Effect of Alloying Elements And

Tarnishing Effects In Sterling Silver Alloys

By Ajit Menon, Director of Technology, United Precious
Metal Refining, Inc.

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

800.545.6566 riogrande.com
 Menon
Effect of Alloying Elements
and Tarnishing Effects
in Sterling Silver Alloys

Ajit Menon
Director of Technology
United Precious Metal Refining, Inc.
Alden, NY, USA
Introduction
From the time silver was found to be a useful metal for making jewelry and deco-
rative articles, there has been a quest to find the most versatile alloy to provide
adequate hardness, good wear and tarnish resistance.
Tarnishing is basically a discoloration of sterling silver due to a chemical reaction
with the surface of the metal. As many as 22 different parameters and elements
have been identified as potential tarnishing agents. As these tarnishing elements
interact with each other in a multitude of combinations, it becomes extremely
difficult to study the exact nature of tarnish resistance for each individual ster-
ling silver alloy. Tarnish-resistance testing usually involves four or five routine
parameters such as artificial sweat, humidity, temperature, ultra-violet rays and
sulfur. It has been found that the addition of certain alloying elements, even in
small quantities, does have an effect on tarnish resistance, hardness and the micro-
structure of the alloy.
This paper will discuss the effect of the addition of selective alloying elements in
sterling silver formulations, and document the data on grain size, Vickers hard-
ness and reflectivity of the surface after exposing it to corrosive tarnishing fumes
(tarnish resistance). In addition, this paper will briefly discuss various types of
sterling silver coatings to prevent early tarnishing.

Effect of Alloying Elements

For this study, sterling silver alloys were made with the addition of ten different
elements (Au, 1%Pt, 3.5%Pt, Pd, Co, Zn, Mn, Si, Ge-Si, & Zn-Sn) and tested for
normal casting of jewelry. Reusability of the alloy, form-filling characteristics and
the presence of casting defects were carefully monitored. The amounts of alloying
elements were adjusted to provide peak casting performance.
For each alloy composition, an ingot (thickness 0.100") was poured and rolled
down to 0.030" thickness. These sheets were then annealed at 676°C (1250°F) for
30 minutes in an atmospheric oven for the metal to recrystallize and form equi-
axed grains. Alloy samples were then sent to an outside analytical laboratory to
measure the grain size and obtain photomicrographs (Tables 1–11).
The effects on tarnishing, Vickers hardness, grain size and microstructure were
studied and compared. The amount of alloying elements were carefully adjusted
so as not to affect the casting and form-filling characteristics. Observations on the
effect of alloying elements are noted below:

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Traditional Silver-Copper: This is the most widely used formulation and is very
popular in the “sterling silver with black antique finish.” Castings have thick
firescale and defects are very common. The metal possesses good hardness and
workability.
Table 1 Traditional sterling silver

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size
Traditional
sterling silver
composition
(92.5Ag 7.5Cu)
formulation.
Microstructure 42 HV 116 HV 11.50
viewed under
polarized light to
see the copper-rich
and silver-rich
phases.

1% Platinum: It is very difficult to get a homogenous mixture with 1% platinum

in sterling silver. Castings often show “hard spots” of undissolved platinum par-
ticles.
Table 2 1% Platinum

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver for-

mulations with 1%
platinum provide
no major increase
in hardness or tar- 37 HV 106 HV 10.00
nish resistance but
does show some
improvement in
grain refinement.

422 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
3.5% Platinum: Unlike the 1% platinum, the addition of 3.5% platinum makes it
comparatively easier to get a homogeneous mixture. Castings do exhibit firescale.
The metal produces a “dark” hue after polishing.
Table 3 3.5% Platinum

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations with
3.5% platinum
provide good
increase in hard-
40 HV 120 HV 13.00
ness and grain
refinement. There
is no improvement
in tarnish resis-
tance.

Palladium: The addition of 0.25% palladium to a standard sterling silver formula-

tion will give a “metallic” hue to the color of the alloy, similar to a nickel-white
gold alloy. There is no major increase in the alloy’s melting and casting tempera-
ture and its form-filling capability remains the same.
Table 4 Palladium based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations with
0.5% palladium
provide good
hardness and 38 HV 100 HV 10.00
grain refinement.
These alloys have
excellent tarnish
resistance.

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Gold: The addition of 0.25% gold to a standard sterling silver formulation will
improve the whiteness appearance of the metal. Under an oxidizing atmosphere,
such as hand-soldering, the metal seems to develop a slight yellowish hue.
Table 5 Gold based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations with
0.5% gold provide
good hardness and
38 HV 107 HV 9.10
grain refinement.
These alloys have
excellent tarnish
resistance.

