High-Carat Golds Do Not Tarnish?

By Dr. Christopher W. Corti, Manager of Technical

Information & Development, World Gold Council

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 High-Carat Golds Do Not Tarnish?

Dr. Christopher W. Corti

Manager of Technical Information & Development
World Gold Council, London

Abstract
It is a generally considered that only low-carat golds tarnish during normal
wear, with 18-carat golds tarnishing on rare occasions. The perceived wisdom
is that high-carat golds do not suffer tarnishing. In India, frequent comments
are made that 22-carat golds go redder in colour on exposure in shop windows
and, more recently, complaints have been heard of 22-carat gold jewellery
which has gone black whilst in normal use by the owner. Is this conventional
tarnishing of high-carat gold or is it due to tarnishing of lower-carat material
such as solders used in their manufacture? Or is there some other cause such
as severe oxidation?
Following a general description of the tarnishing of gold jewellery and possible
causes, this presentation describes an investigation into two samples of
22-carat gold jewellery obtained from India which show such blackening in
recessed areas after wear. The analytical evidence has enabled us to determine
the nature of the blackened surface and to conclude that even 22-carat golds
can tarnish under the relatively severe corrosive conditions that appear to
exist in some households.
Introduction
Over the last 3–4 years, World Gold Council has conducted a number of
technical seminars and workshop visits in the major jewellery manufacturing
centres in India. This is a predominantly 22-carat gold market and the largest
gold jewellery market in the world, consuming over 700 tonnes gold in 1999.
During these visits, we have heard many complaints that 22-carat gold
jewellery goes black during normal wear by the consumer and is often returned
to the retailer. We also hear complaints that 22-carat gold jewellery goes a
darker redder shade when displayed in shop windows.
These problems are unreported in the literature and outside of our experience,
so we were unable to provide satisfactory answers as to the causes. Could both
these phenomena be due to conventional tarnishing such as is seen in low-
carat golds? Surely not! The perceived wisdom is that high-carat golds do not

May 2000 29
tarnish (1). An oft-quoted generalization is that carat golds with a gold
content of 50 atomic % or more do not tarnish. For gold-copper-silver alloys,
50 at. % gold equates to a caratage of between 15.6 and 18 carats, depending
on the copper/silver ratio. This would suggest that 22-carat gold-copper-silver
alloys at 91.7 wt. % gold, being well above this critical gold content, should
not be susceptible to tarnishing during normal use.
In the summer of 1998, I was fortunate to obtain two items of 22-carat gold
jewellery, each from different retailers, which showed this blackening of the
surface and had been returned by their customers. This presented an opportu-
nity to perform a surface analysis to determine the nature of this blackened
surface. The results obtained were rather surprising and form the basis of this
presentation. But let us first look at tarnishing of jewellery in general to serve
as a background to this study.
Tarnishing of Jewellery
Mark Grimwade reviewed current knowledge on the tarnishing of carat gold
alloys at the 1993 Santa Fe Symposium (2), but as this has not yet been
published, it is worthwhile to re-iterate some of the basic facts. Firstly, we
should define “tarnishing.”
Tarnishing is usually defined as a discolouration of a metal surface caused by a
thin, often adherent, layer of a reaction product, such as an oxide or sulphide,
induced by a chemical reaction between the metal and its environment (3).
Thus, tarnishing is a product of a corrosion of the surface. This definition has
been extended to include the fact that such a discolouration renders the item
unsatisfactory for its intended purpose. For jewellery, this must relate to its
appearance, i.e. the loss of its metallic polish or lustre and colour.
Tarnishing of Silver
In silver and its alloys, tarnishing is a well-known phenomenon. The slow
discolouration and unattractive appearance of a black, yellow or brown tarnish,
which forms when silver is exposed to the atmosphere, is an unfortunate
consequence in silver jewellery and decorative ware. Considerable effort has
been expended to develop non-tarnish alloys for the jewellery industry in
recent years, some of which have been reported at this Symposium (4-6).
Tarnishing occurs when silver is exposed to sulphur-containing environments.
Analysis of natural tarnish films shows that they contain mainly silver
sulphide, β-Ag2S, under all conditions, with between 5 and 25% of other
components such as silver chloride, AgCl, silver oxide, Ag2O, and silver sul-
phate, Ag2SO4. For most metals, the oxide is thermodynamically more stable

