The Tarnishing of Silver Alloys:

Causes And Possibilities

By Andrea Basso, Riccardo Bertoncello, Fabio Bottelli,
Jacopo Carli, Joerg Fischer-Buehner & Massimo Poliero
Legor Group Srl

©2011 The Bell Group, Inc. All rights reserved.

800.545.6566 riogrande.com
 Basso
The Tarnishing of Silver Alloys:
Causes and Possibilities

Andrea Basso
Riccardo Bertoncello
Fabio Bottelli
Jacopo Carli
Joerg Fischer-Buehner
Massimo Poliero
Legor Group Srl
Bressanvido, Italy

Abstract
This work provides an overview of the problem of tarnishing and seeks to
present as detailed a picture as possible of its causes and the possibilities for
limiting it by using resistant alloys. The problem of assessing tarnishing is
examined in part two, starting with an analysis of the methods currently in
existence in the various sectors, and hypothesizing the possibility of defining a
specific standard for silver alloys.

Introduction
The term “tarnishing” generically indicates a surface-blackening process, which
renders the objects affected by it aesthetically unacceptable.1,2 In the precious
goods field the problem of tarnishing prevalently involves items made of silver,
whose initial brilliance is compromised in relatively short times.
From the chemical point of view, the phenomenon of tarnishing can be defined
as a process of medium-scale spontaneous corrosion2,3 triggered by the chemical
reaction of silver and the various alloy components with a vast range of
chemical agents present in the atmosphere. The resulting discoloring or browning
is caused by the accumulation of the reaction products in a surface film, which
determines the typical chromatic reaction.
The original definition of tarnishing was primarily associated with the chromatic
alteration (often accompanied by iridescence phenomena) deriving from
the action of hydrogen sulfide, a reaction that envisages the formation of a
yellowish patina that turns towards brown and then takes on bluish colorings.
In a broader sense, it is appropriate to consider all the reactions capable of
causing an alteration of the original color as tarnishing. It is in line with this
latter assessment that this work is developed, with a review of the main chemical
agents responsible for chromatic alterations of silver and its alloys. Part two will

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examine the problems relating to the methods for assessing tarnishing and the
possible prospects for defining ad hoc rules for assessing and classifying silver
alloys on the basis of their resistance to it.

Chemical and Physical Factors Responsible for

Tarnishing
It is practically impossible to list the vast range of chemical factors that can
interact with silver and its alloys. Nevertheless, the present state of knowledge
makes it possible to delineate a description, though not exhaustive, of the main
groups or chemical and physical agents responsible for tarnishing and their
chemical reactions.
Sulfurated compounds These probably constitute the most studied category.
Sulfur-containing compounds react with silver to form silver sulfide (Ag2S), which
has a grey/black coloring.4 Franey et al.5 have described the effect of tarnishing
on pure polycrystalline silver following exposure to hydrogen sulfide gas (H2S),
carbonyl sulfide (OCS), sulfur dioxide (SO2) and carbon disulfide (CS2). Research
has shown that the formation speed of silver sulfide (Ag2S) in the presence of H2S
and OCS would be about 10 times faster than that observed with SO2, while the
formation of silver sulfide by carbon disulfide would be negligible.
Of these compounds, hydrogen sulfide (H2S) acts at extremely low levels of
concentration (0.2µg/m3 or ppb-parts per billion) and it is less common in nature
(0.03-5ppb),6 unlike carbonyl sulfide (OCS), which is much more ubiquitous
(0.3-20ppb). OCS is used as a production intermediate in the chemical industry
and is present in exhaust gases, in the combustion products of carbon, and in the
decomposition of biomasses and vegetable residues. It is particularly present in
marshy areas and lagoons where its concentration can reach values of 60-180ppb.7
It should be considered in any case that, in the presence of humidity, carbonyl
sulfide decomposes and produces hydrogen sulfide (H2S) and carbon monoxide
(CO). With a much higher content (100ppb), but less significant for tarnishing
purposes, is the action of sulfur dioxide (SO2), while carbon disulfide (CS2) is
negligible in terms of both reactivity and of atmospheric concentration.
The chemical reaction that leads to the formation of silver sulfide starting from
hydrogen sulfide and silver is as follows:2,8

2Ag + H2S + 0.5 O2 → Ag2S + H2O

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It is important to note that the reaction requires the presence of oxygen. It should
also be considered that other environmental conditions such as temperature and
humidity are of fundamental importance for the type of reaction that results. An
example of how environmental differences can influence the tarnishing process is
illustrated in Figure 1.

Figure 1 The effect of environmental conditions on the thickness of the reaction film2

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The reaction is mediated by a liquid surface film, which acts as an interface

of exchange between the reagents of the corrosion process. The reactions of
sulfurated compounds with other elements can even turn out to be on a greater
scale than those of sulfide compounds with silver. A list of the main reactions
between silver alloys and chemical agents present in the environment is shown
in Table I.

