as compared to about alloys containing a low proportion of
recently published or readily 35% for the bulk of the metal (2,3). A gold. Gonzalo Fernandez de Oviedo
available practical information for cementation process was described by (1535-1548) wrote (6):
jewellery manufacturers on these Pliny in the first century AD for “... they know very well how to
processes although Rapson has refining gold. In this process, impure gild the objects and items they
reviewed some of the scientific gold is placed in a crucible in intimate make from copper and low grade
reports on selective dissolution and contact with a mixture of salt and brick gold. And they have such ability
corrosion of gold alloys in acid media dust and then heated. Base metals and and excellence in this, and give
(1). This paper is an attempt to silver are gradually removed from the such a high lustre to what they
disseminate some of the information gold and absorbed into the brick dust gild, that it looks like good gold of
so that manufacturers are encouraged leaving behind a residue of relatively 23 carats or more... They do this
to investigate the use of alternative pure gold which can be separated with a certain herb, and it is such a
processes to chemical bombing. from the brick dust by washing. secret that any goldsmith in
Another source of information on Europe or in any other part of
Historical background ancient techniques is the Leyden
It is pertinent to briefly review the Papyrus X, a metallurgical text *This is based on a presentation given at the 13th
Santa Fe Symposium on jewelry manufacturing
historical and archaeological written in the fourth century AD by a technology, held in Albuquerque, N.M., USA in May
evidence for depletion gilding goldsmith, and which contains 1999 (see report, this issue).
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After the completion of the Wet and Dry Colouring suggest that considerable
experimental work, Teresa del Solar There are old established chemical improvement in colour can be
demonstrated the possibilities for treatments, known as wet or dry achieved in lower carat alloys using
depletion gilding using the torch colouring, which were widely used in similar mixtures and it is possible that
heating method on a series of the jewellery trade, if not today, for the important factors of process time
plaques made from the ternary alloy imparting a rich gold colour to the and temperature, mixture
with various designs on their surface. These processes have been composition and caratage and
surfaces. Areas where depletion described in detail by Staton Abbey composition within caratage require
gilding was not desired were covered (12) and Ernest Smith (13). In a more thorough investigation.
with a resist and this was extended to essence, they are depletion gilding Recently, it has been reported that a
give variations in the colour of the processes using the same types of colouring solution containing a black
enriched surface by applying the treatments as described above. Two sludge or powder is being used to
resist at different stages of the heating recommended mixtures* for wet improve the appearance of gold
/washing cycles. The reflectivity of colouring (13) are:- jewellery after immersion. It is said to
the enriched layer was further give an ‘Italian Colour’ to the surface.
enhanced by burnishing and also by No. 1 No.2 It is known that the solution is based
finally heating in the presence of Potassium Nitrate 100 g 100 g on sulphuric acid. Analysis of the
ammonium sulphide or sulphur to Sodium chloride 50 g 50 g solution and the black sludge by
give what is often called an ‘oxidised Hydrochloric Acid 91.3 ml 91.3 ml Inductively Coupled Plasma (ICP)
silver’ finish to the undepleted Water 45.7 ml 53.3 ml Spectroscopy showed what chemical
regions. In fact, the characteristic * Converted to metric measures elements were present but not their
brown-black surface colouration is compound form. Aluminium was
due to the formation of sulphides. It will be noted that the only found in both the solution and the
Examples of the plaques are shown difference is that Solution No. 2 is sludge, where the level was
in Figure 13 (a & b). slightly more dilute. Nevertheless, particularly high. Although trace
Smith claims that this is better for 14 – amounts were found of a number of
18 carat jewellery. He states also that elements, there were significant levels
alloys as low as 9 carat can be treated of lead, tin and cadmium. It is possible
when suitable compositions are that these were impurities rather than
selected, preferably those with a low deliberate additions. It is not possible,
silver content. Some mixtures contain on the basis of these analytical results,
alum, e.g. potassium nitrate (100g), to be sure what the colouring solution
sodium chloride (50g) and alum contains but there is a probability that
(50g). Typical recommended aluminium is present as a sulphate in
procedures (12) are to gently heat, which case the solution is not too
melt and boil the powdered dissimilar from the solution described
compounds together with 40 ml above for depletion gilding and wet
water. Add 7 ml hydrochloric acid, and dry colouring.
reboil and then immerse the work to A ‘Rinse’ powder containing a
(a) be coloured for, say, 4 minutes, mixture of detergent and an
remove and rinse in clean boiling unknown active agent was also being
water. Then 20 ml water is added to used by the same manufacturer.
the colouring pot and then the Analysis by X-ray fluorescence
immersion and rinse process showed the presence of oxygen
repeated as necessary, with more (72%), sulphur (15%), aluminium
water being added between each (5.9%), potassium (2%) and sodium
immersion. (3%) together with silicon and
Dry colouring is similar except that phosphorus. This suggests
the acid and water are not added to aluminium sulphate or alum is the
the melt. Items are immersed directly major constituent with phosphate
(b) in the melt when it boils up and starts and silicones typical of modern
to fume, held for a few seconds until detergents.
the melt sinks down, withdrawn and Warning: Caution! Fumes arising
pickled in hydrochloric acid pickle to from the boiling mixtures and
remove the adhering mixture before solutions described above are
repeating the process. Final injurious to health and adequate
burnishing further improves the rich ventilation and use of a fume
brilliant gold colour. Both Smith and cupboard are essential. Again, care
Staton Abbey state that dry colouring must be taken when adding water to
Figure 13a-b - Decorative plaques given can only be used satisfactorily with these mixture but provided these
varied cycles of torch heating in alum 18 carat or higher quality golds. precautions are taken, the processes
paste and brick dust. However, our experience would are suitable for use in a workshop.