30 The Santa Fe Symposium on Jewelry Manufacturing Technology

than the sulphide, but for silver the reverse is true, i.e. the sulphide is more
stable than its oxide. At ambient temperatures, it is very doubtful whether
silver forms a thin oxide layer on its surface (7).
Tarnishing of silver occurs much more readily when hydrogen sulphide, H2S,
is present in the atmosphere than when only sulphur dioxide, SO2, is present,
but research has shown that oxygen and moisture must be present too (8).
The actual mechanisms involved are reviewed and discussed by Shutt (7).
Tarnishing of Carat Golds
Pure gold does not react with the atmosphere and does not form oxides
or sulphides at ambient temperatures. Thus, tarnishing of carat golds is
attributable to the alloying metals, which typically include copper, silver and
zinc. Solders may include cadmium and indium and white golds either nickel
or palladium in addition.
Grimwade has reviewed the literature on the tarnishing of carat-gold alloys
(2). In general, much of this relates to tarnish testing performed under
artificial conditions in sulphur-containing environments, with the degree of
tarnish assessed indirectly, e.g. by colour measurements. However, there is
much analytical evidence to show that the tarnish films tend to be centered
on silver sulphide, Ag2S, with copper sulphides, CuS & Cu2S, and mixed silver-
gold and silver-copper sulphides present under some conditions (9-13). Where
chlorine is present, chlorides of copper and silver as well as mixed hydroxy-
chlorides are also formed. Chlorine is often present, as sodium chloride, in
human perspiration, of course. The point here of note is that tarnishing of
silver and of carat golds are similar in nature.
There is little information on the chemical nature of naturally formed tarnish films
on carat gold alloys exposed to the normal atmosphere. Ott gives a case study of
tarnish on a 10-carat yellow gold ring in (14) and states that the red-black tar-
nish film is due to silver and copper sulphide, deduced using energy dispersive
X-ray analysis in the scanning electron microscope. In a similar study of tarnished
9-carat yellow gold rings (15), X-ray photo-electron spectroscopy (XPS) analysis
of the tarnish layer showed both silver and copper sulphides present (XPS allows
the chemical state of the element to be determined).
From a thermodynamic standpoint, the relative stabilities of the oxides and
sulphides of copper, silver and zinc are, in ascending order:
Ag2O – Ag2S – CuS – Cu2S – AgCl – CuCl – CuO – Cu2O – ZnS – ZnO
As we can see, copper sulphides are more stable than silver sulphide but in
gold alloys the relative amounts of silver and copper may play a role. If zinc is

May 2000 31
present, its sulphide and oxide are the most stable, but their presence has not
been reported in tarnish films. The chlorides of silver and copper lie between
cuprous sulphide and cupric oxide.
From our accumulated knowledge of tarnishing, the following general points emerge:
• Multiphase alloys tarnish more readily than single phase alloys of the
same gold content. The metallurgical condition, particularly heat treat-
ments, can affect tarnishing rate.
• Tarnishing occurs more readily as the silver/copper ratio increases at the
same gold content. In two-phase alloys, the silver-rich phase tarnishes
preferentially.
• Zinc additions generally improve tarnish resistance, often through stabiliz-
ing a single phase structure. However, in the absence of silver, high-zinc
low-carat golds are more susceptible to tarnishing (16).
• Tarnishing occurs more readily as the gold content is reduced. However,
the overall picture with regard to tarnish resistance of low-medium carat
gold alloys is complex and it is not wise to generalize and relate tarnish
resistance directly to gold content.
Causes of Tarnishing
The nature of tarnishing clearly points to the presence of sulphur in some
form being necessary, together with moisture and oxygen. Sulphur is normally
present in the atmosphere, typically as sulphur dioxide and particularly in
industrially polluted atmospheres.
However, there are a number of other potential sources of contact with
sulphur-containing substances, often organic sulphur-containing chemicals.
These include:
• Human perspiration. The body chemistry of people is different and some
may be more prone to exude sulphur-containing compounds as well as
sodium chloride, which will tend to exacerbate any corrosion reaction,
particularly if a sulphur-rich diet is enjoyed.
• Food. Many foods are rich is sulphur, such as onions, eggs, fruit juices,
pickles and spices. Food preparation in the kitchen may be a vulnerable
situation from a tarnishing standpoint.
• Perfumes and deodorants, household cleaners, etc. Many sprays may
use sulphur-containing propellants and the actual contents being sprayed
or applied may also contain sulphur compounds.
• Jewellery storage boxes, plastic bags, etc. A common source of tarnish-
ing (14,15) is storage of jewellery in boxes where the lining material or
glue used contains sulphur compounds. The sulphur compounds evaporate
and contact the jewellery in a relatively static air atmosphere. Storage in
plastic bags can also lead to such sulphur emission.