Manganese: Small additions (0.25%) of manganese provide good hardness and

luster to the metal. Melt temperature increases by 10°C and the metal exhibits a
“high white” or sparkling effect when molten.
Table 6 Manganese based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations with
0.25% manganese
provide good
hardness but no 42 HV 108 HV 8.50
major grain refine-
ment. These alloys
have low tarnish
resistance.

424 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
Germanium-Silicon: Addition of about 0.2% germanium in combination of 0.15%
silicon increases the firescale and tarnishing resistance of the alloy. The metal
exhibits good fluidity, hardness and form-filling characteristics.
Table 7 Germanium-silicon based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size
Sterling silver
formulations with
0.20% germa-
nium and 0.15%
silicon provide
good hardness 42 HV 105 HV 7.00
and excellent tar-
nish resistance.
Microstructure
shows larger
grain size.

Zinc: The addition of about 5% zinc shows enhanced firescale resistance and
work-hardening abilities.
Table 8 Zinc based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations with
5.0% zinc are
relatively soft in
as-cast condition
35 HV 105 HV 8.50
but exhibit good
work hardening.
Microstructure
exhibits larger
grain size.

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Cobalt: The addition of 0.15% cobalt to a standard sterling silver formulation will
reduce the grain size by 50%. This effective grain refiner also increases the hard-
ness of the alloy.
Table 9 Cobalt based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size

Sterling silver
formulations
with 0.2% cobalt
provide excel-
lent hardness and 49 HV 115 HV 12.50
grain refinement.
These alloys also
have moderate
tarnish resistance.

Zinc-Tin: Additions of 2.50% zinc and 0.20% tin greatly enhances the form-filling
characteristics and exhibits good solidification gradients for large-surface cast-
ings.
Table 10 Zinc-tin based

As-cast 60% cold- ASTM

Description hard- rolled grain Image
ness hardness size
Sterling silver
formulations with
2.5% zinc and
0.2% tin are rela-
tively soft in as-
cast condition but 35 HV 105 HV 9.00
will exhibit good
work hardening.
Microstructure
exhibits larger
grain size.

426 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
Grain Size Measurements
Grain size photomicrographs and measurements were completed at a mate-
rial analysis lab. A cross-section of each sample was mounted in epoxy, metal-
lographically prepared to a one-micron finish. The samples were then polished,
and etched using a mixture of ammonium hydroxide and hydrogen peroxide
for examination using a light optical microscope. Grain-size measurements were
obtained for equiaxed grains in accordance with ASTM E-112-96 (2004)E2.
Table 11 Ranking according to hardness
(effect of alloying elements on grain size and hardness)

60% cold rolled ASTM grain size

Rank Alloying element
hardness (HV) grain size number
1 3.5 Pt 120 13.00
2 Traditional sterling 116 11.50
3 Cobalt 115 12.50
4 Manganese 108 8.50
5 Gold 107 9.10
6 1 Pt 106 10.00
7 Zinc-Tin 105 9.00
8 Zinc 105 8.50
9 Germanium-Silicon 105 7.00
10 Palladium 100 10.00

What is “Tarnish”?
When sterling silver or alloys with a high-silver content are subjected to small
amounts of chemicals, such as sulfur and/or chlorine salts, and then exposed
to a hot and humid environment, an electrochemical reaction takes place on the
surface of the alloy. This reaction results in the formation of different compounds
that discolor the surface and render a lusterless, dull appearance, which will often
darken to a thick, black color if exposed for longer periods.
The black discoloration routinely found on sterling silver is a combination of
blackish cuprous sulfide (Cu2S), brownish cuprous oxide (Cu2O), whitish silver
sulfate (Ag2SO4), bluish silver chloride (Ag-Cl) and brownish-black silver sulfide
(Ag2S). Research indicates that the silver content of a material must be greater than
85% for any of the silver-based tarnishing compounds to be formed.

“Relative Tarnish-Testing” Equipment

A modified desktop desiccator unit, divided into two chambers, was used in
the study (Figures 1 and 2). The top “sample chamber” was fitted with a slowly
rotating circular carousel, drilled with twelve 12.5mm (0.5-inch) exposure holes
located around the circumference. The lower “exposure chamber” was fitted with
two hotplate/magnetic stirrers, a UV light source and a temperature/humidity
reader. For this test, flat-rolled samples 25 x 25 x 0.75mm (1" x 1" x 0.030") were

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taped on top of each of the carousel holes, thereby exposing a 12.5mm (0.5-inch)
round surface area to the environment within the exposure chamber. Tarnishing
agents of varying concentrations were placed on the hot plate/stirrers in the
lower chamber and the UV light was activated. The temperature and humidity of
the lower exposure chamber were carefully monitored.