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Various concentrations of cyanide solder surface was depleted of gold acid and 20 g water for thinner
in solution have been reported and that the anticipated surface articles and one of 100 g potassium
ranging from 13 – 110 g/l but since enrichment as a result of depletion of nitrate, 65 g sodium chloride and 80 g
cyanide is potentially very base metals was not found in the hydrochloric acid for general use.
dangerous, the use of the lower presence of the corrosion product. Filigree work will necessitate a
concentrations is recommended (21). This might indicate that surface further dilution, i.e. 50 g hydrochloric
Indeed, Schneller has emphasized enrichment during ‘bombing’ occurs acid and 50 g water.
that there is no advantage in using by re-deposition of gold onto the It may well be that some research
higher concentrations and that the surface from the solution. and development work is needed to
process can be more efficient at the Normandeau concludes that a simple establish the best additives and
lower concentrations (22). He has solution to the problems of corrosion concentrations for particular
stated that 13 g/l is not only quite and the dangers of spillage and toxicity caratages and alloy compositions.
adequate but is safer. The reaction, in would be to eliminate chemical The advances in analytical
terms of weight loss, reaches a ‘bombing’ as a finishing process. procedures will greatly assist in
maximum at about 25 g/l and understanding the mechanisms of
reduces at higher concentrations. Concluding Remarks depletion and surface enrichment.
According to Normandeau and The time has come, perhaps, to re- It is hoped that this paper will
Faccenda, the base metals are examine some of the colouring and stimulate an interest in re-discovering
dissolved in the cyanide leaving a surface enrichment processes in use techniques for surface enrichment
thin surface layer enriched in gold. It in workshops earlier this century. At and colouring, particularly if they can
may be necessary to repeat the the time they suffered from a replace the hazardous operation of
process a number of times to achieve disadvantage that the surfaces chemical ‘bombing’.
the desired result, particularly if obtained were matt or porous and it
lower concentrations of cyanide are was necessary to burnish articles, References
used. Rapson and Groenewald say usually by scratch brushing with soap 1 W.S. Rapson, “Advances in
that the process can be used to lubricants. This may be acceptable Knowledge Relating to Gold
restore the colour of white golds if for a few items but it hardly lends Alloys and their Use in
they have developed a yellow tinge; itself to modern mass production Jewellery”, Proc. Santa Fe
presumably nickel-white golds due processing and was, perhaps, one Symposium, p65, 1995. Ed. D
to phase separation. reason why chemical ‘bombing’ Schneller, Met-Chem Research
Surprisingly, little seems to have appeared to be an attractive Inc., Boulder, Colorado.
been published on the mechanisms alternative. However, considerable 2 J.F. Healy and A.S. Darling,
of dissolution in chemical bombing. advances have been made in recent Nature, 231, p443, 1971.
One might expect that the base years in mass finishing equipment 3 J.H.F. Notton “Ancient Gold
metals and silver and gold will all be and processing. Refining”, Gold Bull., 7(2), p50,
selectively dissolved but that the rates The use of pastes and absorbent 1974.
of solution may vary with cyanide materials such as brick dust are 4 E.R. Caley, “The Leyden
concentration. There is an extensive unlikely to be suitable for factory Papyrus X”, J. Chem. Ed., 3,
review of the reactions with cyanide operations, although they may be for p1149, 1926.
in the book “The Metallurgy of Gold” small workshops, but the use of 5 L.B. Hunt, “The Oldest
by Rose and there it is stated that the solutions for immersion followed by Metallurgical Handbook”, Gold
rate of dissolution of gold goes rinsing and re-treatment, if necessary, Bull., 9(1), p24, 1976.
through a maximum with increasing should not present a problem. A final 6 “The Gold of El Dorado”,
cyanide concentration and is reduced burnishing treatment using modern Catalogue of Exhibition held at
at high concentrations (23). machinery may produce the desired the Royal Academy, London,
Normandeau has discussed also a finish in terms of gold enrichment 1979.
further problem with chemical and colour. 7 H. Lechtman, “Ancient Methods
‘bombing’ when using 10 carat There are a number of variations of Gilding Silver”, Science and
cadmium-free solders which contain when considering solutions. Boiling Archaeology. p2, 1971. Ed. R.H.
indium (20). Indium cyanide may be in a solution of 40 g/100 ml of Brill, M.I.T. Press, Cambridge,
deposited as a discoloured corrosion potassium aluminium sulphate Mass, U.S.A.
product on the jewellery, requiring (alum) for two hours certainly 8 H. Lechtman, “The Gilding of
removal by additional finishing produced an acceptable result with Metals in Pre-Columbian Peru”,
operations such as abrasive the 9 carat gold-silver and gold-silver- Proc. Third Sem. (1970) on
polishing. This, in turn, may produce copper alloys and it is probable that Application of Science in the
a toxic dust and precautions would some of the other solutions given Examination of Works of Art,
be required against inhalation. The earlier in the paper will give equally Boston, Mass., 1973.
corrosion problem was not observed good results in perhaps a shorter 9 D.M. Jacobson, and J.S.
with 14 and 18 carat solders time. Reference 15 quotes an earlier McKenzie, “Transmutation of
containing indium. worker who recommends an etch of Base Metals into Gold”,
Energy dispersive X-ray analysis 100 g of potassium nitrate, 65 g Interdisciplinary Science Rev.,
showed that the chemically ‘bombed’ sodium chloride, 60 g hydrochloric 17(4), p326, 1992.
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