32 The Santa Fe Symposium on Jewelry Manufacturing Technology

• Microporosity in cast gold jewellery. Surface microporosity may trap
pickling solutions, many based on sulphuric acid, during final finishing
or may absorb perspiration, perfumes and other liquids during wear,
leading to localized tarnishing which gradually spreads over the surface
of the jewellery.
In general, tarnishing is unsightly but is not a hazard to health, although it
can result in black smudging of the skin, which is undesirable but not harmful.
With this background on tarnishing, we can now move to the examination of
the two blackened 22-carat gold jewellery samples:
Examination of blackened 22-carat gold jewellery
The Jewellery Pieces

Sample A Front and reverse

Sample A was a flower-shaped pendant in 22-carat yellow gold with a central
red-coloured gemstone, received from Sri Rathna Jewellers, Rajapalayam.
Substantial blackening of the surface in some areas of the front side is appar-
ent (the reverse side does not exhibit this tarnishing), as shown in Sample A.
The exact processing history of this sample is not known, but it appears to be
made from a number of stampings soldered together.

May 2000 33
Sample B Front and Reverse
Sample B was another 22-carat yellow gold pendant, heavily gem-set and
rectangular in shape from Kumbakonam Jewellers, Salem. Again, considerable
blackening of the front side is apparent, but the reverse side is unaffected.
The following observations were made by the donor:
• The problem seems to occur mostly with stone-studded jewellery.
• The blackening occurs after a few days or months or even years in some
cases. In many instances the item is reheated (annealed?) and repolished
and returned to the owner.
• Many jewellers suffer this problem and feel its source is in the polishing
process. A typical polishing procedure is as follows:
1 A solution is prepared comprising 8g ordinary wax, 10g of a solidified
resin, four tablets of cyanide in 1 litre of water. The wax and resin give a
better colouring, it is claimed.
2 Two cyanide tablets are mixed in water, boiled and another two added.
One gram of 24-carat gold thin sheet, cut into pieces, is made soluble in
a cup of aqua regia acid mixture, dissolved by heating and then mixed
with a glass of water and added to the first solution.
3 The jewellery piece to be electropolished is brushed and made the anode
with pure gold as the cathode, presumably using the prepared solution as
the electrolyte.
4 After electropolishing, the jewellery is rinsed in tamarind water and cleaned.
5 The jewellery is stone-set.

Analytical examination
Each jewellery item was examined by two techniques: (a) by XPS spectroscopy,
which is a very sophisticated surface analysis technique, analyzing just a very

34 The Santa Fe Symposium on Jewelry Manufacturing Technology

thin surface layer, just atoms thick, and (b) by X-ray energy dispersive analysis
(EDA) in a scanning electron microscope (SEM), which analyzes a thicker sur-
face layer, some tens of microns thick. Both techniques measure which chemi-
cal elements are present at the surface, but the XPS technique can identify the
chemical state of each element, i.e. if it is unreacted or is chemically bound to
another element. The XPS technique measured an area of about 2mm x 2mm.
The energy dispersive analysis can examine the distribution of element concen-
tration over an area.
One aspect that was of concern was to check that each piece was actually
22-carat/917 fineness and/or the solders used were also 22-carat gold. It is not
uncommon for lower carat components and solders to be used in manufacture.
A cross-section of Sample A was taken and metallographically prepared. Exam-
ination under an optical microscope revealed no evidence of penetration by the
corrosion product, suggesting that a firestain type of problem due to internal
oxidation of copper, as seen in silver alloys, is not pertinent in this case.
Results
(a) XPS Analysis
Blackened areas of both samples A and B were examined and compared to
“clean” areas on each. The results are given in Table 1 (note that surface
contamination gives rise to high values for carbon):
Table 1. XPS Analysis (Concentrations in atomic %).

