16

Introduction
The techniques of surface enrichm ent
of jew ellery and other artefacts m ade
from alloys containing gold have
been practised for w ell over 2000
years. The techniques are know n as
Depletion Gildingor Mise en Couleur
and, in essence, the process involves
the rem oval of base m etals and silver
from the surface layers to leave them
considerably enriched in gold. This is
obviously radically different from
other gilding processes such as
electroplating, electroless plating and
the older techniques of w ater gilding
and fire gilding w here gold is applied
from an external source onto a
substrate, usually of base m etal or silver.
Sim ilar changes in surface
com position to enhance the colour and
finish of carat gold jew ellery are
achieved now adays using processes
such as W et and D ry Colouring, bright
acid dipping and pickling and chem ical
bom bingw ith cyanide/peroxide
m ixtures although these do not
necessarily all involve surface
enrichm ent of gold. The last nam ed
process is particularly hazardous
because of dangers of spillage and
toxicity and there are other
disadvantages as w ill be seen later.
There appears to be very little
recently published or readily
available practical inform ation for
jew ellery m anufacturers on these
processes although Rapson has
review ed som e of the scientific
reports on selective dissolution and
corrosion of gold alloys in acid m edia
(1). This paper is an attem pt to
dissem inate som e of the inform ation
so that m anufacturers are encouraged
to investigate the use of alternative
processes to chem ical bom bing.
Historical background
It is pertinent to briefly review the
historical and archaeological
evidence for depletion gilding
The Surface Enrichment of Carat Gold
Alloys Depletion Gilding*
MARK GRIMWADE
Consultant, UK
because the treatm ents described
have a relevance to som e of the m ore
m odern processes such as w et and
dry colouring.
The fact that base m etals and silver
can be rem oved by chem ical m eans
from gold alloys is w ell know n. For
exam ple, w hen gold is assayed by
cupellation (fire assay), parting w ith
nitric acid is used to rem ove silver
leaving behind a residue of fine gold.
Sim ilarly, refining by inquartationis
done by alloying gold scrap w ith
copper such that the gold content is
not greater than about 25% . It can then
be treated w ith nitric acid to rem ove
silver and the base m etals to leave
gold. M any early cultures in different
parts of the w orld used chem ical
m eans for the surface enrichm ent of
gold-containing alloys and even for
gold refining before nitric acid w as
available. In Europe, for exam ple,
nitric acid has only been in use since
the tw elfth century
Mediterranean Cultures
Analysis of fifth and fourth century BC
G reek w hite goldand electrumcoins
has show n the existence of a gold-
enriched surface layer w ith
concentrations of over 70% gold being
found in places, as com pared to about
35% for the bulk of the m etal (2,3). A
cem entation process w as described by
Pliny in the first century A D for
refining gold. In this process, im pure
gold is placed in a crucible in intim ate
contact w ith a m ixture of salt and brick
dust and then heated. Base m etals and
silver are gradually rem oved from the
gold and absorbed into the brick dust
leaving behind a residue of relatively
pure gold w hich can be separated
from the brick dust by w ashing.
Another source of inform ation on
ancient techniques is the Leyden
Papyrus X, a m etallurgical text
w ritten in the fourth century AD by a
goldsm ith, and w hich contains
recipes for refining, testing, alloying
and soldering of gold, for gilding
silver and other m etals, and for the
preparation of base m etal alloys. An
English translation of the text w as
published in 1926 (4) and discussed
m ore recently by H unt (5). O f
particular interest in the context of
depletion gilding is Recipe N o. 25:
For treating gold or for thoroughly
purifying it and rendering it
brilliant: m isy 4 parts; alum 4 parts;
salt 4 parts. Pulverize w ith w ater
(to m ake a paste) and having
coated the gold w ith it place in an
earthenw are vessel put in a
furnace and luted w ith clay (i.e.
sealed w ith clay) and heat until
above nam ed substances have
becom e m olten; then w ithdraw it
(the gold) and scour carefully.
A ccording to Pliny, m isy is either
iron or copper pyrites or their
oxidation products, i.e. the sulphates.
