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INTRODUCTION
Throughout history, gold plating silver and copper-alloy jewelry, statues,
figurines, coins, and other metal items
served a variety of purposes. In addition
to its decorative effect, which often appeared in combination with other techniques (e.g., inlay or relief decoration),
gold plating improved corrosion resistance and created the deliberate impression of a completely gold object. The
earliest gilded-metal objects, circa the
third millennium B.C., were produced by
covering the artifacts with gold foil and
then mechanically attaching it (e.g., by
folding the foil around the object) by
riveting or, later, hammering the edges
of the gold foil into grooves cut into the
substrate.1 Gold leaf was subsequently
used, which was produced by hammering the gold to a thin gage and then
attaching it with an adhesive. Pliny (c.
70) mentioned the use of egg-white for
this purpose,2 while resin or drying oil
were possible alternatives.
Over the last 30 years, there has been a discernible increase in the number of scholars who have focused their research on early industrial organizations, a field of study that
has come to be known as Archaeotechnology. Archaeologists have conducted fieldwork geared to the study of ancient technologies in a cultural context and have drawn on
the laboratory analyses developed by materials scientists as one portion of their interpretive program. Papers for this bimonthly department are solicited and reviewed by Robert
M. Ehrenreich of the National Materials Advisory Board of the National Research Council.
58
(~ Au3Hg)
(Au2Hg)
Temperature C
100
(Hg)
1
surface has a matte appearance.
an adhesive (typical thickness of
Twisted tubular amalgam particles,
0.10.4 m). 3,4 This is explained by
0 10 20 30 40 50 60 70 80 90 100
formed in the grinding process
the
fact that fire gilding is a diffuAu
Hg
Weight Percent Mercury
during preparation of the Au2Hg/
sion-bonding process; the role of
the mercury is to ensure a close
Hg paste, survived on the gilded
contact of substrate and plating. Because
avoid overheating the object because of
surface of the experimental samples preof the diffusion of copper or silver from
coppers tendency to oxidize in air at
pared for this study (Figure 2). This and
the substrate into the gold, plating with
high temperatures. Due to the porosity
the fact that the coating did not run
a thickness of less than 12 m would
of the gold amalgam, a black copperwhen samples were fired in an upright
show visible discoloration. On the other
oxide layer also forms beneath the gold,
position indicated that the gold amalhand, a thickness of more than 10 m not
the thickness of which increases with
gam did not become liquid at any point.
only meant unnecessary expense, but, as
temperature and length of time of the
Thus, the mercury must sublime directly
the experiments showed, often remained
heating. This layer eventually causes the
from Au2Hg.
uneven after burnishing.
plating to flake off. In the case of silver,
After heating, the object is burnished
To determine the influence of variawhich can be brought to a red heat in air
with an agate or steel burnishing tool to
tions in firing temperature on the rewithout oxidizing, the temperature is
compress the porous structure and crelimited by the rate of interdiffusion between the gold plating and the silver
substrate. If silver is overheated, the gold
will discolor or even disappear into the
substrate altogether, which restricts the
maximum firing temperature to approximately 350C. The best results were obtained in the laboratory when samples
were heated just beyond the color change
(i.e., 250350C) for heating times not
exceeding 1015 minutes.
Several authors1,9,10 have argued that
amalgam gilding could also be per20 m
20 m
formed without heating by using merFigure 1. A secondary electron image of the
Figure 3. A secondary electron image of the
cury as an adhesive and leaving the obsurface of an amalgam gilding replication
surface of an amalgam gilding replication
ject in open air until the excess mercury
sample before burnishing.
sample after burnishing.
59
90
Bunker et al. and Twilley
80
Hg
60
ing the firing temperaAu
50
ture by the assumption
Ag
40
that gold amalgam
30
would melt in the pro
20
10
5
dence, such as the fact
20
25
0
5
10
15
that amalgam gilding did
Relative Distance (m)
not run over the surface
Figure 5. An electron-microprobe element concentration profile
in the furnace and that
across fire gilding gold amalgam paste on silver. The sample
twisted amalgam parwas heated for ten minutes at 305C. Note the narrow mercury
ticles from the preparapeak (<20% mercury) between the silver and gold.
wt. %
wt. %
100
Hg
90
80
Au
70
Ag
60
50
40
30
20
10
0
5
15
20
25
10
Relative Distance (m)
Figure 4. An electron-microprobe element concentration profile
across gold foil applied to a silver surface pretreated with
mercury. The sample was heated for ten minutes at 305C.
Note the 10 m thick silver amalgam layer (3040% mercury)
between the silver and gold.
20 m
Figure 6. A secondary electron image of an
amalgam gilded surface on Cu-20Pb-10Sn
after 25 minutes of heating at 300C, showing
the gold-lead amalgam crystals in liquid mercury.
20 m
Figure 7. A secondary electron image of an
amalgam gilded surface on Cu-20Pb-10Sn
after ten minutes of heating at 400C, showing the network of gold-lead amalgam crystals with a few droplets of liquid mercury
(arrow).
61
have led to gas porosity in the solidifying metal. From the experiments reported here, it is evident that a low lead
content was certainly desirable, but the
reason why a bronze higher-tin was not
chosen for the horses remains obscure.