SAMPLE A SAMPLE B
Blackened Clean area, Blackened Clean area,
area, at % at % area, at % at %
Carbon 73.3 71.3 70.8 60.0
Oxygen 7.7 6.9 14.4 20.7
Gold 12.7 17.3 1.1 5.7
Silver 1.9 0.8 3.6 0.6
Copper 1.5 1.6 1.2 1.5
Sulphur 1.2 sulphide 1.0 sulphide 2.4 sulphide -
Chlorine 0.8 0.4 0.4 -
Sodium 0.8 0.7 0.6 0.8
Gold/silver ratio 6.7 24 3.3 9.5
Gold/copper ratio 8.5 10.8 0.9 3.8
Silver/sulphur ratio 1.6 0.8 1.5 -

May 2000 35
In Sample A, there were increases in concentration in both silver and sulphur
in the blackened area with the sulphur identified as being in the sulphide
state. Likewise, in Sample B, there were increases in silver and sulphur content
in the blackened area; in addition, no sulphur was detected in the clean area.
No cadmium or indium, common constituents of gold solders, was detected on
the surface of either sample.
From the measured binding energies, it is possible to conclude that the
sulphur in the blackened areas of both Sample A and Sample B is present as a
sulphide. For the silver, its low level precluded determining whether it was
present as the oxide or sulphide, although the latter is more probable. For
copper, we can state that it is in the cuprous (Cu[I]) chemical state but cannot
differentiate between oxide and sulphide as the binding energies are very simi-
lar. The clean areas of both samples also indicate that the silver and copper are
in the oxidized state, even though no sulphur was measured in Sample B.
(b) Energy-dispersive analysis in the SEM.
The aim here was to examine the blackened areas of both samples, to examine
the soldered joints of Sample A and to examine the composition of the clean
back of Sample B.
The areas examined and analyzed are marked in red on the scanning electron
micrographs (equivalent to photographs of the surface). These can be taken by
examining the secondary electron image or the backscattered electron image.
The backscattered image will show elemental contrast with heavy elements
(such as gold) appearing brighter. Elemental analysis is made by measuring
the emitted X-rays and is only semi-quantitative. Note that the X-ray peak for
sulphur is obscured by that of gold and so has not been reported.

36 The Santa Fe Symposium on Jewelry Manufacturing Technology

Sample A

Figure 2 (a) SEM Micrographs of Sample A, secondary electron image

Figure 2 (b) SEM Micrographs of Sample A, backscattered electron image

May 2000 37
Figure 2 (a) is a low-magnification (note 1mm scale) secondary electron image
of part of the item and Figure 2 (b) is the backscattered electron image of the
same area which is brighter due to elemental contrast effects. There is no
obvious contrast difference between bulk alloy and soldered areas, suggesting
that there are no major differences in gold content. The edge of the gemstone
—top center—can be seen as a dark area, as would be expected.

Figure 3 (a) Analysis of tarnished solder area, Sample A

Secondary electron image showing measurement area

38 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 3 (b) Analysis of tarnished solder area, Sample A
Energy-dispersive X-ray analysis

Figure 3 (a) shows a tarnished soldered area which has been analyzed. The
X-ray spectrum generated from the area examined is given in Figure 3 (b). As
well as gold (Au), silver (Ag) and copper (Cu), both cadmium (Cd) and Indium
(In)—constituents of solder—and some calcium (Ca) are present.

May 2000 39
Figure 4 (a) Analysis of gold alloy, Sample A
Secondary electron image showing measurement area

Figure 4 (b) Analysis of gold alloy, Sample A

Energy dispersive X-ray analysis

40 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 4 shows another area of the bulk gold alloy. Only gold, silver and copper
are detected. Based on relative peak heights, Fig. 4(b), the silver and copper
are at lower concentrations than seen in the tarnished solder area of Fig. 3.

Figure 5 (a) Spot analysis of dark solder area, Sample A

Electron image showing position of spot analysis

May 2000 41
Figure 5 (b) Spot analysis of dark solder area, Sample A
Energy-dispersive X-ray analysis
Figure 5 shows a spot analysis of a blackened area of solder (marked with a red
cross). Here we see not only gold, silver, copper with cadmium and indium but
also magnesium, aluminium, chlorine, calcium and iron as impurities. Sulphur
is probably present too, but is obscured by the gold peak. Again, based on
peak heights and compared to those of Fig. 4 (b), the silver and copper
contents are higher in this spot.