Pre-Columbian Goldsmiths
The pre-Colum bian cultures of Central
and South Am erica w ere highly skilled
at m etal w orking, and archaeologists
have draw n attention to the m ethods
that w ere used to produce gold-
enriched surfaces on item s m ade from
alloys containing a low proportion of
gold. G onzalo Fernandez de O viedo
(1535-1548) w rote (6):
... they know very w ell how to
gild the objects and item s they
m ake from copper and low grade
gold. A nd they have such ability
and excellence in this, and give
such a high lustre to w hat they
gild, that it looks like good gold of
23 carats or m ore... They do this
w ith a certain herb, and it is such a
secret that any goldsm ith in
Europe or in any other part of
*This is based on a presentation given at the 13th
Santa Fe Sym posium on jew elry m anufacturing
technology, held in Albuquerque, N .M ., U SA in M ay
1999 (see report, this issue).
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Christendom , w ould soon becom e
a rich m an from this m anner of
gilding.
The depletion gilding techniques
that w ere m ost likely to have been
used by the pre-Colum bian Indians
have been investigated by Lechtm an
(7,8). The alloys used w ere generally
of tw o types. O ne type w as know n as
tumbaga, reddish, bronze-coloured
copper-gold alloys produced w ith
differing gold contents, and probably
containing silver as an im purity. The
other type w ere pale greenish-w hite
ternary silver-gold-copper alloys
containing a high proportion of
silver. These w ere not dissim ilar to
the electrumof the M editerranean
w orld and appear to have been
w idely used in Peru.
The m ethods used by the pre-
Colum bian goldsm iths also fall into
tw o groups. The first is Mise en
Couleur, a nam e given in
archaeological circles to processes
for depletion gilding objects m ade
from tum baga, in w hich the alloy w as
rubbed w ith the juice of a plant and
then heated so that it assum ed a gold
coloration due to the rem oval of
copper from the surface layer. This
process could be repeated m any
tim es to increase the thickness of the
gold-enriched layer and im prove its
colour. It is believed that the plant
w as a species of oxalis and that the
juice contained oxalic acid. It is
possible that am m onium carbonate
soaked in urine w as also used.
Lechtm an has pointed out that
although depletion gilding of
tum baga w orks w ell w ith these
processes, they do not rem ove any
silver that m ight be present in the
alloy.
G old alloys of the electrum type
containing high silver w ere probably
gilded using a cem entation process
or by using special aqueous pastes.
In the cem entation process, the
object to be gilded w as placed in a
crucible and surrounded w ith a
pow dered m ixture w hich invariably
contained alum (potassium
alum inium sulphate), com m on salt
(sodium chloride) and brick dust.
The crucible and its contents w ere
heated and the m ixture reacted w ith
the surface of the alloy to form
chlorides of silver, copper and other
im purity m etals. The m olten
The Vicus culture w as follow ed by
the M ochicas w ho excelled in a
variety of m etalw orking techniques,
such as raising, forging, chasing and
lost w ax casting using m ainly the
high silver-containing alloys, sim ilar
to electrum . They in turn w ere
follow ed by the Chim u (1000-1470
A D ) w ho w ere highly skilled in
depletion gilding objects m ade from
tum baga and electrum type sheet.
Jacobson and M cK enzie (9) and
Scott (10) put forw ard the argum ent
that low gold alloys containing
copper w ere first heated in air to
produce a black copper oxide scale
and then treated to selectively
rem ove the copper and silver.
chlorides w ere then absorbed by the
brick dust. A dditional ingredients
m ay have been am m onium chloride,
potassium nitrate, copper and iron
sulphates, vinegar and urine. A fter
cooling, and subsequent w ashing to
rem ove residues, the brilliance of the
gold-enriched surface w as im proved
by burnishing.
A n alternative m ethod w as to
im m erse an object to be gilded in an
aqueous paste or solution of alum ,
iron sulphate and salt at room
tem perature. After about ten days, it
w as taken out and w ashed in a strong
salt solution to rem ove surface scale.
The object w as then heated to
convert the spongy, gold-enriched
surface to a sm ooth com pact richly
coloured surface. B oth the
cem entation and the aqueous paste
m ethods w ork equally w ell on alloys
w ith a high silver content and w ith
tum baga.
Figure 1 show s discs w hich w ere
m ade in Peru probably during the
early Vicus period. The classical Vicus
period w as betw een 400 BC and 100
AD , although there w as a later period
w hich extended to about 700 AD . It is
thought that these particular discs are
from the earlier period because of the
lack of surface decoration. The discs
had lain buried for m any centuries
and traces of black corrosion
products m ay be seen in the
m icrographs of cross sections of the
discs, Figure 2. A thin, gold-rich layer
is clearly visible, w hich is surrounded
by corrosion products in places. Tiny
flecks of gold can be seen w ithin
corrosion products, Figure 3. These
particular discs w ere m ade from
tum baga having high copper and low
gold contents.
