An Update On Hardening of Sterling

Silver Alloys By Heat Treatment

By Dr. Jörg Fischer-Bühner, Head of Division of Physical
Metallurgy & Precious Metals Research, The Research
Institute for Precious Metals (FEM)

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 An Update on Hardening of Sterling
Silver Alloys by Heat Treatment
Dr. Jörg Fischer-Bühner
Head of Division of Physical Metallurgy
& Precious Metals Research
The Research Institute for Precious Metals (FEM)
Schwäbisch Gmünd, Germany

Abstract
Sterling silver alloys are comparably soft in the as-cast state (60-70 HV). A higher
strength is often required (e.g., for filigree items) and has a positive influence
on polishing properties. The hardness of sterling silver alloys can be increased
significantly up to ca. 140 HV by suitable heat-treatments. Although the process
has been well known in principle for decades, it is seldomly applied because it
is time-consuming, and significant improvements are sometimes not easy to
achieve in an industrial environment.
More recently, new sterling silver alloys have been developed with grain
refinement, fire-stain resistance and improved investment casting properties.
The as-cast hardness of these alloys is even lower than for standard sterling
silver (down to 50 HV), so that hardening by subsequent heat treatment possibly
will gain larger importance.
The paper first reviews the basics of strengthening sterling silver alloys by
age-hardening. The range of suitable heat treatment parameters is discussed for
standard sterling silver. This is followed by an overview on hardening properties
of the new sterling silver alloys. The influence of the main alloy constituents,
namely Cu, Zn, Si, Ge, Ir and B, is discussed as well as possible advantages/dis-
advantages of the new alloys compared to standard sterling silver. The paper
continues with some results on hardening directly from the as-cast state
without the high-temperature homogenisation anneal, which is usually required
before age-hardening. Finally, some examples for realisation of hardening of
industrial castings are presented.

Background
The possibility of hardening sterling silver by heat treatment is already
mentioned in early publications (e.g. by E. Raub1). The metallurgical principles
of “age-hardening” or “precipitation hardening” of sterling silver were presented
in detail by Mark Grimwade and Aldo Reti at earlier Santa Fe Symposia.2–4 With

May 2003 29
reference to the Ag-Cu-phase diagram shown in Figure 1, the usual process for a
binary 925Ag alloy, i.e., with 7.5wt% Cu can be shortly summarised as follows:
• Homogenisation (or solution treatment) above ~ 745°C to dissolve all the
copper in the silver matrix
• Rapid quenching in water, which prevents formation of coarse Cu-rich
precipitates (ineffective in causing hardening), and results in a super-
saturated state
• Aging at low temperatures, typically 300°C for one hour, which results in
formation of very fine Cu-rich particles (very effective in causing hardening)

Figure 1 Binary silver-copper phase diagram

Compared to standard 925 sterling silver, the copper content is significantly

reduced in modern commercial alloys, especially firestain-resistant alloys (see
Table 1). The influence of this reduction, as well as of the different alloying ele-
ments contained in these alloys, has not been reviewed so far.
Further issues which are of relevance in this context are: danger of grain
coarsening during homogenisation, ductility of hardened material, hardening of
soldered items, cost efficiency of heat treatments in mass production, as well as
possible solutions for hardening of stone-in-place castings (no quenching
allowed).

30 The Santa Fe Symposium on Jewelry Manufacturing Technology

Experimental
Some details on the alloys included in this study are given in Table 1:
Alloy Cu % Zn % Other
925Ag 7.5 --- ---
935Ag 6.5 --- ---
925Ag & Ir 7.5 --- 0.01% Ir
925Ag & B 7.5 --- 0.005% B
930Ag Zn20 5.0 2 ---
930/935Ag Zn20 Ir 4.5–5 2 0.01% Ir
925 Leg.Or* ~5 ~2 Si, Ge, B, …
927 Apecs G7 4 2.6 Si, Ge
* Two Leg.Or alloys were included, namely Ag108M and SF928CH
Table 1