42 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 6 (a) Analysis of “clean” area of solder, Sample A
Electron image showing position of analysis

Figure 6 (b) Analysis of “clean” area of solder, Sample A

Energy-dispersive X-ray analysis

May 2000 43
Figure 6 shows the analysis of a clean area of solder. Again we note the
presence of cadmium and indium as well as gold, silver and copper, but little
of the impurities seen in the previous figure. Again, based on peak heights,
Fig. 6 (b), the solder surface layer appears to be of lower gold content.
In all soldered areas examined, the silver and copper concentrations appear
higher than in the clean bulk gold alloy, Figure 4, when peak heights for each
are compared with those of gold. This may be indicative of a tarnish layer of
silver and copper sulphides and/or a lower-carat solder. The latter seems a
more likely explanation as the area examined in Figure 6 was “clean,” i.e not
blackened, but we cannot exclude the former.

Sample B

Figure 7 (a) SEM Micrograph, Sample B

Secondary electron image

44 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 7 (b) SEM Micrograph, Sample B
Backscattered electron image
The low-magnification secondary and backscattered electron images are shown
in Figure 7 (a and b respectively). The gemstones show up as dark circles in
Figure 7 (b). The images show the bottom portion of the pendant, upside-down.

May 2000 45
Figure 8 (a) Analysis of tarnished area, Sample B
Electron image showing position of analysis

Figure 8 (b) Analysis of tarnished area, Sample B

Energy-dispersive X-ray analysis

46 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 9 (a) Analysis of “clean” gold area, Sample B
Electron image showing position of analysis

Figure 9 (b) Analysis of “clean” gold area, Sample B

Energy-dispersive X-ray analysis

May 2000 47
A blackened/tarnished area is shown in Figure 8 at 10x higher magnification,
where the presence of magnesium, aluminium, chlorine, calcium and possibly
a trace of iron impurities are evident as well as gold, silver and copper. An
analysis of an adjacent clean gold area is shown in Figure 9, where only gold,
silver and copper are evident.

Figure 10 (a) SEM Micrograph of reverse side, Sample B

Secondary electron image

48 The Santa Fe Symposium on Jewelry Manufacturing Technology

Figure 10 (b) SEM Micrograph of reverse side, Sample B
Backscattered electron image

Figure 11 (a) Analysis of reverse side, Sample B

Electron image showing total area of analysis

May 2000 49
Figure 11 (b) Analysis of reverse side, Sample B
Energy-dispersive X-ray analysis
The low-magnification secondary and backscattered electron images of the
clean back of the item are shown in Figure 10 (a and b respectively). There
are no obvious contrast effects, suggesting a relatively uniform composition.
A general analysis of the whole area shown in Figure 11 (a) is shown in Figure
11 (b). The presence of only gold, silver and copper is noted. A quantitative
analysis of this back gave the following figures: gold 89.7%; silver 4.5%;
copper 5.8%. The figure for gold 89.7% versus 91.7% for 22-carat gold
suggests some undercarating but it may just be a measurement error rather
than a low figure, as the measurement technique is not fully quantitative.
Based on relative peak heights, the tarnished area of Figure 8 shows higher
copper and silver, i.e. lower gold content. As discussed for Sample A, this may
be an indication of a layer of silver and copper sulphides in the tarnished area
combining to give a lower average figure or a lower gold content of the
underlying alloy in the tarnished area. The former seems more probable.
Discussion of Results
In this investigation, the blackening of both samples of jewellery appear
similar in that the blackening is on the front side only, in the recessed/
soldered areas less amenable to natural polishing off of any tarnish layer as
it forms by rubbing contact with clothes or skin. The blackening is clearly a
surface tarnish layer of some sort and repolishing removes the layer and