Figure 1 Tarnish-testing apparatus

Figure 2 Schematic drawing of tarnish-testing apparatus

Samples were first polished and finished utilizing six-micron grit paper. The
exposure locations for each sample were then marked. Pre-exposure color mea-
surements were taken for each sample using the Gretag-Macbeth Color-Eye
unit (Figure 3). Reflectivity and yellowness index data were also obtained for
each sample. The samples were then subjected to the corrosive fumes of 0.05%

428 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
ammonium-sulfide and 0.5% sodium chloride solutions for a period of 20 hours.
Post-exposure color, reflectivity and yellowness index measurements were taken
on the exposed section of each sample after testing (Figure 4). The results of the
comparison of pre- and post-exposure measurements, which indicate the loss of
reflectivity and/or the change in the reflectivity measurements for each sample,
were compiled (Table 12).

Figure 3 Pre-exposure measurements

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Figure 4 Post-exposure measurements

The reflectivity (L*) parameter of the color coordinate was used to measure the
reflectivity of the alloy “before” and “after” the accelerated chemical test. This
parameter allowed the grading of samples using a number, instead of judging by
the eye, after all the samples were simultaneously exposed to corrosive chemicals.
The higher the L* value, the higher was the reflectivity. This parameter was used
as a standard to measure, which formulation or sample was least affected and
which sample was affected the most by the corrosive tarnishing fumes.
Reflectivity change for each sample was graded accordingly. A ranking of the
reflectivity grading for all the sampled materials is noted in Table 12.

430 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
Table 12 Reflectivity measurements

Sterling silver reflectivity ranking before tarnish testing

Rank Alloying element L* (reflectivity)
1 Gold 95.991
2 Palladium 95.949
3 Cobalt 95.936
4 Zinc 95.850
5 Manganese 95.747
6 Traditional silver 95.733
7 Zinc–Tin 95.727
8 Germanium–Silicon 95.630
9 Platinum, 3.5% 95.536
10 Platinum, 1.0% 95.514

Sterling silver reflectivity ranking after tarnish testing

Rank Alloying element L* (reflectivity)
1 Palladium 81.771
2 Gold 71.782
3 Germanium–Silicon 69.430
4 Zinc 58.364
5 Zinc–Tin 56.642
6 Cobalt 50.460
7 Manganese 50.054
8 Platinum, 1.0% 48.420
9 Platinum, 3.5% 46.529
10 Traditional silver 45.656

Removing Tarnish from Silverware and Jewelry

There are two basic methods to remove tarnish from sterling silver.

1) Physical—removal using an abrasive compound

There are numerous polishing compounds available in the market. These com-
pounds contain various abrasives, which remove the silver sulfide or oxidized
layer mechanically. Once polished, the shiny surface may be coated with an anti-
tarnish chemical that will protect the metal surface by creating a very thin, passive
layer of oxide. This method will result in some minor loss of the metal.

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2) Chemical—reversing the reaction and turn back silver sulfide into silver
During the tarnishing process, an electrochemical reaction occurs where silver
metal reacts with sulfur (from the environment), loses electrons and increases its
oxidation number. Silver-sulfide is produced, which is dark brown or black in
color, and deposits on the surface of the metal (Figure 5).
The chemical method of tarnish removal basically reverses this electrochemical
reaction. In order to reverse this reaction, and turn silver sulfide back into silver,
we need to use another metal, which has low ionization energy (energy required
to remove electrons from an atom) so it can donate electrons to silver.

Figure 5 Tarnished sterling silver bowl

As aluminum has lower ionization energy than silver, it makes a fine electron
donor for this process. When tarnished sterling silver articles are made to react
with aluminum foil (in an alkaline medium), an electrochemical reaction (a small
electric current) takes place. The aluminum gets oxidized (loses electrons) and the
silver is reduced (gains electrons).
The black tarnish starts to reverse itself (from the silver articles) and deposits
onto the aluminum foil (Figure 6). The items used for this method are depicted
on Figure 7.