In order to arrive at results without interference with deficiencies of as-cast

states (inhomogeneous grain size, porosity, etc.), some work was performed with
small bars of ~50g material melted and cast in protective atmosphere and
afterwards, rolled to ~60–70% (section reduction). Material was then cut into
samples suitable for heat treatment and hardness testing. This approach was
chosen for identifying the possible influence of the major alloying constituents,
namely copper and zinc, as well as of the grain refiners iridium and boron.
Hardening with as-cast material was studied using material from trees of ~300g
with a standardised test tree set-up (Figure 2), which was cast using standard
vacuum-assisted investment casting equipment and parameters (flask ~500°C,
casting temperature 970°C).

Figure 2 Standard casting tree (~300g) for

silver investment casting trials
May 2003 31
In order to evaluate the influence of hardening on ductility, as-cast wires of
925Ag and 930Ag20ZnIr - material were drawn from a diameter of 10mm down
to 2mm, heat treated and cut into samples suitable for tensile testing. Yield
strength, tensile strength and elongation until failure were recorded during room
temperature tensile tests using conventional equipment.
All heat treatments were carried out in protective nitrogen atmosphere with
temperatures/times specified later in the paper. After high temperature solution
treatment, samples were removed quickly from the furnace and quenched into
water immediately. After aging at low temperatures samples were cooled on air.
All samples were the subject of standard metallographic examination and
hardness testing on prepared cross-sections, using a conventional Vickers
hardness tester and a load corresponding to HV 1.

Review of Suitable Heat Treatment Parameters in

Standard Sterling Silver
A screening of aging properties was carried out on rolled sheets of 935Ag. An
unusually high homogenisation temperature of 800°C was chosen to ensure
complete solution of the copper in the silver matrix during 0.5–1 hour anneal-
ing. Water quenching of the samples was followed by aging at 150–350°C for
0.5–16 hours. Selected results of the screening are shown in Figure 3.
It is confirmed that:
• in 925Ag, an optimum hardening effect occurs for material annealed
at ~300°C for 0.5–1 hour.
At 250°C, the same hardness level is achieved only after ~4 hours. Prolonged
annealing at 300°C, as well as annealing at 350°C, leads to over-aging and
loss in strength.
However, homogenisation at too high temperatures leads to grain coarsening.
As already discussed by Aldo Reti,4 this can be suppressed in 925Ag if homogeni-
sation is carried out slightly below the usual borderline value of 745°C, e.g.,
at ~730°C, so that grain boundaries are effectively pinned by rests of eutectic
or Cu-rich phase. The microstructures shown in Figure 4 illustrate this issue.

32 The Santa Fe Symposium on Jewelry Manufacturing Technology

 Figure 3 Influence of aging temperature and time on age-hardening of 935Ag
after rolling (~66%) and homogenisation (800°C/1h/water quench)

a) 925Ag, 730°C/1h b) 925Ag, 800°C/1h

Figure 4 Microstructure of 925 after rolling (~66%) and

homogenisation at 730°C and 800°C/1h/water quench

May 2003 33
In agreement with the statements in Reti4, some rests of undissolved phases can
be tolerated in the aging process. Figure 5 shows the results of a screening on a)
rolled sheets and, b) cast material of 925Ag after homogenisation at 650°C–800°C
for 1 hour, water quenching, followed by aging at 300°C for 0.5–1 hour.
It is concluded that:
• in 925Ag, significant hardening still occurs if the temperature of homogen-
isation is lowered to 730°C (~140HV1) and even 700°C (~120HV1),whereas
a drastic reduction or almost no hardening after homogenisation at 650°C/
1 hour (the effect of longer annealing times at 650°C was not studied).