Table I List of the main chemical reactions involved in the tarnishing processes. The
second column shows an equilibrium constant, which indicates the tendency of the
reaction to occur at a temperature of 25ºC/77ºF. A value of the equilibrium constant that
is greater than 1 indicates that the reaction takes place spontaneously. High values of K
indicate a high tendency for the reaction to occur. Vice-versa, values of the equilibrium
constant below 1 show that the reaction does not tend to occur spontaneously.8,24

Equilibrium
Compound Color24
Reaction constant
name
(K, 25°C)
silver
2Ag + H2S + 0.5O2 → Ag2S + H2O 6.117 x 1042 black, grey-black
sulfide
copper
2Cu + H2S +0.5O2 → Cu2S + H2O 6.568 x 1050 blue-black
sulfide
copper
Cu2O + H2S → Cu2S + H2O 8.197 x 1024 blue-black
sulfide
germanium
GeO2 + 2H2S → GeS2 + 2H2O 19.36 black
sulfide
stannic brown-black,
SnO + H2S → SnS + H2O 2.89 x 1010
sulfide grey
ZnO + H2S → ZnS + H2O 2.292 x 1014 zinc sulfide white
silicon
SiO2 + 2H2S → SiS2 + 2H2O 6.840 x 10-35 white or grey
sulfide
boron
B2O3 + 3H2S → B2S3 + 3H2O 1.761 x 10-59 white-yellow
sulfide
copper
Cu + O2 + 2NO2 → Cu(NO3)2 2.736 x 1037 blue
nitrate
silver
Ag + NO2 → AgNO2 6.426 x 105 yellow-grey
nitrite
silver
Ag + 0.5SO2 + 0.25O2 → 0.5Ag2SO3 5.682 x 109 ---
sulfite
copper
Cu + 0.5SO2 + 0.5O2 → 0.5Cu2SO4 1.117 x 1031 green
sulfate
silver
2Ag + Cl2 → 2AgCl --- white
chloride

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In particular, the reactions between hydrogen sulfide and copper indicate a high
tendency to form copper sulfides, even higher than the tendency to form silver
sulfides. In this case, too, the formation of copper sulfides is particularly visible as
they have a black-blue coloring. In the silver-copper alloys, in which a problem of
miscibility in the solid state between silver and copper (standard sterling silver)
exists, the biphasic structure, which derives from it, is particularly attacked,
especially in the high copper-content phase (Figure 2).

Figure 2 Silver-copper 925 alloy subjected to sulfurization

tests by means of thioacetamide (TAA). The sulfurization
reaction is particularly evident in the copper-rich phase.

Compounds containing nitrogen Nitrogenous compounds, commonly indicated as

NOx, prevalently derive from emissions of exhaust gases from motor vehicles
and industries. Among these, particular consideration should be given to the
effect caused by the nitrogen dioxide (NO2),1 which is quite reactive with
copper, leading to the formation of blue-colored copper nitrates (Cu(NO3)2).8
This gas can react in a humid environment, giving rise to the formation of
aggressive compounds such as nitric acid (HNO3) or decompose in the presence
of light and volatile organic substances, giving origin to the formation of ozone
(O3).8,9 Ozone at room temperature is a powerful oxidant of many metals
including silver, on which it provokes blackening as a result of the formation
of silver oxides11 (Ag2O, colored black and AgO, colored grey). Finally, it was
ascertained that nitrogen oxides (particularly NO2) can act as catalysts for the
sulfurization reaction from hydrogen sulfide by increasing the aggressiveness of
the reaction.10
Compounds containing chlorine Internal experiences have highlighted the high
susceptibility, in general, of silver alloys following immersion in dilute solutions
of bleach (Figure 8). Experience shows that the action of active chlorine (such
as hypochlorite, ClO-),1 the presence of which can be found in swimming pool

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water and drinking water in concentrations around 1-1.5ppm, produces a surface

brightness loss effect that is far from negligible. Chlorine attacks silver and
generates silver chloride (AgCl2). Silver chloride has a whitish color but with
exposure to the light, it can lead to the blackening of the sample as a result of
photochemical decomposition with the production of chlorine and finely
dispersed metal silver.19 Finally, the aggressive action of the chlorides should
be considered. Chloride-based solutions are particularly important for the high
electrical conductivity they bring to the solution (with consequent exaltation of
the galvanic corrosive phenomena) and for their high depassivating power.
Metal oxide-based compounds Silver is heavily attacked by ozone as we have already
mentioned above. The same can be said about the main alloy components such
as copper. In the form of gaseous oxygen (O2), the reaction at room temperature
is modest, while it is significant in the phase with a high copper content (CuO,
colored brown-black and Cu2O, colored brown-red).
The effect of light Exposure to natural or artificial light is considered to be a
possible cause of discoloring effects on silver and its alloys. As already mentioned
above, the ultraviolet component of light (Figure 3) can encourage the formation
of highly reactive compounds such as ozone (O3). In the case of artificial light,
the incandescent lamps (traditional filament or halogen ones) currently available
on the market emit negligibly in the ultraviolet region (Figure 3b), unlike those
used until a few years ago. On the other hand, a greater UV emission can be
attributed to other categories of lamps such as triphosphor fluorescent and
mercury vapor lamps. It is probable that the infrared component of natural light
and incandescent lamps could have a heating effect on the surfaces of silver
objects (e.g., during exposure to daylight or inside illuminated display cases),
resulting in higher surface temperature and therefore greater reactivity of silver
objects to the various chemical agents present in the environment.

