Massimo Poliero

Legor and JTF President

Bressanvido, Vicenza, Italy

Massimo Poliero is Chief Executive of the Legor group

and President of the JTF. During many years he
worked in the field of jewellery production as research
metallurgist and production manager, gaining a deep
knowledge of jewellery technology. He joined Legor
as technical manager and presently coordinates
strategic programs and technical and trade activities
of the Legor group. He is author or co-author of
several technical presentations on jewellery
technology.

The correlations between the mechanical

characteristics of carat gold alloys and the
requirements of the different production techniques
(with the exception of investment casting) have been
highlighted. Guidelines are given for the selection of
the most suitable alloys for the different production
techniques.

Authors:
Massimo Poliero, Andrea Basso, Andrea Friso
Legor Srl, Bressanvido, Vicenza, Italy
Selection of gold alloys for mechanical working and
optimisation of the production process

Introduction

The different gold alloys currently available on the market have been originated by
the different needs of different specialised manufacturing applications. At present, it
is possible to define very well the composition of an alloy as a function of the specific
needs of the customer. On the other side it is not so easy to select the most suitable
alloy. Usually each production activity represents an unique case, and this is
particularly true for jewellery production, where hand manufacturing is still very
important. Therefore it is necessary to be able to suggest specific solutions, that take
into account the production process to which the alloy will be submitted. In an ideal
case such solution should consider all technological and process parameters and
all possible sources of defects, such as used equipment, type of production
process, risks of pollution, product design an many more possible causes that could
bring to the fore any weak point of the alloy.
The purpose of this paper is to focus on jewellery production by plastic deformation,
starting from some basic concepts of physical metallurgy. A description of the
fundamental parameters of the different types of mechanical working will follow, with
an indication of the more suitable alloys for the different processing techniques.
Finally technical specifications will be outlined with the use of these parameters,
considering the acceptable tolerance for a given mechanical working process.

Alloys for jewellery production

Two production processes are prevailingly used in the field of jewellery and
silverware production: investment casting and mechanical working.
The standard carat gold alloys used for jewellery production, i.e. the alloys based on
the gold-silver-copper and gold-nickel-copper systems show good workability and
good castability and are the basis for both types of production process. However these
basic alloys are not sufficient to overcome some commonly occurring problems. So
additions of further alloying elements are required, to get improved performance.
The ternary systems are also very versatile regarding the different obtainable colours:
from the deep yellow of pure gold, to red alloys with increased copper content. Large
silver additions can give nearly green-yellow colour, or even white colour for lower
caratage alloys, even if the white colour is more marked when alloying additions with
stronger bleaching power are used, like nickel, palladium or manganese.
Moreover a variety of caratages are required by the market. Alloys with similar colour
can show widely different mechanical, chemical and technological characteristics as
a function of precious metal fineness. Therefore different compositions could be
required even for working with the same production process.
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Some problems to be faced in the production process of gold alloy jewellery by
mechanical working are:

• Oxidation of some alloying elements during melting

• Coarse grain size
• Insufficient strength
• Strong work hardening and low deformability
• Brittleness
• Poor solderability and/or weldability
• Low corrosion resistance
• Annealing temperature and cooling rate not always optimised
• Low response to hardening heat treatment.

The standard composition of an alloy can be modified to overcome some of the above
problems. But the alloying additions used for this purpose must avoid to modify too
much the other properties of the alloy, mainly the colour. The most frequently used
alloying elements are zinc, tin, germanium, indium and gallium.
Indium, ruthenium and cobalt (1) can be used as grain refiners. Silicon, lithium and
phosphorus can be used as deoxidisers in the melting process.
It should be underlined that the effect of an addition is strictly dependent on
concentration, solid state solubility and distribution homogeneity in the cast
semifinished product. For example, a too large addition of an element that in the
correct amount acts as a grain refiner can originate hard spots on the surface of the
final product (2).
An incorrect addition of deoxidisers can cause embrittlement of the pieces in the
subsequent stages of mechanical working.
Usually it is recommended to use homogenised binary alloys.
We will now describe the properties of some alloying elements commonly added to
gold alloys for mechanical working.

Zinc: Zinc is the most commonly added element in gold alloys. Since long time it is
used in low caratage coloured golds and in nickel white golds, with a concentration
ranging up to about 10%wt. In the gold-nickel-zinc system, zinc is used for lowering
liquidus and solidus temperatures. Zinc affects the colour and improves castability.
Low caratage alloys are not homogeneous single phase alloys and may be subjected
to intergranular corrosion and stress corrosion. Zinc oxide can form during melting in
air and is difficult to remove from the melt, while copper oxide can be more easily
removed. Thin films of zinc oxide can remain inside the alloy and cause typical
defects. Zinc improves workability in the alloys for mechanical working. Zinc also
reduces the melting range in the gold alloy solders.