a) 925Ag, rolled material (~66%)

b) 925Ag, investment cast material

Figure 5 Influence of homogenisation temperature (650-800°C/1 hour/water

quench) on age-hardening of 925Ag after a) rolling and b) investment casting

34 The Santa Fe Symposium on Jewelry Manufacturing Technology

a) as-cast state b) cast & 650°C/1 hour

c) cast & 730°C/1 hour d) cast & 800°C/1 hour

Figure 6 Microstructure of 925Ag after investment casting

and homogenisation at 650°-800°C/1 hour/water quench

Figure 6 illustrates the change of an as-cast microstructure during homogenisa-

tion. Note the presence of still large amounts of Cu-rich phases in the matrix
after homogenisation at 650°C, whereas only some rests of eutectic phase are
present after homogenisation at 730°C. Note also that no obvious grain
coarsening of the as-cast microstructure occurred during annealing at 800°C, but
that obviously partial melting of the sample took place due to the high amounts
of low-melting (780°C) eutectic phase in the investment cast state (Figure 6d).

May 2003 35
What is the Influence of Hardening on Ductility?
Table 2 shows results of tensile testing of wires drawn from 925Ag and
930AgZn20Ir -castings. Data are given for samples in the homogenised state in
comparison to samples with subsequent aging at 300°C.

Table 2 Influence of hardening on tensile ductility and strength

HV 1 0.2% Y.S. UTS Elongation
(N/mm2) (N/mm2) (%)
925Ag, 730°C/1h 66 112 276 29
925Ag, 730°C/1h 142 333 405 9
+ 300°C/1h
930AgZn20Ir, 700°C/1h 70 121 267 40
930AgZn20Ir, 700°C/1h
+ 300°C/0.5h 127 302 372 19
930AgZn20Ir, 700°C/1h
+ 300°C/1h 127 293 347 14

The results clearly show that the strengthening effect is not encompassed by an
embrittlement, but that there is:
• a marked reduction in tensile ductility in sterling silver by age-hardening.
The data also illustrates the positive effect of grain refining additions since, in
the material grain-refined with Ir, the tensile elongation is higher for both
conditions, and the reduction by hardening is less pronounced. Hence, usage of
grain-refined material is recommended in cases where the material or the
product needs to tolerate relevant plastic deformation after the hardening
treatment, e.g., sizing of rings.

36 The Santa Fe Symposium on Jewelry Manufacturing Technology

What is the Influence of Alloy Composition on Age-
Hardening with Regard to the Grain Refiners Ir and B,
as Well as Zn, Si and Ge?
The listed elements are typical additions of the modern firestain-free alloys and
in sum lead to a significant reduction of the Cu content (compare to Table 1).
In a first set of experiments, rolled sheets of 925Ag, 935Ag, 930AgZn20, 925Ir
and 925B were homogenised at 650°C–800°C for 1 hour, water quenching,
followed by aging at 300°C for 0.5–1 hour. Hardness data are given in Figure 7
and are compared with the data given in Figure 5; selected microstructures are
shown in Figure 8. It turns out that there is:
• no major influence of the grain refiners Ir and B on age-hardening of ster-
ling silver under the present conditions.
It is also clear that, although the grain refinement after homogenisation at
730°C is pronounced, there is no reduction of grain coarsening at 800°C
by Ir- or B-additions (Figures 8 a–d).

Figure 7 Influence of copper/zinc content and grain-refining additions

on age-hardening of sterling silver, after a–d: rolling (~66%)
and homogenisation (650-800°C/1 hour/water quench)

May 2003 37
a) 925Ag+Iridium, 730°C/1hour b) 925Ag+Iridium, 800°C/1hour

c) 925Ag+Boron, 730°C/1hour d) 925Ag+Boron, 800°C/1hour

Figure 8 Microstructure of 925Ag + grain refiners (Ir, B) after rolling (~66%)

and homogenisation at 730°C and 800°C/1 hour/water quench

a) 935Ag, 730°C/1hour b) 935Ag, 730°C/1hour

Figure 9 Microstructure of 935Ag after rolling and homogenisation. Note
complete solution in b) and resulting grain coarsening in a) compared to 4a)

It is somehow surprising that there is little influence of the Cu-content (varied

here between 7.5 and 5%) on the hardening effect under the present conditions.