6 The Tarnishing of Silver Alloys: Causes and Possibilities

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Figure 3 The emission spectra of sunlight (a) and of various types
of lamps: traditional incandescent or halogen types (b), triphosphor
fluorescent tubes (c), and mercury vapor lamps (d)12

The effect of temperature and humidity The mere presence of pollutants in the
air does not mean that the role played by humidity and temperature in the
tarnishing reaction can be overlooked. The humidity in the environment plays
a fundamental role in the speed of formation and in the extension and thickness
of the dark patina. The film of water, with the thickness of a few atomic layers
absorbed on the surface, plays a role in encouraging the reaction kinetics as it acts
as an interface of exchange between the reagents of the corrosion process. The
natural diffusion of oxygen on the film of humidity, which deposits on a surface,
also contributes towards accelerating the development of the reaction.
The temperature induces an acceleration of the reaction kinetics and provokes
an increase in the degree of blackening with identical exposure times. The effect
exercised by humidity and temperature on the thickness of the surface patina is
illustrated in Figure 4. The graph shows a behavior on the basis of the temperature
in which the thickness of the water film deposited on the metal surface appears
to be crucial.
It is possible to observe a drop in the speed of growth of the layer of sulfur as
the temperature passes from 20°C to 30°C (68ºF to 86ºF), in concomitance with
a reduction of the thickness of water adsorbed; this indicates corrosion of the

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humid type, which requires water molecules for accelerating the course of the
reaction. When the temperature is increased above 40°C (104ºF), the conditions
are achieved for proceeding with a type of corrosion that is similar to the one that
takes place in a dry environment.2,5

Figure 4 The thickness of the film of Ag2S after total exposure to

100ppm/h of H2S or OCS as a function of the temperature. The broken
line represents the thickness of the water film (R.H. 94%).5

Characteristics of the surface oxidation layer

Studies carried out on samples of sterling silver and Argentium® alloy8 show how
the products of the alloys’ reaction with the various environmental agents lead to
the formation of a film composed prevalently of sulfides and oxides of silver and
of the alloy metals. Depending on the conditions, the thickness of the oxidation
layer has been found to fall between 50 and 160nm.
The characteristics of the film are such as to create a sort of barrier that places
itself between the alloy below and the chemical agents, and progressively slows
the thickening process. If, therefore, the speed of growth of the oxidation film at
the beginning is particularly associated with the environmental concentration of
the chemical agents, as the reaction proceeds it is their ability to diffuse through
a surface film (diffusivity) that becomes the component effectively regulating the
reaction speed.
The speed of diffusion through the surface oxidization film depends on various
factors such as the nature of the chemical agent, the compactness of the

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oxidation patina, and the tortuousness of the pores that put the external
environment into communication with the surface of the alloy. Davis8 suggests
that there is a relationship of a linear type between the thickness of the oxidation
film and the square root of the product of the time, concentration and diffusivity
of a given chemical agent.

The influence of the surface quality and the state of the material
on the tarnishing
With the same composition, the surface reaction speed is strongly influenced by
the characteristics of the surface and of the state in which the material is found (e.g.,
casting blanks, hardened, annealed). Considering that the tarnishing processes in
normal environmental conditions can mainly be ascribed to corrosion processes
caused by humidity, thanks to the presence of a thin liquid film that covers the
surfaces, the characteristic of the corrosive processes is based on the formation
of galvanic cells, the porosity and asperity of which in general constitute the
component most easily subject to corrosion (anodic part). For this reason, the
porous, rough or sharp-edged surfaces constitute the parts most easily attacked
by the various chemical agents compared with perfectly smooth surfaces.
An example is shown in Figure 5 and relates to the enlargement under an optical
microscope of a plate of sterling silver subjected to sulfurization tests (TAA). It is
easy to observe from the marked area of corrosion surrounding the pores (easily
distinguishable from the brown color) how these micro-cavities have undergone
a greater marked process of degradation than the surrounding area. It can be
deduced that with the same composition, the surface characteristics of the object
constitute an aspect of fundamental importance for its resistance to tarnishing.
On the other hand, as far as the state of the material (casting blanks, hardened,
annealed) is concerned, better conditions of stability can be achieved by reducing
the surface reactivity to a minimum, a condition which can be obtained by
eliminating everything that can create stress and tension situations.

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Figure 5 Microphotograph of the surface of a sterling silver alloy after

a sulfurization test (TAA). It shows how the attack by hydrogen sulfide
is concentrated around two cavities (pores) in the center of the photograph.