Figure 1 - D epletion gilded tum baga
discs from the Vicus Period, Peru
Figure 2 - C ross-section of Vicus disc
show ing depletion gilded layer. x200
Figure 3 - Vicus disc show ing gold flecks
in corrosion products. x200
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experim ents. U sing electrically
heated ovens or m uffle furnaces,
tem peratures in the range 100 to
600C and treatm ent tim es ranging
from 15 m inutes to several hours
w ere investigated. The follow ing
trends w ere observed.
At tem peratures in the range 100-
150C, enriched layers of up to 7 m
in thickness w ere obtained but these
had a patchy grey surface
discolouration and grey inclusions
w ere found w ithin the layer. It is
thought that these w ere due to the
form ation of silver chloride w hich
could not be rem oved and absorbed
either by the porous crucible or by
brick dust at these relatively low
tem peratures.
B etter results w ere obtained in
the range 150-200C w ith only a few
greyish patches being visible on the
surface. Figure 4 show s a
m icrosection of a 9 carat sam ple after
7 hours at 165C in the alum paste
w ithout brick dust but in an
earthenw are pot. The layer thickness
is 10-12 m .
At tem peratures in the range 400-
600C, there w as depletion of silver
in the grain boundaries adjacent to
the surface layer, Figure 5.
Although both the alum and iron
salt pastes yielded depletion gilded
layers, the latter tended to give
blackened surfaces as w ell as grey
patches and inclusions and superior
results w ere obtained w ith the alum
paste.
A nother variation in technique
proved equally successful. In this,
sam ples w ere placed in the alum
paste w ith brick dust in an
earthenw are pot and gently heated
w ith a torch for 3 m inutes such that
the paste m elted but did not dry out.
A lthough tem peratures w ere not
m easured, the paste had an
appearance sim ilar to that w hen
furnace heating to 150-170C. A fter
w ashing, the treatm ent could be
repeated, w ith interm ediate w ashing,
as m any tim es as necessary to build
up the thickness and obtain the
desired surface.
Som e of the sections w ere
subjected to electron probe
m icroanalysis (EPM A) to analyse the
variation of gold and silver contents
in from the surface. Figures 6 and 7
show the gold and silver distributions
inw ards from the surface and Figures
Depletion Gilding Experiments
and Workshop Trials
In 1981, the author of this paper,
together w ith Teresa del Solar, an
archaeology graduate from Peru w ho
w as studying silversm ithing and
jew ellery at the C ity of London
Polytechnic, did som e experim ents
and w orkshop trials on depletion
gilding using cem entation and
aqueous paste treatm ents sim ilar to
those described earlier. The aim of
this short research program m e w as to
see w hether the techniques could be
successfully applied to 9 and 14 carat
gold-silver alloys (11).
The alloys w ere prepared using
fine gold and silver grain by m elting,
casting, forging and rolling to 1m m
thick strip w ith interm ediate and final
anneals. The hardnesses of the
annealed strips w ere H V40.5 and 42.5
for the 9 and 14 carat alloys,
respectively. The 9 carat alloy w as
w hite, w hereas the 14 carat alloy had
a distinct pale greenish-yellow tinge.
Tw o different pastes w ere
prepared by m ixing the pow dered
chem ical com pounds together w ith
sufficient distilled w ater to form a
thick paste. These w ere:
Alum paste
Potassium N itrate 10 g
Sodium Chloride 9 g
Potassium A lum inium Sulphate
(Alum ) 5g
Iron salt paste
Ferrous Sulphate 10 g
Sodium Chloride 5 g
Potassium N itrate 5 g
In som e experim ents, the pastes w ere
used alone w ith sam ples cut from the
alloy strips w hereas, in the
cem entation trials, the pastes w ere
m ixed in equal parts w ith brick dust.
Three types of crucible w ere used,
nam ely, glass, porcelain, and porous
earthenw are pots used for assaying.
The glass crucibles w ere unsuitable
as only thin depletion gilded layers of
poor quality w ere obtained.