38 The Santa Fe Symposium on Jewelry Manufacturing Technology

In theory, lowering of the Cu-content should result in a lower volume fraction of
precipitations and less pronounced hardening. It can be speculated, however,
that this is levelled off by the fact that at a given temperature of homogenisation,
e.g., 730°C, solution of Cu in the silver matrix is more complete for an alloy with
lower Cu-content. In any case, the latter is the reason that during homogenisation
at 730°C, some grain coarsening occurs in 935Ag (or other alloys with even
lower copper content), in contrast to 925Ag (Figure 9, compare to Figure 4a).
In a second set of experiments, investment cast samples of 925Ag, 935Ag20ZnIr
and of the firestain-resistant alloys with Si, Ge–additions were homogenised
at 700°C and 730°C for 1 hour, water quenched, and age-hardened at 300°C
for 0.5–1 hour.
From the hardness data given in Figure 10, it is obvious that:
• the peak hardness is lower in these firestain-free alloys, compared to
standard 925Ag.

Figure 10 Influence of additions of firestain-resistance alloys on

age-hardening of different sterling silver alloys after: Investment
casting and homogenisation (700–730°C/1 hour/water quench)

Since a corresponding lowering of the peak hardness is also observed in the

935Ag20ZnIr- sample, this effect cannot be attributed alone to the Si- and Ge-
additions in the firestain-free alloys, but must be related to the high zinc content
and the resulting low copper content (4-5% in these alloys, see Table 1).
The latter is somehow contradictory to the results presented before, which were
obtained on rolled sheets. The reasons are not clear, but the data that are
presented for the firestain-free alloys are consistent with data measured by the

May 2003 39
corresponding alloy suppliers under same aging conditions.6 However, their data
consistently show that a slightly higher and optimum peak hardness of ~120HV
can be obtained during aging at 260°C/1.5 hour (Leg.Or) and 250°C
for 1–2 hour (Apecs), see Figure 11.

Figure 11 Age-hardening of 927 Apecs G7 alloy under various conditions

(data are shown with kind permission of Anthony P. Eccles6)

Special care needs to be given to the choice of the homogenisation temperature

of the firestain-free alloys. Low-melting phases (containing Cu + Ge and/or Si)
with a solidus temperature around 700°C are present in the as-cast state, so that
homogenisation should not be carried out above 700°C. In any case, an
enhancement of age-hardening by homogenisation at higher temperature is
not evident (Figure 10).

40 The Santa Fe Symposium on Jewelry Manufacturing Technology

Some Comments on the Interplay Between
Age-Hardening and Soldering Processes
Solder alloys for silver jewellery have solidus temperatures down to 600°C.
Homogenisation of a soldered item at temperatures required for subsequent
hardening is not possible because it would result in melting of the solder and
failure of the joint. Soldering an already age-hardened piece is not an option
either, because the soldering process will inevitably lead to a local loss in hard-
ness in the heat-affected zone. In some cases, a possible solution can be to carry
out the homogenisation anneal right before soldering and to perform the aging
afterwards as a final step. For soldering as-cast items, another option is also
available on the basis of the following results.

Is It Possible to Age-harden the Material Directly

from the As-cast State After Investment Casting
Without In-between High Temperature Annealing?
The motivation to study this aspect is obvious: silver jewellery often is a mass
product, with considerable demands concerning the cost-efficiency of the pro-
duction process. Moreover, the fear to increase firestain problems by prolonged
annealing at high temperatures is always present. However, simply skipping the
homogenisation treatment of castings has often proved to lead to no age-
hardening effect during aging, no matter at what temperature the aging was car-
ried out. During the conventional slow cooling of the flasks after casting, coarse
Cu-precipitates grow in the Ag-matrix and eliminate any potential for age-hard-
ening during a following aging treatment.
Hence, quenching of the flasks after casting would be a pre-requisite. The
following results show, however, that the parameters need to be chosen carefully.
Trees of ~300g size of 925Ag were cast by standard investment casting processes
and quenched in water at different times after casting (2–15 minutes). The
corresponding approximate metal temperatures at the time of quenching were
recorded and are reported in Figure 12, together with hardness data obtained
during subsequent aging at 300°C.