The development of alloys with a high resistance to tarnishing

Surface reaction processes that give rise to the phenomenon of browning cannot
be eliminated as silver and its alloys tend to transform themselves spontaneously
into compounds that are thermodynamically more stable than at the metallic
state. This tendency cannot be annulled but it is, however, possible to control it
from the kinetic point of view, namely manage or, better still, reduce the speed
with which this reaction tends to occur spontaneously. In other words, it is
possible to reduce the tarnishing phenomenon significantly.
The development of alloys with a high resistance to tarnishing in recent years has
fundamentally pursued the goal of creating formulations capable of eliminating
some particularly sensitive components or reducing them to a minimum and of
reducing the surface reaction speed with the broadest possible number of the
chemical agents normally present in the environment. Many approaches have
been used to achieve this goal and have led to advantages and disadvantages,
depending on the type of chemical agents involved and the specific
environmental conditions. The main directions toward which the improvement
process has moved are fundamentally the following, as already reviewed by
Strauss:3
a) The reduction or elimination of phases that are more susceptible to corrosion
The presence of structures with several phases can lead to an
acceleration of the corrosive processes because of the corrosion of the
phase richest in copper (less noble) and the start of processes of the
galvanic type. The best-known situation regarding an alloy with a
two-phase structure is that of a silver-copper alloy (92.5Ag7.5Cu or
standard sterling silver), whose poor resistance to tarnishing by

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sulfurated compounds is well acknowledged. One possibility for
reducing the susceptibility to the tarnishing reaction can be to reduce
the extension of the copper-rich phase by adding other alloy elements.
b) The addition of elements with a higher degree of nobility and consequently
with greater resistance to corrosion
The addition of precious metals as noble metals to the silver alloys
constitutes another way to obtain an increase in the resistance to
corrosion. The addition of precious metals is based fundamentally on
the statistical concept of replacing a certain number of atoms of silver
and of other alloy components with atoms of noble metals in order to
reduce the number of atoms that react with the atmospheric agents.
There are various alloys on the market in which palladium, gold and
platinum17 are added in different concentrations and whose resistance
to tarnishing should be greater as an effect of these additions. Based
on our experience, a simple addition of precious metals is not
necessarily leading to a superior tarnish resistance. An example of
comparison of tarnish-resistance properties between precious and
non-precious metal-containing alloys is reported in Figure 6.
Furthermore, the disadvantages are obviously linked to the cost
of the precious metal-containing alloys.
c) The addition of elements capable of producing surface films that can protect the
metal surface from corrosion (passivation)
The addition of elements such as germanium and silicon capable of
forming thin, dense surface films (passivation) constitutes a particularly
important approach for increasing anti-tarnish properties.
d) The addition of elements whose products form reaction with environmental
agents and are fairly colorless or even transparent
As we have already mentioned, the selection of the alloy component
on the basis of the coloring of the reaction products constitutes another
point that can contribute to the reduction of the visual effect of the
corrosion process.
e) Increasing the purity of the alloy and particularly its oxygen content
It is reported that some elements present as impurities such as
selenium (Se) and tellurium (Te) can, for example, worsen the
resistance to tarnishing.21 As a general rule, the presence of impurities
or inclusions can increase sensitivity to the tarnishing phenomenon and
encourage the triggering of the reaction.
f) Reduction of the crystal level and segregation
It is known that a fine-grain material with a homogeneous composition
presents greater stability and resistance as regards corrosion
phenomena.

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1 2 3
Figure 6 Tarnishing results after 30 days of exposure to external environment
(2nd floor south-oriented window, Legor Group Laboratories, Bressanvido(VI),
Italy – September 2009) between 1) a precious metal-free, copper-germanium-
containing 935 silver (Argentium® 935 “Original”); 2) a binary silver-
platinum 960:40 alloy; 3) a binary silver-palladium 960:40 alloy. Note the
higher severity of tarnishing reaction of Alloys 2 and 3 compared to Alloy 1.

Examples of alloys with a high resistance to tarnishing

The development of alloys with a high resistance to tarnishing takes account
of more than one of the aspects considered above, balancing the various
components in such a way as to accumulate the advantages. Among the
formulations that have become particularly known for their anti-tarnish
properties is the triple silver-copper-germanium alloy that is distributed under
the Argentium® trade name.3,8,14,15,16 The main resistance mechanism seems to stem
from the formation of a thin passivation film with a thickness of a few
nanometers, which appears to form spontaneously at room temperature. On
the basis of the experience acquired by Johns14 and Davis,8 the heat hardening
treatment at a temperature of around 300°C (572ºF), as well as simple heating at
about 100°C (212ºF), increases the compactness of the passivation film and further
increases resistance to tarnishing.
As well as the property of providing bright castings suitable for precision casting
with stones, silicon-based alloys have anti-tarnish properties that can be
particularly high, also when silicon is combined with other alloy components.
Internal experiences have monitored the stability of Argentium® 930 “Casting,”
currently considered to be one of the most resistant anti-tarnish alloys (Figure 7)
on the market in a wide variety of environmental situations.
Finally, the development of a formulation with innovative characteristics named
Legor Ag-liteTM (patent pending) should be recalled. This is a single-phase alloy
without copper and with small additions of precious metals. Tests carried out
have shown that this alloy possesses particularly marked properties of resistance
to sulfurization and active chlorine (Figure 8).