Porcelain crucibles w ere satisfactory
only w hen brick dust w as present.
The porous earthenw are pots w ere
necessary to absorb the m olten
reaction products containing silver
from the surface layers in the absence
of the absorbent brick dust.
It is only necessary to sum m arise
the results from the m any
Figure 4 - 9ct gold-silver alloy treated 7
h at 165C in alum paste. x250
Figure 6 - EPM A analysis show ing gold
distribution inw ards from the surface of
9ct gold-silver alloy given 9 cycles of torch
heating in alum paste and brick dust.
Figure 5 - 9ct gold-silver alloy treated 15
m inutes at 600C in alum paste. x250
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19
8 and 9 show the corresponding
changes in concentration. The higher
gold content at the surface can be
clearly seen and w as calculated to be
69% for this particular 9 carat gold-
silver alloy sam ple, w hich had been
given nine cycles of torch heating for
3 m inutes follow ed by w ashing.
Because the gold-silver binary alloys
w ere considered to be too soft for
general jew ellery applications,
experim ents w ere done also on a
ternary 9 carat gold alloy containing
57.5% silver and 5% copper prepared as
before. The annealed strip, w hich w as
again w hitish in colour, had a hardness
of H V 70. The results w ith regard to the
quality and thickness of the depletion
gilded layers w ere sim ilar to those
achieved w ith the binary alloys.
Additional treatm ents, not tried w ith
the binary alloys, gave interesting
results. A sam ple of the ternary alloy
w as heated for 14 hours at 450C in a
m ixture of alum paste and brick dust
in an earthenw are pot. The surface
layer produced w as found to have an
intriguing structure, Figure 10. The
depleted layer w as about 75 m thick
but contained islands of relatively
undepleted m aterial w hich EPM A
indicated contained m ore copper than
did the bulk of the sam ple. This m ight
suggest that the silver is rem oved at a
faster rate than the copper. The
average gold content for this depleted
layer w as 51% . Sim ilar structures have
been observed in studies on the
corrosion behaviour of gold-silver
alloys in nitric acid, as w ill be
discussed later.
O ne sam ple of the ternary alloy
w as heated in a boiling solution of
alum (40g alum per 100 m l distilled
w ater) for tw o hours. The resulting
depletion gilded layer had a thickness
of about 2 m but w as com pact and
had a good gold colour, Figure 11.
The torch heating and w ashing
technique w as equally successful w ith
the ternary alloy. Figure 12 show s a
sam ple given nine cycles of 3 m inutes
in the alum paste/brick dust m ixture
w ith interm ediate and final w ashings.
The coating is 8-10 m and of good
quality. The advantage of these tw o
techniques is that they are relatively
easy to use in a w orkshop situation
and the tim e to produce a layer of,
say, 10 m thickness is m uch shorter
than w ith a single treatm ent in a
furnace.
Figure 7 - As Figure 6 show ing the silver
distribution.
Figure 8 - EPM A analysis show ing the x-
ray intensity distribution of gold. G old
peak calculated to be 69% .
Figure 9 - As Figure 8 show ing the x-ray
intensity distribution for silver.
Figure 10 - 9ct gold-silver-copper alloy
heated 14 h at 450C in alum paste and
brick dust. x200
Figure 11 - 9ct gold-silver-copper alloy
heated 2h in a boiling solution of alum .
x400
Figure 12 - 9ct gold-silver-copper alloy
given 9 cycles of torch heating in alum
paste and brick dust. x400
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A fter the com pletion of the
experim ental w ork, Teresa del Solar
dem onstrated the possibilities for
depletion gilding using the torch
heating m ethod on a series of
plaques m ade from the ternary alloy
w ith various designs on their
surfaces. A reas w here depletion
gilding w as not desired w ere covered
w ith a resist and this w as extended to
give variations in the colour of the
enriched surface by applying the
resist at different stages of the heating
/w ashing cycles. The reflectivity of
the enriched layer w as further
enhanced by burnishing and also by
finally heating in the presence of
am m onium sulphide or sulphur to
give w hat is often called an oxidised
silverfinish to the undepleted
regions. In fact, the characteristic
brow n-black surface colouration is
due to the form ation of sulphides.
Exam ples of the plaques are show n
in Figure 13 (a & b).