May 2003 41
 Figure 12 Age-hardening 925Ag directly from the as-cast
state: influence of quenching time and temperature
(right column: reference data for cast & homogenised material)
It is concluded that:
• significant hardening of 925Ag to ~110 HV 1 directly from the as-cast
state is possible, i.e., without the in-between homogenisation anneal at
high temperatures, but only if the flasks are quenched in water within a
critical range of time after casting.
The suitable time of quenching after casting will certainly depend on individual
casting parameters (especially casting and flask temperatures, and tree weight),
but is about 4 minutes in the presented case. Later quenching leads to marked
reductions and finally elimination of the age-hardening effect. Interestingly,
quenching too early also reduces the hardening effect. Obviously, some effective
homogenisation already occurs during cooling within the first minutes after
solidification, so that hardness in the as-cast state drops from 80 HV 1
(2 minutes) down 60 HV 1 (4 minutes), which gives the potential for subsequent
age-hardening from the as-cast state.
The resulting hardness in 925Ag is markedly lower compared to the hardness that
can be obtained by the conventional process. Furthermore, the process is less
controlled and some scattering of properties will occur depending on the position
of items on the tree, due to different cooling conditions over the length of a tree.
The level of hardness that can be obtained with alloys different from 925Ag
has not been studied yet.
42 The Santa Fe Symposium on Jewelry Manufacturing Technology
Can all this be transferred to Industrial Environment?
In the following, some results of industrial trials on hardening 925–935Ag,
starting from castings of usual industrial size (Figure 13a), will be discussed.
Both the conventional 2-step age-hardening process, as well as the shortened
process directly from the quenched as-cast state, have been tested out.
In the first case presented here, an industrial partner supplied several heat treated
935Ag test samples for hardness measurement at FEM (Figure 13b), which were
randomly taken from different positions of multiple trees. The results obtained
during a sequence of trials are shown in Figure 14. After a first trial, the
homogenisation temperature was increased to 750°C (on the display of the
furnace) in order to ensure effective homogenisation of the castings, but aging
during 300°C still was ineffective for the 0.5 hour anneal, which indicates that
heating rate was lower than during lab-scale research. However, age-hardening
for 1 hour at 300°C proved to be reproducible and without large scatter within
the sets of samples (+/- 10-15 HV). Controlled quenching of trees led to a
surprisingly good result for hardening directly from the as-cast and quenched
state, without a marked increase in scatter of properties.

a) 930Ag, as-cast tree

b) 925Ag, as-cast and age-hardened samples (bottom/top row respectively)

Figure 13 Examples of material used in industrial trials

May 2003 43
 Figure 14 Sequence of age-hardening trials of 935Ag by an industrial partner

Figure 15 illustrates the results of trials carried out with another partner, who
routinely casts a 930Ag20ZnIr- alloy. Samples from the top, middle and bottom
position of a tree were supplied to FEM for heat treatment and hardness testing.
The results show that homogenisation at 700°C is effective in eliminating the
mutual differences between samples on a tree, which may result during cooling
of a flask, and that a constant hardness of 120 HV 1 was obtained.

Figure 15 Sequence of age-hardening trials of 930Ag20ZnIr

by an industrial partner; temperature of homogenisation 650°C–700°C
Note the minor influence of sample position on the tree.

44 The Santa Fe Symposium on Jewelry Manufacturing Technology

The last case study focuses again on hardening directly from the as-cast state of
a third industrial partner. The 925Ag castings were quenched ~4 minutes in water
after casting. Again, samples from the top, middle and bottom positions were
supplied to FEM for heat treatment and hardness testing. The results shown in
Figure 16 illustrate that, although a hardening effect occurred, the optimum
parameters were not yet identified in this case. Note also that the influence of
the sample position on the tree increases if quenching is not carried out at the
optimum time, or under best conditions (stirring of flasks in the water can have
an influence).