50 The Santa Fe Symposium on Jewelry Manufacturing Technology

restores a gold lustre. The timescale involved in tarnishing is variable and can
happen over an extended period when worn by the customer.
Possible Causes of Blackening
Of black layers known to form on gold-silver-copper jewellery alloys, there are
two obvious candidates:
1 Black copper (cupric) oxide—which often forms during annealing in air,
for example, and can be removed by pickling and mechanical polishing.
2 Silver and copper sulphides—which are the most common form of tarnish
on silver and low-medium carat golds.
As we have discussed earlier, tarnishing is very common on silver jewellery
where sulphur compounds and moisture are present in the environment and,
for gold alloys, is generally seen only in the lower-carat golds: 8–10 carat;
occasionally 14 and 18 carat. It is the base metals, particularly copper, and
the silver that are attacked by the corrosive agent(s). Copper oxides are red-
black and silver and copper sulphides are black, although the tarnish films may
be more complex in nature, such as hydrated oxide/sulphide mixtures, together
with chlorides, which may be yellow-brown in colour.
Analysis Results
The results of the XPS analysis clearly indicate that the tarnish is based on
silver sulphide, possibly in the form of the more complex oxy-sulphides and
including some copper. This is evident from the increased silver/lower gold
content and the presence of sulphur in the sulphide state at the surface of the
blackened areas.
In Sample A, the blackened tarnished areas appear to be primarily associated
with the soldered areas. The sulphides of cadmium and indium, metals present
in the solder, would tend to be a dirty red-yellow colour, if present, although
this was not picked up in the XPS analysis of the surface layer, suggesting that
they were not present in significant amounts.
The presence of metals such as magnesium, aluminium, calcium and iron and
chlorine, seen associated with tarnished areas are not easily explained. They
could be remnants of polishing compounds, burnished into the surface, but if
so, why are they not seen in other non-tarnished areas? Possibly the source is
also the same as the source of the sulphur that causes the tarnishing or from
the impure water used in pickling solutions. Chlorine may be the residue of
pickling solutions, possibly as insoluble chlorides of metals such as silver, but
the more likely source is human sweat, which is sodium chloride rich.
In my observations of workshops in India, hot dilute sulphuric acid is often

May 2000 51
used to pickle jewellery and give a bright gold colour. Any acid trapped and
dried on the surface may give rise to the presence of sulphur and hence lead
to silver sulphide formation. Porosity in soldered areas or microporosity in
castings could be a source of acid entrapment.
Another common source of sulphur-containing compounds is organic vapours
in jewellery boxes and display materials in shop windows, but for tarnishing
that occurs during use by the customer, the more likely source is foodstuffs
(onions, for example, are very high in sulphur compounds) and/or deodorant
and perfume sprays and household cleaners. Preparation of food must be a
favourite and may also explain the other metals found! The Indian cuisine,
with its heavy use of spices, would appear to be a sulphur-rich environment
and Indian women are known to wear their jewellery continually. However,
we cannot discount atmospheric pollution arising from industry and traffic
as a contributory cause.
The big question here is not what is the cause of tarnishing, but how can it
occur on 22-carat gold jewellery? The accepted wisdom is, as stated above,
that high-carat golds are not susceptible to tarnishing by silver sulphide
formation. Possible explanations for such tarnishing are:
a) The jewellery is significantly undercarated and so is susceptible to
“normal” tarnishing. This is not borne out by the analytical results.
The gold content is — or is close to — 22 carat: 91.7% gold in Sample B
and well above the accepted 50 atomic % gold threshold.
b) The jewellery composition is unusual and so more prone to tarnishing.
Not true: these are standard gold-silver-copper alloys.
c) The solders used are of lower carat and susceptible to tarnish. But
Sample B is not obviously soldered apart from the end fitting and it is
the bulk alloy that has tarnished. That said, the semi-quantitative analysis
based on peak heights of the spectra could be interpreted as the solders
and tarnished areas are of lower gold content and thus the underlying
alloy is of lower caratage.
d) The surface of the jewellery has been chemically treated; e.g. pickled,
and this has resulted in a loss of gold/enhancement of copper and silver
from the surface layer. This seems unlikely as most acid pickling solutions
will tend to preferentially dissolve the baser metals, leaving a gold-
enriched surface.
Details of an electropolishing process used in manufacturing were
provided. The electrolyte is a gold-based cyanide solution containing
wax/resin compounds. It is possible that, under certain conditions, gold
is preferentially removed from the surface, leaving a copper-silver enriched
polished surface. Gold dissolves faster in cyanide solution than silver,
according to Rose (17). There is no direct evidence for this but it cannot