Wet and Dry Colouring
There are old established chem ical
treatm ents, know n as w et or dry
colouring, w hich w ere w idely used in
the jew ellery trade, if not today, for
im parting a rich gold colour to the
surface. These processes have been
described in detail by Staton A bbey
(12) and Ernest Sm ith (13). In
essence, they are depletion gilding
processes using the sam e types of
treatm ents as described above. Tw o
recom m ended m ixtures* for w et
colouring (13) are:-
No. 1 No.2
Potassium N itrate 100 g 100 g
Sodium chloride 50 g 50 g
H ydrochloric Acid 91.3 m l 91.3 m l
W ater 45.7 m l 53.3 m l
* Converted to m etric m easures
It w ill be noted that the only
difference is that Solution N o. 2 is
slightly m ore dilute. N evertheless,
Sm ith claim s that this is better for 14
18 carat jew ellery. H e states also that
alloys as low as 9 carat can be treated
w hen suitable com positions are
selected, preferably those w ith a low
silver content. Som e m ixtures contain
alum , e.g. potassium nitrate (100g),
sodium chloride (50g) and alum
(50g). Typical recom m ended
procedures (12) are to gently heat,
m elt and boil the pow dered
com pounds together w ith 40 m l
w ater. A dd 7 m l hydrochloric acid,
reboil and then im m erse the w ork to
be coloured for, say, 4 m inutes,
rem ove and rinse in clean boiling
w ater. Then 20 m l w ater is added to
the colouring pot and then the
im m ersion and rinse process
repeated as necessary, w ith m ore
w ater being added betw een each
im m ersion.
D ry colouring is sim ilar except that
the acid and w ater are not added to
the m elt. Item s are im m ersed directly
in the m elt w hen it boils up and starts
to fum e, held for a few seconds until
the m elt sinks dow n, w ithdraw n and
pickled in hydrochloric acid pickle to
rem ove the adhering m ixture before
repeating the process. Final
burnishing further im proves the rich
brilliant gold colour. Both Sm ith and
Staton Abbey state that dry colouring
can only be used satisfactorily w ith
18 carat or higher quality golds.
H ow ever, our experience w ould
suggest that considerable
im provem ent in colour can be
achieved in low er carat alloys using
sim ilar m ixtures and it is possible that
the im portant factors of process tim e
and tem perature, m ixture
com position and caratage and
com position w ithin caratage require
a m ore thorough investigation.
Recently, it has been reported that a
colouring solution containing a black
sludge or pow der is being used to
im prove the appearance of gold
jew ellery after im m ersion. It is said to
give an Italian Colourto the surface.
It is know n that the solution is based
on sulphuric acid. A nalysis of the
solution and the black sludge by
Inductively C oupled Plasm a (IC P)
Spectroscopy show ed w hat chem ical
elem ents w ere present but not their
com pound form . A lum inium w as
found in both the solution and the
sludge, w here the level w as
particularly high. A lthough trace
am ounts w ere found of a num ber of
elem ents, there w ere significant levels
of lead, tin and cadm ium . It is possible
that these w ere im purities rather than
deliberate additions. It is not possible,
on the basis of these analytical results,
to be sure w hat the colouring solution
contains but there is a probability that
alum inium is present as a sulphate in
w hich case the solution is not too
dissim ilar from the solution described
above for depletion gilding and w et
and dry colouring.
A Rinsepow der containing a
m ixture of detergent and an
unknow n active agent w as also being
used by the sam e m anufacturer.
A nalysis by X -ray fluorescence
show ed the presence of oxygen
(72% ), sulphur (15% ), alum inium
(5.9% ), potassium (2% ) and sodium
(3% ) together w ith silicon and
phosphorus. This suggests
alum inium sulphate or alum is the
m ajor constituent w ith phosphate
and silicones typical of m odern
detergents.
Warning: Caution! Fum es arising
from the boiling m ixtures and
solutions described above are
injurious to health and adequate
ventilation and use of a fum e
cupboard are essential. A gain, care
m ust be taken w hen adding w ater to
these m ixture but provided these
precautions are taken, the processes
are suitable for use in a w orkshop.
Figure 13a-b - D ecorative plaques given
varied cycles of torch heating in alum
paste and brick dust.
(b)
(a)
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21
Acid Pickling
A cid pickling has long been
practised, prim arily as a m eans for
rem oving oxide film s and flux
residues after heat treatm ent and
soldering operations.