Figure 16 Sequence of age-hardening trials of an industrial

partner on 925Ag castings quenched after ~4minutes. Note the influence
of sample position on the tree on the resulting hardness if hardening
is carried out without in-between homogenisation.

Obviously, it needs to be assessed on a case-by-case basis whether hardening

directly from the as-cast state is a suitable option that gives reproducible prop-
erties, or if the conventional process needs to be chosen for safety. Furthermore,
it turned out that for standard sterling silver, the annealing atmosphere for
homogenisation needs to be carefully controlled in order to avoid extended
internal oxidation and increased problems with firestain. In principle, treatment
in normal furnaces with a nitrogen flow is sufficient. But a safer and still
inexpensive solution is to treat the items in closed stainless steel vessels, again
with a continuous nitrogen flow inside the vessel. Quick quenching times after
homogenisation need to be assured in all cases, however.

May 2003 45
Summary
Generally speaking, the influence of Zn, Si, Ge and grain-refiner additions on the
age-hardening of sterling silver is low. The lower Cu-content in the firestain-
resistant alloys, as well as the need for lower homogenisation temperatures (low
melting phases), leads to a lower peak hardness in these alloys, 110–120 HV 1
after 700°C/1 hour/water quench, compared to 140 HV 1 in 925Ag after
730°C/1 hour/water quench, followed by aging at 300°C/1 hour.
The obvious advantage of the firestain-free alloys is that the resistance against
firestain is also maintained during the homogenisation treatment. For alloys
without Si or Ge additions, the annealing atmosphere for homogenisation needs
to be carefully controlled in order to avoid extended internal oxidation and
increased problems with firestain.
As expected, the tensile ductility of age-hardened material is significantly lower
than for soft material. Choice of a grain-refined material is recommended for
applications where larger plastic deformation needs to be tolerated by the
hardened material.
Applying hardening processes to soldered items needs further analysis and
trials. Although not discussed in the paper so far, hardening of stone-in-place
castings by heat treatment obviously is not advisable, since quenching steps are
involved in any case and will result in damage to the stones.
Significant hardening of 925Ag to ~ 110 HV 1 directly from the as-cast state is
possible, i.e., without the in-between homogenisation anneal at high tempera-
tures, if the flasks are quenched in water within a narrow and critical range of
time after investment casting (~4 minutes). The scatter of properties may be
increased, however, and the optimum parameters as well as the suitability of this
shortened hardening process need to be assessed on a case-by-case basis.

Acknowledgements
The author is especially grateful to the co-workers from the metallurgical
department at FEM for the realisation of all the research work. Fruitful
discussions with Dieter Ott and Valerio Faccenda are gratefully acknowledged.
Furthermore, the author likes to thank the industrial partners that contributed
with supply of material and their own trials: Daub, Quinn Scheurle, C. Hafner, (all
Germany), Leg.Or (Italy) and Apecs (Australia).

46 The Santa Fe Symposium on Jewelry Manufacturing Technology

References
1 Raub, E., “Die Edelmetalle und ihre Legierungen” J. Springer, 1940
2 Grimwade, Mark, “The nature of metals and alloys” Proceedings, Santa Fe
Symposium on Jewelry Manufacturing Technology 2001, p. 151
3 Grimwade, Mark, “Heat treatment of precious metals” Proceedings, Santa
Fe Symposium on Jewelry Manufacturing Technology 1991, p. 241
4 Reti, Aldo, “Understanding sterling silver” Proceedings, Santa Fe
Symposium on Jewelry Manufacturing Technology 1997, p. 339
5 Eccles, Anthony, “The evolution of an alloy” Proceedings, Santa Fe
Symposium on Jewelry Manufacturing Technology 1998, p. 203
6 Basso, Andrea (from Leg.Or), and Eccles, Anthony (from Apecs), private
communication, 2003

May 2003 47