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Figure 7 Samples of alloys after 24 months of exposure in an internal
bath with production shower. The comparison with sterling silver (a) and
Argentium® 930 “Casting” (b) shows the higher resistance of the latter.

Figure 8 The effect of corrosion on samples of silver alloys (a) Legor Ag-LiteTM,
and sterling silver (b) before and after immersion in a 1/10 solution of bleach
(corresponding to about 500ppm of sodium hypochlorite) for 4 hours at 30°C/86ºF. The
strong corrosive action on the silver-copper alloy (b) compared to alloy (a) is quite clear.

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The assessment of the properties of resistance to tarnishing of

silver alloys
In light of the above, it appears obvious that the phenomenon of tarnishing is
a complex problem and probably not yet completely clear. Nevertheless, there
is a need to define what is intended for resistance to tarnishing and when an
alloy or an object can be defined as resistant or not. The jewelry sector does not
have its own standards for making assessments of the resistance, and that is why
standards are often adopted regarding corrosion tests derived from the steel,
dental, textile, footwear and eyewear sectors. Nor is it clear what the test
conditions are and what parameters provide the basis for defining when an object
can be resistant to tarnishing or not. This whole situation engenders a certain
confusion that is worth clarifying.
A list of the main official standards and internal methods – certainly not
exhaustive – that has been used to date in the gold and silver sector is summarized
in Table 2 below and can provide an idea of the regulatory framework regarding
procedures for assessing surface corrosion.

Table 2 List of the main standards regarding the assessment of

corrosion processes. The list refers to a series of standards derived
from the steel, footwear, textile, dental and eyewear sectors.
Chemical/
Description physical Duration
Reference Note
of the test agents of in hours
reference
UNI EN ISO 4538 Thioacetamide Hydrogen 24 This is probably the most commonly
corrosion test sulfide (H2S) used test. The objects are placed in a
(TAA test) hermetic container inside which H2S is
released by the decomposition of the
TAA. The toxicity of the
thioacetamide is considered. Test
temperature: 20°C/68ºF.

UNI ISO 4524-2 Sulfur dioxide Sulfur dioxide 8 The test consists of keeping the
resistance test (SO2) samples in question inside a
temperature-controlled chamber at
25°C/77ºF inside which a 200g/l solution
of sodium thiosulfate and sulfuric acid
is placed.
Peruzzo18, Davis8 Sulfurization Hydrogen 4 The samples are exposed to vapors of
test sulfide (H2S) (Ref.18) hydrogen sulfide released by a solution
of ammonium sulfide (NH4)2S. The two
sources mentioned refer to different test
conditions.

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Chemical/
Description physical Duration
Reference Note
of the test agents of in hours
reference
Tuccillo-Nielsen Sulfurization _ Hydrogen 0.5 The samples are mounted on a rotary
sulfide (H2S) wheel and are cyclically exposed to air
and immersed in a solution of sodium
sulfide Na2S. This test is much more
aggressive than the TAA test as the S2-
ions come into contact with the surface in
a much higher quantity and,
furthermore, the solution-air alternation
favors the reaction, which leads to the
formation of silver sulfides.
Faccenda19 Accelerated Sulfur 96 max The samples are suspended in a beaker
test in a sulfur compounds, containing a 2% solution of cosmetic
atmosphere chlorides, sulfur soap. The solution is made to
others bubble by inputting air in such a way
that the samples are immersed in the
resulting foam.
UNI EN ISO Test of Chlorides, 24 This standard is applied to the eyewear
12870:2009 resistance to others sector. The test consists of keeping the
artificial sweat samples resting on a layer of cotton wool
soaked in a solution simulating human
sweat. Test temperature: 50°C/122ºF.
UNI EN 3160-2 Test of Chlorides, 16 The test consists of keeping the samples
resistance to others resting on a layer of cotton wool soaked
artificial sweat in a solution simulating human sweat.
Test temperature: 40°C/104ºF.
UNI EN ISO Test of Chlorides, 72 The test consists of keeping the samples
105-E04:2009 resistance to others resting on blotting paper soaked in a
artificial sweat solution simulating human sweat.
UNI EN ISO Resistance to Chlorides, The test consists of keeping the samples
105 E-02:1998 salt water others in salt water for 4 hours. The purpose of
this test is to look for any damage caused
by the presence of salt on the sample.
UNI EN ISO Test of This standard is applied to the footwear/
22775 resistance to metal accessories sector. The standard
corrosion specifies two methods for
determining the propensity of a metal
surface to change appearance after
contamination because of atmospheric
pollution.
UNI EN ISO Test of Active chlorine The test simulates the de-coloring
105-E03:1998 resistance to effect of chlorinated water (swimming
chlorinated pool test) on fabrics. The samples are
water immersed in chlorinated water for 1
hour.
Legor Test of resis- Sodium 0.5 The test evaluates the aggressive effect
tance to active hypochlorite of a fresh commercial solution of bleach
chlorine diluted 1/10 at 30°C/86ºF. The test is
particularly aggressive.
UNI EN ISO Resistance Nitric acid The test simulates the de-coloring effect
105-G01:1998 to nitrogen vapors of nitrogen oxides on fabrics.
oxides