A variety of pickling solutions, in
term s of the acid strength, type of
acid and bath tem perature, have
been used depending on the caratage
and com position w ithin caratage of
the gold jew ellery being treated.
Sm ith (13) give a good account of
com m on pickles and should be
referred to if m ore inform ation is
required.
Im portantly, acid pickles can
selectively dissolve out the base
m etals and silver from the surface
layers. Rapson and G roenew ald (14)
state that hydrochloric acid, sulphuric
acid and aqua regia acid m ixture
have been used for colouring but that
special procedures have to be
follow ed if m ore than superficial
surface enrichm ent is to be achieved.
They state also that som e gold is
dissolved in addition to the other
m etals but is re-deposited onto the
surface by electrochem ical
replacem ent m ethods. The technique
w orks best w ith copper-rich alloys of
14 carat or low er.
These procedures have been
outlined in one of a series of articles
appearing in a trade journal
published in G erm any probably
during the 1960s (15). Relatively
strong acid solutions have to be used,
otherw ise only the copper is
rem oved, leaving discoloured gold-
silver surfaces. A solution of 1:1
sulphuric acid: w ater is
recom m ended at 80C. This dissolves
som e silver from the surface.
Warning: Caution! Alw ays add the
acid to the w aterin a thin stream w ith
constant stirring. Never add water to
the acid as heat is rapidly evolved,
leading to boiling and violent
ejection of acid, giving the risk of a
serious accident to personnel.
For gold-silver-copper alloys, the
follow ing etchants are recom m ended
(15). W ater and chloride-free nitric
acid m ixed in the proportions 1:1 or
2:1. Both copper and silver dissolve
in nitric acid but Reference 15 says
that the copper dissolves earlier so
that, after a short etching tim e, the
colour appears too light. It is
necessary to etch for a longer tim e to
obtain the desired gold colour. It is
also noted that if chlorides are
present in the solution, silver chloride
m ay be form ed w hich is re-
precipitated back onto the surface,
causing discoloured patches.
It has been practice in m any
w orkshops (15) to gold boilthe
higher caratage gold w ares in pure
hydrochloric acid to obtain a deep
gold colour. Since the acid is non-
oxidising, the silver or gold is not
attacked and silver chloride is not re-
deposited. H ow ever, there is a
danger that w ith severely cold-
w orked, unannealed parts, the risk of
stress corrosion cracking m ay be
increased.
It should be noted that parts
should not be held by clam ps or
w ires of non-precious m etal w hen
im m ersed in acid pickles since these
w ill be attacked and go into solution,
causing re-deposition and unsightly
coatings of the m ore noble m etals.
A num ber of w orkers have studied
selective dissolution from noble
m etal alloys. N otably, Forty and
D urkin (16) and Forty and Row lands
(17) have studied the selective
dissolution in gold-silver and gold-
copper alloys in nitric acid and
proposed a m odel by w hich the
surface is enriched w ith gold. This
w ork w as review ed by Forty (18) and
discussed by Rapson at the 1995
Santa Fe Sym posium (1). Briefly, the
m echanism proposed is corrosion
tunnelling, w hereby the silver or
copper atom s are rem oved, leaving
gold atom s in the surface w hich form
islands and grow by a reordering
process involving surface diffusion,
Figure 14. A lloys containing m ore
than 50% gold rapidly form a
continuous gold surface and
passivate, i.e. the reaction is
effectively stopped w hereas w ith
low er caratage alloys, the enriched
surface w ill rem ain spongy and
porous and continue to increase in
thickness. It w ill be recognised that
this is the principle of inquartation
referred to earlier, w hereby excess
silver or copper has to be added to
higher caratage gold alloys to obtain
fine gold w hen boiling in nitric acid
for assaying or refining.
Chemical Bombing
In the early 1970s, a procedure for
brightening gold alloys by chem ical
m eans w as patented w hich has
becom e w idely know n as chemical
bombing (19). N orm andeau
described the process in som e detail
at the 1990 Santa Fe Sym posium (20).
Essentially, jew ellery w ares are
placed in a hot sodium or potassium
cyanide solution at 80-85C in a
suitable reaction vessel. A roughly
equal volum e of 30-50% hydrogen
peroxide (H
2
O
2
) is added and alm ost
im m ediately there is a violent
foam ing and explosive reaction
liberating oxygen gas. The reaction
should be quenched w ith cold w ater
just before it boils over. It can be
appreciated that this is a hazardous
operation and, at the very least, it
should be perform ed in an efficient
fum e cupboard. The full safety
precautions taken w hen using
cyanides m ust be observed.