Large casts such as these would have
been difficult enough with a lower melting bronze.
CONCLUSIONS
It was previously assumed by most
authors that fire gilding was a hightemperature technique in which an object was heated at least to the boiling
point of mercury or even as high as
500C. This study has shown that the
gilding process was, in fact, carried out
For craftspeople,
there was no need
to measure the
temperature: they
heated an object to
the point of color
change or slightly
beyond.
at a much lower temperature; it was a
solid-state reaction that did not involve
melting the gold amalgam. As a
nonequilibrium process, it also cannot
be described in terms of the phase diagram.
For craftspeople, there was no need to
measure the temperature: they heated
an object to the point of color change or
slightly beyond. They knew that overheating spoiled the gilding, however,
and restricted the gilding temperature
to the 250350C range, which left 8
25% mercury in the gold. Thus, fire gilding should be readily identifiable with xray fluorescence analysis of the surface.
If mercury is only detectable with much
more sensitive methods like atomic absorption spectroscopy or emission spectrometry, it is likely that it was only
present as a contaminant.
Aesthetically, the wide range of possible mercury contents in fire gilding (8
25% mercury) does not have any significant effect on the color of the gold. This
is quite surprising given the fact that the
gilding consists of one of two different
gold-mercury phases or a mixture of
botha solid solution of mercury in gold
with up to 15% mercury and Au3Hg
with 2025% mercury. Much more important to the final color is the degree of
interdiffusion with the substrate, copper or silver, that leads to a red or pale
discoloration if the gilding is too thin or
is overheated. Additional coloring of the
gilding with preparations of corrosive
salts was widely practiced by goldsmiths
and gilders.
ACKNOWLEDGEMENTS
The author thanks Peter Northover for
valuable discussion. The experimental work
was carried out with a grant from the German Ministry for Research and Technology/
German Academic Exchange Service.
References
1. A. Oddy, Metal Plating and Patination, ed. S. La Niece and
P. Craddock (Oxford: Butterworth-Heinemann, 1993), pp.
171181.
2. Pliny, Naturalis Historia, 33, chapter 33 (c. 70).
3. K. Anheuser, D.Phil. thesis, University of Oxford (1996).
4. P. Northover and K. Anheuser, (paper presented at the
Am. Inst. for Conservation Gilded Metals Symposium, St.
Paul, MN, June 1995).
5. B. Cellini, Dell Oreficeria, chapter 26 (1568).
6. Pliny, Naturalis Historia, 33 (c. 70), chapter 6465. The use
of alum for the cleaning of silver is also attested by a
fire-gilding recipe in the late 3rd or 4th century Egyptian
Leiden Papyrus X, recipe 41. R. Halleux, ed., Les A Ichimistes
Grecs, Vol. 1: Leiden Papyrus X, Stockholm Papyrus, Fragments
(Paris: Les Belles Lettres, 1981).
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Bulletin 12 (1979), pp. 3539.
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(St. Germain-en-Laye: Musee des Antiquites Nationales,
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C.S. Smith and J.G. Hawthorne, Transactions of the American
Philosophical Society, New Series, 64 (4) (1974), pp. 3128. (For
fire-gilding see recipes 55 and 219).
21. C.S. Smith and M. Teach Gnudi, eds., The Pirotechnia of
Vannoccio Biringaccio, Book IX, chapter 4 (New York: Dover,
1990). English translation only.
22. M.M. Mango and A. Bennett, Journal of Roman Archaeology Supplementary Series, 12 (1994).
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24. M. Berthelot and C.-E. Ruelle, eds., Collections des Anciens
A Ichimistes Grecs, 3 volumes, 1888 (Osnabruck: Otto Zeller,
1967). For stopping-out pastes see book VI, recipes 21, 23,
and 29. Further recipes are given in Cellinis Dells Oreficeria,
chapter 33.
25. A. Oddy et al., Small Bronze Sculpture from the Ancient
World, ed. M. True and J. Podany (Malibu, CA: J. Paul Getty
Museum, 1990), pp. 103124.
26. S.F. Moran, Artibus Asiae, 31 (1969), pp. 5565.
27. A. Oddy, S. La Niece, and N. Stratford, Romanesque
Metalwork: Copper Alloys and Their Decoration (London: British Museum, 1986).
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Various Arts, 1st Edition (London: Thomas Nelson, 1961).
29. P. Jett, Metal Plating and Patination, ed. S. La Niece and P.
Craddock (Oxford: Butterworth-Heinemann, 1993), pp. 193
200.
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205223.
31. M.J. Hughes, J.P. Northover, and B.E.P. Staniaszek,
Oxford Journal of Archaeology, 1 (1982), pp. 359364.
32. M. Ratka and P. Sahm, (paper presented at the 13th
International Bronze Congress, Harvard, 28th May1st June
1996). and M. Ratka and P. Sahm, Der betende Knabe, Original
und Rekonstruktion, ed. G. Zimmer and N. Hacklander (Frankfurt: Peter Lang), pp. 67-80.
33. A. Oddy, MASCA Journal, 2 (1982), pp. 4547.