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Chemical/
Description physical Duration
Reference Note
of the test agents of in hours
reference
UNI EN ISO Xenotest – Sunlight, The test checks the de-coloring of fabrics
105-B-02:2004; Test of humidity, following exposure to sunlight in the
resistance temperature presence of particular weather
UNI EN ISO to sunlight conditions. It provides little useful
105 B-04:2000 information for application to jewels and
the like.
Peruzzo18 UV radiation UV-A, UV-B, 1 Exposure of the samples to a broad
test UV-C spectrum UV lamp. The test simulates
the effect of exposure for about 50 hours
at an altitude of 3000m in the month of
July. The aggressive action on the surface
is also due to the action of ozone, which
forms as an effect of the ultraviolet
radiations.
Trentin et al.20 Test of Sunlight, Adapted version of the Xenotest.
resistance to humidity, Evaluation of the results by means of the
light by means temperature “L” coordinate (CIELAB).
of exposure to
sunlight
ISO9227 Salt mist Chlorides The test involves spraying a sodium
corrosion test chloride solution on the samples inside a
specific climatic chamber.
CASS test Copper-salt Sodium The test involves atomizing a solution of
mist corrosion chloride, acetic sodium chloride, acetic acid and copper
test acid, copper chloride on the samples inside a specific
chloride climatic chamber. The CASS test is more
aggressive than ISO9227.
EN4611 Resistance to Vapor The test consists of keeping the samples
humid heat in a temperature-controlled test chamber
at 40°C/104ºF in an atmosphere
saturated with moisture for 96 hours.
The purpose of the test is to check for
damage caused to the sample by the
presence of humidity.

Above all, the list of test methods raises the problem of extrapolating useful
elements for defining ad hoc tests for the gold and silver sector. The second
problem is to define what is intended by “resistant to tarnish” and what
measurable reference values can be used to declare it.
It is also necessary to clarify if the assessment of resistance to tarnishing should
regard the properties of the material (the alloy) or the finished object as a whole.
In the first case the test should exclude any reference that does not concern
the formulation of the alloy; in the second case, the development of a test for
assessing the end product (the piece of jewelry) must not only take into account
the characteristics of the material but also the conditions in which it was produced
and its surface state, factors that weigh in a significant manner on the end result
but are not necessarily or solely linked to the characteristics (formulation) of the
material (alloy) used. As well as this, it is also necessary to clarify if the solution

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can be found in the development of a combined test capable of simulating all the
aggressive factors as a whole, as happens in reality, or if it is preferable to assess
the main aggressiveness factors in separate tests.
It is the opinion of the authors that the development of a combined test capable
of simulating real life conditions and providing predictions regarding resistance
to tarnishing, though desirable, is difficult to propose in reality. More plausible is
the idea of basing an assessment of tarnishing on a series of tests that are easy to
realize, in which the main chemical agents are tested by separate tests or in simple
combinations.
On the basis of the observations made above, a possible hypothesis for a test for
assessing resistance to tarnishing applied to the materials (silver alloys) should
take into account the following points:
1. Characteristics of the sample: The material must have compact surfaces as
free as possible from pores. The surface should be polished to a mirror finish
or in any case to levels comparable to the levels of finish applied in the gold
and silver sector. A possible solution could be constituted, for example, by a
plate encapsulated in resin for metallography and polished with a final pass
with 1µm diamond suspension.
2. Chemical/physical agents: The samples prepared in accordance with the
observations in point 1 would be subjected to the main aggressive agents in
separate tests that are easy to realize. The tests could include the following:
• Hydrogen sulfide (H2S)
• Active chlorine
• Chlorides (e.g., from synthetic sweat)
• Nitrogen oxides
• Light (UV, ozone), humidity, temperature
3. Measurement: The possible approaches could include:
• Measurement of the thickness of the reaction film (e.g., Auger, XRF,
GDOES)
• Weight variation per unit of surface area
• Measurement of the color variation
4. Definition of the critical values for defining the “antitarnish status”: At
present, some results would indicate the possibility of defining a criterion for
classifying silver alloys by measuring their color. An example of use of the
DE parameter for classifying resistance to tarnishing by sulfurization is
provided by criteria used by the Birmingham Assay Office. The following
reference values are defined according to the procedure drawn up:
• DE<4: absence of tarnishing
• 4<DE<7: slight tarnishing
• 7<DE<9.5: moderate tarnishing
• DE>9.5: consistent tarnishing
The Birmingham Assay Office makes reference to the application of an internal

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method based on the use of thioacetamide (TAA), without, however, specifying

the procedure in detail.