Faccenda suggests that the process is
gradually being abandoned and that
relatively few com panies are using it
and then only w ith special closed
circuitequipm ent (21) to ensure
safety.
Figure 14 - C orrosion and diffusion re-
ordering m odel by selective dissolution.
After Forty et al (15,16)
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Various concentrations of cyanide
in solution have been reported
ranging from 13 110 g/l but since
cyanide is potentially very
dangerous, the use of the low er
concentrations is recom m ended (21).
Indeed, Schneller has em phasized
that there is no advantage in using
higher concentrations and that the
process can be m ore efficient at the
low er concentrations (22). H e has
stated that 13 g/l is not only quite
adequate but is safer. The reaction, in
term s of w eight loss, reaches a
m axim um at about 25 g/l and
reduces at higher concentrations.
A ccording to N orm andeau and
Faccenda, the base m etals are
dissolved in the cyanide leaving a
thin surface layer enriched in gold. It
m ay be necessary to repeat the
process a num ber of tim es to achieve
the desired result, particularly if
low er concentrations of cyanide are
used. Rapson and G roenew ald say
that the process can be used to
restore the colour of w hite golds if
they have developed a yellow tinge;
presum ably nickel-w hite golds due
to phase separation.
Surprisingly, little seem s to have
been published on the m echanism s
of dissolution in chem ical bom bing.
O ne m ight expect that the base
m etals and silver and gold w ill all be
selectively dissolved but that the rates
of solution m ay vary w ith cyanide
concentration. There is an extensive
review of the reactions w ith cyanide
in the book The M etallurgy of G old
by Rose and there it is stated that the
rate of dissolution of gold goes
through a m axim um w ith increasing
cyanide concentration and is reduced
at high concentrations (23).
N orm andeau has discussed also a
further problem w ith chem ical
bom bingw hen using 10 carat
cadm ium -free solders w hich contain
indium (20). Indium cyanide m ay be
deposited as a discoloured corrosion
product on the jew ellery, requiring
rem oval by additional finishing
operations such as abrasive
polishing. This, in turn, m ay produce
a toxic dust and precautions w ould
be required against inhalation. The
corrosion problem w as not observed
w ith 14 and 18 carat solders
containing indium .
Energy dispersive X -ray analysis
show ed that the chem ically bom bed
solder surface w as depleted of gold
and that the anticipated surface
enrichm ent as a result of depletion of
base m etals w as not found in the
presence of the corrosion product.
This m ight indicate that surface
enrichm ent during bom bingoccurs
by re-deposition of gold onto the
surface from the solution.
N orm andeau concludes that a sim ple
solution to the problem s of corrosion
and the dangers of spillage and toxicity
w ould be to elim inate chem ical
bom bingas a finishing process.
Concluding Remarks
The tim e has com e, perhaps, to re-
exam ine som e of the colouring and
surface enrichm ent processes in use
in w orkshops earlier this century. At
the tim e they suffered from a
disadvantage that the surfaces
obtained w ere m att or porous and it
w as necessary to burnish articles,
usually by scratch brushing w ith soap
lubricants. This m ay be acceptable
for a few item s but it hardly lends
itself to m odern m ass production
processing and w as, perhaps, one
reason w hy chem ical bom bing
appeared to be an attractive
alternative. H ow ever, considerable
advances have been m ade in recent
years in m ass finishing equipm ent
and processing.
The use of pastes and absorbent
m aterials such as brick dust are
unlikely to be suitable for factory
operations, although they m ay be for
sm all w orkshops, but the use of
solutions for im m ersion follow ed by
rinsing and re-treatm ent, if necessary,
should not present a problem . A final
burnishing treatm ent using m odern
m achinery m ay produce the desired
finish in term s of gold enrichm ent
and colour.
There are a num ber of variations
w hen considering solutions. Boiling
in a solution of 40 g/100 m l of
potassium alum inium sulphate
(alum ) for tw o hours certainly
produced an acceptable result w ith
the 9 carat gold-silver and gold-silver-
copper alloys and it is probable that
som e of the other solutions given
earlier in the paper w ill give equally
good results in perhaps a shorter
tim e. Reference 15 quotes an earlier
w orker w ho recom m ends an etch of
100 g of potassium nitrate, 65 g
sodium chloride, 60 g hydrochloric
acid and 20 g w ater for thinner
articles and one of 100 g potassium
nitrate, 65 g sodium chloride and 80 g
hydrochloric acid for general use.