52 The Santa Fe Symposium on Jewelry Manufacturing Technology

 be discounted. It is also possible that electropolishing leaves a film of
wax/resin on the surface which is sulphur-containing. Electropolishing of
jewellery has been seen in some workshops where relatively crude, home-
made equipment is used, often with the jewellery and cathodes connected
electrically by bare copper wires. It is possible, therefore, that copper is
dissolved in the electrolyte and then re-deposited on the surface of the
jewellery. A case of darkening of colour during electropolishing of 22-carat
yellow gold jewellery was seen in India in 1999, which we attributed to
this cause and gives credence to this hypothesis. The use of chemical
“bombing” in cyanide-peroxide mixtures would have similar effects to
those of electropolishing in terms of depleted layers.
e) The jewellery is subjected to particularly severe tarnishing (corrosion)
conditions—sulphur, moisture and temperature—during wear that leads to
tarnishing even in high-carat golds. The localized nature of the tarnish-
ing, for example in recessed areas not subject to rubbing and the absence
of tarnishing on the reverse side, would lend some support to this view.
There is no conclusive evidence of why this 22-carat gold jewellery tarnishes.
The most probable factors are the latter two above; i.e. that the processing
leaves a thin gold-depleted layer on the surface and that the jewellery is
exposed to severe sulphidising conditions during wear; e.g from food prepara-
tion or household/personal sprays and cleaners, possibly in combination with
sweat (sodium chloride). Chloride ions are well known for accelerating corro-
sion reactions. It is possible that the solder used in Sample A is of lower gold
content, too.
If this thesis is correct, then the problem should be alleviated by changing the
finishing procedures and/or by electroplating the jewellery with a thin “flash”
of pure gold. It is less likely to be worn away in the vulnerable recessed areas
of the jewellery where the tarnishing is most seen. Regular cleaning of the
jewellery and hand polishing by the wearer should also reduce the retention
of corrosive products on the surface and hence the extent of any tarnishing.
This study has highlighted a previously unreported fact that even high-carat
gold alloys can tarnish. More work needs to be carried out to investigate this
phenomenon more thoroughly and understand how it arises.
Reddening of 22-Carat Jewellery on Display
It is worthwhile to comment on the other claimed problem: the reddening of
yellow 22-carat gold when displayed in shop windows. This could also be a
form of tarnishing—not yet proven—in which a tarnish layer of red-black
copper and/or silver sulphides or even red cuprous oxide forms under the
strong sunlight conditions of the shop window environment.

May 2000 53
Alternatively, the reddening may be due to the formation of cadmium sulphide,
which is a darkish red colour, as cadmium is used extensively in solders in
India. Traditional Indian jewellery is typically heavily soldered, usually with
gold-cadmium solders. Cadmium is volatile at soldering temperatures and it
could easily condense on to neighboring surfaces to give a thin cadmium-rich
surface layer. Sulphur may be present in the display materials and in the
general atmosphere. There is also a high humidity and there is possibly a
photo-catalytic effect under the strong sunlight conditions. Against this
speculation is the fact that reddening does not appear to be a feature of
18- and other lower-carat golds elsewhere in the world.
Maybe the reddening is associated with “burning in” of red rouge polishing
compound into the surface during manual polishing on the wheel? Rouge is
iron oxide–based and the red colour may deepen on exposure, giving the
jewellery a deeper red colour. All this is can only be speculation! Until a
sample of such jewellery is available for examination, we cannot be sure
what is the cause and nature of this phenomenon.
Conclusions
1. The blackened areas on the jewellery are tarnish films due to silver and
copper sulphide formation. This has been proven by XPS analysis.
2. There is no conclusive evidence as to the cause of the tarnishing. The
alloys are 22 carat and no appreciable undercarating of the gold alloy was
evident. Such high-carat alloys are not normally considered susceptible to
tarnishing. The evidence suggests that the solder may be of lower gold
content but is not quantitatively proven.
3. The most likely cause is that the jewellery is subjected to a particularly
severe corrosive (sulphidising) environment during wear. It is possible
that this situation occurs, for example, during the preparation of food and
is exacerbated by a gold-depleted surface layer arising from the final
stages of finishing during manufacture. Further research is needed to
arrive at a definite conclusion.
Acknowledgements
I am grateful to the two retailers, Sri Rathna Jewellers and Kumbakonam
Jewellers, for supplying examples of blackened jewellery for examination. I
thank Tony Busby and Alan Stubbs of the Johnson Matthey Technology Centre,
U.K., for carrying out the analytical examinations, and Roy Rushforth at the
Birmingham Assay Office for advice and additional analysis. Also, I thank Mark
Grimwade for making available his Santa Fe Symposium paper and for helpful
discussions. Lastly, I thank World Gold Council for their support and permission
to present this paper.

54 The Santa Fe Symposium on Jewelry Manufacturing Technology

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