Experimental Part
The purpose of the test was to assess the feasibility of evaluating tarnishing by
colorimetry. Silver alloys already known and available on the market were used
for the test.
• Argentium® 930 “Casting”
• Legor Ag-LiteTM
• Argentium® 960 “Britannia”
• An alloy of traditional sterling silvers (92.5Ag7.5Cu) was used for the
comparison.
The alloys were produced and cast in a flask at a temperature of 1000°C/1832ºF
and cooled immediately in water. The plates obtained, measuring 20 x 20 x 5mm,
were then embedded in resin and subjected to smoothing and polishing with a
1µm diamond suspension. The samples underwent an adapted version of the
thioacetamide test. The samples were incubated for 24 hours in a temperature-
controlled chamber at 20°C/68ºF (Figure. 9).

Figure 9 Plan of the incubation chamber in which the

thioacetamide test (TAA) is carried out

The color was measured at the end of the test using a Macbeth Color I7 (Gretag
Macbeth) colorimeter. The measurements concerned the determination of the
CIELAB coordinates (brilliance), a* (total variation from green to red) and b* (total
variation from blue to yellow) and the associated derived variables such as the
Yellowness Index (YI)22 and the DE calculated using the following formula:
DE = [(L2-L1)²+(a2-a1)²+(b2-b1)²]0.5

18 The Tarnishing of Silver Alloys: Causes and Possibilities

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Results and Discussion
The results of the tests are shown in Tables 3 and 4.

Table 3 Colorimetric evaluation of sterling silver samples after

a sulfurization test using thioacetamide (TAA)
Encapsulated sample (polishing at 1mm)
L* a* b* c* YI DE
Before
96.7 -0.4 3.5 3.5 6.3
tarnish
After
77.5 7.2 52.3 52.8 92.1 53.0
tarnish
77.3 7.9 49.2 49.9 89.5 50.3
79.5 4.9 49.1 49.3 85.2 49.0
77.9 7.0 51.5 52.0 90.8 52.1
80.3 4.3 48.9 49.1 83.9 48.5

Average 78.5 6.3 50.2 50.6 88.3 50.6

SD 1.3 1.6 1.6 1.7 3.6 1.9
CV (%) 1.7% 25.0% 3.1% 3.3% 4.0% 3.8%
DX 18.2 6.6 46.7 47.1 82.1

Sample polished by brushing

L* a* b* c* YI DE
Before
96.0 -0.2 3.7 3.7 7.8
tarnish
After
44.3 7.6 5.0 9.1 28.3 53.1
tarnish
52.3 6.7 12.9 14.5 44.9 45.9
58.6 5.2 13.3 14.3 50.5 39.7
53.6 6.2 13.5 14.8 44.9 44.7
45.1 8.9 11.1 14.2 48.0 53.0

Average 50.8 6.9 11.2 13.4 43.3 47.3

SD 6.0 1.4 3.6 2.4 8.7 5.7
CV (%) 11.9% 20.3% 32.0% 18.0% 20.1% 12.1%
DX 45.2 7.1 7.5 9.7 35.5

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The data in Table 3 provide some important information regarding the state
of the surface and the interpretation of the color. The main tendency is to use
the global chromatic variation expressed by the variable DE as the criterion for
assessing the degree of tarnishing.15 A comparison of the data for coordinate b*
(blue-yellow tonality) shows that the values found for the embedded and polished
plate are notably different. In reality, the variation reflects what is normally noted
in a tarnishing process in which a surface yellowing/browning phenomenon is
observed, followed by a change towards bluish tonalities.
As a consequence of this with the progress of the tarnishing reaction, a rise in
the value of b* (yellow tonalities) would be observed first of all and would be
followed by a drop associated with the color change towards blue. Effectively
it can be observed that despite the great difference in the reaction to tarnishing
between the two samples, the value DE is even lower in the case of the plate. This
observation is substantially in line with what Trentin already observed.20 Davis8
has also highlighted that there is no significant correlation between the coordinate
b* and the thickness of the reaction film.
The same authors have also revealed significant correlations between the
coordinate a* and the severity of the tarnishing reaction, while both experiences
have shown a fairly good degree of correlation (0.53) between the thickness and
the logarithm of the L* coordinate. It should be considered that the variability
in the color measurements between the two samples of sterling silver (CV) is
notably more accentuated in the case of the brush-polished plate. This indicates
that measurements made on surfaces that are not perfectly polished and are in an
advanced state of tarnishing increase the dispersion of the data and can therefore
negatively influence the precision of the color measurement.
The measurements made on the samples embedded at 1µm reveal interesting
results as regards the coordinate DL (row DX, column L), the variability of which
(CV = SD/Average) is particularly limited in all the samples tested and
better from this point of view compared with all the other parameters measured.
A summary comparison with experiences reported by Grimwade15 and by the
Birmingham Assay Office by D. Manchanda23 is shown in Table 5 with regard to
the parameter DE.