Figure 6 Surface showing Figure 7 Items required for

tarnish-free and tarnished areas chemical removal of tarnish

432 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys
 Menon
The chemical reaction can be described as follows:

a) Intermediate reactions:
3Ag2S(s) + 2Al(s) + 3H2O (l) = 6Ag (s) + Al2O3(s) + 3H2S(g)
3NaHCO3 (aq) + 3H2S (l) = 3NaHS (aq) + 3H2O (l) + 3CO2 (g)

b) Final reaction:

3Ag2S(s) + 2Al(s) + 3H2O (l) 6Ag (s) + Al2O3(s) + 3NaHS (aq)

+ 3H2O (l) + 3CO2 (g) = + 3NaHCO3 (aq)

Coatings for sterling silver products

A. Electroplating
Chromate conversion coating: These are mainly chromate, or non-chromate
based, solutions with an organic inhibitor. Immersing sterling silver products in
this solution, which coats the metal with a transparent organic protective layer,
forms a “passivation layer.” Such coatings will enhance the shelf life of the jewelry
product, by a few months, from the date of manufacture.
• Although electroplating sterling silver with fine silver will increase the shelf
life, it is not a permanent solution to tarnishing.
• Lately, some overseas manufacturers of silver jewelry have been electro-
plating their products with palladium flash-plating followed by a rhodium-
plating. Such electroplated jewelry will have excellent protection and will be
tarnish-free as long as the electroplated surface is not removed by use.
B. Non-electrolytic solvent-based chemical coating
There are various methods of applying a chemical based anti-tarnish coating for
sterling silver products. These may be classified into the following categories:
1) Chromate based coating solutions: This method comes as a one-
or two-step dipping procedure consisting of an electroplating step
followed by a dipping step. The two-step coating method will have
superior coating strength and provides a longer shelf life. One of the
main concerns of using chromate-based chemicals is the disposal of
the spent solutions and rinse water. As most of the solutions contain
hexavalent chromium, proper detoxification and disposal has to be
followed. Federal and local regulations should be followed when
disposing of these fluids.
2) Non-chromate based coatings: This multi-step method is mainly
tin-chloride based chemicals involving; 1) electro-cleaning; 2) acid
activation dipping; 3) stannous-chloride immersion for two minutes;
and 4) final DI water-rinsing and drying.
3) E-coat or electrophoresis: This method involves electroplating a clear,
water-based acrylic coating onto the surface of highly polished sterling
silver, followed by a baking process.

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C. Lacquer-spray coating
Lacquer coatings are still very popular with the sterling silver jewelry manufac-
turers. Water-based lacquers are easily put on the jewelry items by simple immer-
sion followed by a drying process.
Lacquers are also coated on by electrophoresis. A durable acrylic water-based
coating is deposited on the jewelry article in a process similar to electroplating.
After electroplating this clear polymer-resin base onto the jewelry article, the coat-
ing is further cured by heating it in an oven to produce a uniform, hard durable
coating.

Conclusion
Small additions of precious metals, such as palladium and gold, greatly enhance
the tarnish resistance of these alloys, whereas small additions of platinum, cobalt
or manganese provide good grain refinement and hardness for the alloy.
Studying the effects of various alloying elements on hardness, grain refinement
and tarnish resistance will help us understand the effects on metallurgical and
mechanical properties of sterling silver alloys. It will greatly help the industry in
the future development of superior sterling silver alloys with desirable proper-
ties.
While using different alloying elements to achieve certain desired properties in
sterling silver alloys, it is of utmost importance, to maintain the ability of the alloy
to be “user-friendly” for production purposes. All our efforts in achieving the
best tarnish resistance, or an alloy with superior hardness or best grain structure
will be futile if the product does not perform well in casting/fabrication or other
production methods expected from the alloy.

Acknowledgements
The author is indebted to Mr. Mel Bernhard—United Precious Metal Refining,
Inc. —for his advice and guidance in publishing this paper; Mr. John Tomsik of
Coleman Company for his assistance in providing technical abstracts regarding
different kinds of coating process for the sterling silver; Mr. Dippal Manchanda
of Birmingham Assay Office on the tarnishing of sterling silver; Mr. Keith Horn—
United Precious Metal Refining, Inc.—for his assistance in editing and formatting
the paper; and to IMR Test Labs, Lansing, NY, for their assistance in metallo-
graphic studies and analysis of different sterling silver samples.

References
1. Erich W. Salomon, “The Use of Cathodic Electrophoretic Lacquer Coatings
for Jewelry and Jewelry Finishes,” In The Santa Fe Symposium on Jewelry
Manufacturing Technology 1998, ed. Dave Schneller (Albuquerque: Met-Chem
Research, 1998): 374–376.
2. Dr. Christopher Raub, “Use of Silver in Jewelry,” In The Santa Fe Symposium
on Jewelry Manufacturing Technology 1989, ed. Dave Schneller (Albuquerque:
Met-Chem Research, 1989): 241–255.

434 Effect of Alloying Elements and Tarnishing Effects in Sterling Silver Alloys