Filigree w ork w ill necessitate a
further dilution, i.e. 50 g hydrochloric
acid and 50 g w ater.
It m ay w ell be that som e research
and developm ent w ork is needed to
establish the best additives and
concentrations for particular
caratages and alloy com positions.
The advances in analytical
procedures w ill greatly assist in
understanding the m echanism s of
depletion and surface enrichm ent.
It is hoped that this paper w ill
stim ulate an interest in re-discovering
techniques for surface enrichm ent
and colouring, particularly if they can
replace the hazardous operation of
chem ical bom bing.
References
1 W .S. Rapson, A dvances in
K now ledge Relating to G old
A lloys and their U se in
Jew ellery, Proc. Santa Fe
Sym posium , p65, 1995. Ed. D
Schneller, M et-Chem Research
Inc., Boulder, Colorado.
2 J.F. H ealy and A .S. D arling,
Nature, 231, p443, 1971.
3 J.H .F. N otton A ncient G old
Refining, Gold Bull., 7(2), p50,
1974.
4 E.R. C aley, The Leyden
Papyrus X , J. Chem. Ed., 3,
p1149, 1926.
5 L.B . H unt, The O ldest
M etallurgical H andbook, Gold
Bull., 9(1), p24, 1976.
6 The G old of El D orado,
Catalogue of Exhibition held at
the Royal A cadem y, London,
1979.
7 H . Lechtm an, Ancient M ethods
of G ilding Silver, Science and
Archaeology. p2, 1971. Ed. R.H .
Brill, M .I.T. Press, Cam bridge,
M ass, U .S.A.
8 H . Lechtm an, The G ilding of
M etals in Pre-Colum bian Peru,
Proc. Third Sem . (1970) on
A pplication of Science in the
Exam ination of W orks of A rt,
Boston, M ass., 1973.
9 D .M . Jacobson, and J.S.
M cK enzie, Transm utation of
B ase M etals into G old,
Interdisciplinary Science Rev.,
17(4), p326, 1992.
22
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10 D .A . Scott, D epletion G ilding
and Surface Treatm ent of G old
Alloys, J. H ist. M et. Soc., 17(2),
p99, 1983.
11 T. del Solar and M .F.G rim w ade,
The Art of D epletion G ilding,
Aurum, 12, p46, 1982.
12 Staton Abbey, The G oldsm iths
and Silversm ithsH andbook,
2nd Ed. Publ. by The Technical
Press, London, 1968.
13 E.A . Sm ith, W orking in
Precious M etals. Re-published
by N .A .G . Press, C olchester,
Essex, England, 1978.
14 W .S. Rapson and T.
G roenew ald, G old U sage.
Publ. by A cadem ic Press Inc.,
London, 1978.
15 A non., K leine
Edelm etallkunde: K ursus fr
G old und Silberschm iede,
Section 2.1.4.1. (This course
appears in a series of articles in
G old und Silber, U hren und
Schm uck extending over a
num ber of years.)
16 A .J. Forty and P.D urkin,
Phil.M ag., 42, p295-318, 1980
17 A .J. Forty and G . Row lands,
Phil. M ag., 1980, review ed in
(18) .
18 A .J. Forty, Gold Bull., 14 (1),
p25-35, 1981.
19 G . M ulnet, French Patent
2,137,296, 1972.
20 G . N orm andeau, C adm ium -
Free G old Solders: A n U pdate.
Indium Toxicity and Potential
W orkplace Exposures, Proc.
Santa Fe Sym posium , p239,
1990. Ed. D . Schneller, M et-
C hem . Res. Inc., B oulder,
Colorado.
21 V . Faccenda, H andbook on
Finishing in G old Jew ellery
M anufacture, Published by
W orld G old Council, 1999.
22 D . Schneller, Safety
O verview s. G iven at each
annual Santa Fe Sym posium .
23 T.K . Rose and W .A.C. N ew m an,
The M etallurgy of G old,
Chap.XIII, 7th Ed. Re-published
by M et-C hem . Res. Inc.,
Boulder, Colorado, 1986.
23
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