20 The Tarnishing of Silver Alloys: Causes and Possibilities

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Table 4 Colorimetric evaluation of samples of various silver alloys encapsulated
and polished at 1µm after a sulfurization test using thioacetamide (TAA)

Copper/silver alloy (standard sterling silver)

L* a* b* c* YI DE
Before
96.7 -0.4 3.5 3.5 6.3
tarnish
After
77.5 7.2 52.3 52.8 92.1 53.0
tarnish
77.3 7.9 49.2 49.9 89.5 50.3
79.5 4.9 49.1 49.3 85.2 49.0
77.9 7.0 51.5 52.0 90.8 52.1
80.3 4.3 48.9 49.1 83.9 48.5

Average 78.5 6.3 50.2 50.6 88.3 50.6

SD 1.3 1.6 1.6 1.7 3.6 1.9
CV (%) 1.7% 25.0% 3.1% 3.3% 4.0% 3.8%
DX 18.2 6.6 46.7 47.1 82.1

Argentum® 930 “Casting”

L* a* b* c* YI DE
Before
93.5 -0.4 3.6 3.6 6.5
tarnish
After
84.3 2.2 21.5 21.6 42.4 20.3
tarnish
85.5 2.4 17.9 18.1 36.2 16.6
87.0 1.2 14.3 14.3 28.4 12.6
85.7 1.8 15.0 15.1 36.0 14.0
86.1 2.0 18.3 18.4 36.3 16.6

Average 85.7 1.9 17.4 17.5 35.9 16.0

SD 1.0 0.5 2.9 2.9 5.0 2.9
CV (%) 1.1% 24.0% 16.6% 16.7% 13.9% 18.4%
DX 7.8 2.3 13.8 13.9 29.4

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Legor Ag-Lite™
L* a* b* c* YI DE
Before
93.7 0.9 4.4 4.5 9.0
tarnish
After
87.6 0.7 12.1 12.2 24.0 9.8
tarnish
88.4 0.5 11.6 11.6 22.7 8.9
88.1 0.7 12.1 12.1 23.8 9.5
87.5 0.8 12.5 12.5 24.7 10.2
88.1 0.7 12.1 12.2 24.0 9.5

Average 87.9 0.7 12.1 12.1 23.8 9.6

SD 0.4 0.1 0.3 0.3 0.7 0.5
CV (%) 0.4% 16.1% 2.6% 2.7% 3.0% 4.8%
DX 5.8 -0.2 7.7 7.6 14.8

Argentium® 960 “Britannia”

L* a* b* c* YI DE
Before
95.4 -0.3 2.8 2.8 5.0
tarnish
After
86.6 0.6 10.6 10.6 21.3 11.8
tarnish
88.0 0.3 10.4 10.4 20.5 10.6
89.5 0.1 9.3 9.3 18.0 8.8
87.0 0.5 10.5 10.5 21.1 11.4
90.0 0.1 9.1 9.1 17.7 8.3

Average 88.2 0.3 10.0 10.0 19.7 10.2

SD 1.5 0.2 0.7 0.7 1.7 1.6
CV (%) 1.7% 71.3% 7.2% 7.2% 8.8% 15.4%
DX 7.2 0.6 7.2 7.2 14.7

Grimwade and Manchanda used modified versions of the TAA test. On the basis
of this comparison, though a summary, it is possible to note that repeatability is
poor in the absence of a precise test procedure that provides accurate definitions
of the procedures for preparing the samples and the test conditions.

22 The Tarnishing of Silver Alloys: Causes and Possibilities

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Table 5 DE values measured in other experiments

Standard sterling Argentium® 930

Legor Ag-lite™
silver “Casting”
Grimwade15 19.4 – 24.9 --- ---
Manchanda 23 11.1 7.6 4.4

The last observation regards the possibility of providing reference values for
the TAA sulfurization test in order to define when an alloy can be considered
resistant to tarnishing by sulfurization. On the basis of the results obtained by the
Legor R&D laboratory, one possible classification hypothesis could be as follows
(Table 6):

Table 6 Proposal of reference values for classifying silver alloys

on the basis of their resistance to the sulfurization test

DL DE
Alloy with high resistance to tarnishing by
<10 <20
sulfurization
Alloy with moderate resistance to tarnishing by
10<DL<15 20<DE<35
sulfurization
Alloy with poor resistance to tarnishing by
DL>15 DE>35
sulfurization

Conclusions
The considerations made in the introductory section reveal the complexity of the
tarnishing phenomenon. On the basis of the observations and data provided in
this work, the possibility exists, in our view, of defining targeted tests capable
of separately testing the sensitivity of the various factors responsible for the
chromatic alteration of silver alloys. The adoption of the analysis of the L*
coordinate would appear to provide useful information if carried out on flat,
perfectly polished surfaces. Finally, it is important to remember that greater
repeatability of the measurement data can be obtained if the test is carried out
at the initial stage of the tarnishing process. The same type of approach could
probably be used for assessing other aggressive factors.

May 2010 23
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Acknowledgements
We would like to thank:
- Dr. Massimo Peruzzo for his suggestions and the information regarding the
existing regulatory framework
- Dr. Elio Poma and Dr. Eng. Andrea Friso for a critical reading of the
manuscript
- Dr. Eng. Giuseppe Maronato for the information on the properties of lamps

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