Nickel (11): Nickel white golds are widely used in the whole world for jewellery
production, thanks to the low cost of the alloying elements, to the melting
temperature lower than 1000°C and to the good white colour. An increased nickel
content causes a marked whitening effect, but increases also the hardness of the
216 Jewelry Technology Forum
alloy. These effects are somewhat conflicting: there are alloys containing 9-10wt.%
nickel showing a very good white colour, that can be used only for applications
where large deformations are not required. Other alloys contain only 4-5wt.% nickel:
these alloys show very good mechanical characteristics, but rhodium plating is
required to improve colour and corrosion resistance is limited.

Palladium (11): It is considered as a more “noble” substitute for nickel in white gold.
Palladium enables to obtain the best “nickel free” white golds, whit a very good colour,
good workability and very good corrosion resistance. An addition of 10 to 12 wt.%
palladium is required to obtain a good white colour. High cost and high density affect
the final cost of the product. The high melting temperature of palladium white golds (>
1100°C) makes them more difficult to use.

Grain refiners (iridium, ruthenium and cobalt) (9): As cast yellow and red golds
tend to show a markedly dendritic structure and a rather coarse grain size. A coarse
grain can cause the “orange peel” effect and reduce alloy ductility. These grain
refiners show low solubility in the gold alloys and this characteristic form the basis of
the effect of grain refiners. Very fine and homogeneously dispersed particles can form
in the molten metal during casting or in the solid alloy during annealing. In both cases
these particles form nucleation sites for the growth of new grains. So a sufficient
number of nucleated grains prevents excessive growth of the new grains, Figure 1.

Figure 1 - Comparison of two alloys with different content of grain refiners -

observation under the optical microscope (100x)

Iridium is frequently added to gold alloys for grain refining: 0.01wt.% Ir is sufficient to
obtain a fine grain size in 14 and 18 ct alloys. Iridium, like ruthenium, acts before alloy
solidification, with formation of finely dispersed solid particles in the molten metal.
The use of ruthenium is already known from dentistry and ruthenium is used also for
jewellery production, particularly in nickel white golds. Ruthenium solid state
solubility in white gold is low, but sufficient for the use: it shows a very good grain
refining effect with a concentration in the range of .002 to .02wt.%.
Cobalt is an effective grain refiner only in the solid state, when annealing cold worked
material. Cobalt concentration in the range of .1 to .5wt.% is used for 14 and 18 ct
carat golds. Cobalt does not cause the same effect in the casting process, because
in this case different cooling rates can modify the size of the precipitated particles
June 2005 217
with possible adverse effects. When correctly used, cobalt increases hardness and
strength of the alloys, leaving malleability unaffected. Cobalt enables to obtain a
better control of heat treatment and guarantees a higher thermal stability of the alloy
with unchanged aesthetic characteristics.
Similar grain refining effects can be obtained (with a slightly different mechanism) by
using elements with high affinity with oxygen, that can form finely dispersed oxides,
like yttrium, boron, barium and calcium, or fine dispersions of intermetallic
compounds (zirconium/boron, cobalt/boron).

Deoxidisers (silicon, lithium, phosphorous) (10): Yellow golds based on the

ternary Au-Ag-Cu system should not need deoxidiser additions, because only
copper oxides can form that are readily removed, if slightly reducing conditions are
kept in the crucible. However sometimes deoxidisers are added to reduce copper
oxide and to form more stable oxides. On the other hand, in the case of alloys
modified with the above mentioned alloying elements, the deoxidiser should prevent
the oxidation of these elements, thanks to its stronger affinity with oxygen (Figure 2)
(Data on the free energy of reaction can be found in the scientific literature).

Figure 2 - Comparison between a cast tree produced with an alloy with deoxidiser (a)
and an alloy without deoxidiser (b)

Silicon is frequently used as an addition for investment casting, but does not show
appreciable solid state solubility in pure gold and silver. Solid state solubility of
silicon in copper is higher, and gold alloyed with a sufficient amount of copper can
tolerate small amounts of silicon, without suffering from grain boundary segregation.
Silicon is used to improve castability and as a deoxidiser. The recommended silicon
concentration is lower than .02 wt.% in 18 ct gold and between .03 and .05 wt.% in
9 and 14 ct gold. Silicon additions can cause some undesirable side effects: alloy
embrittlement, caused by grain boundary segregation of low melting, brittle phases,
and grain coarsening that increases the risk of cracking.

Lithium and phosphorus are deoxidisers of the melt. They are beneficial only if the
amount strictly required for removing oxygen is added. Particularly, an excess of
phosphorus can have very adverse effects and cause alloy embrittlement.
218 Jewelry Technology Forum
Mechanical deformation for jewellery production

Metallic materials are polycrystalline aggregates and usually solidify with a

nucleation and growth mechanism. In normal conditions, the liquid to solid phase
transformation starts from mould walls or from impurity nuclei present in the molten
mass. The result is a solid body formed by a large number of microscopic parts,
each formed by a regular lattice, having a structure similar to a single crystal. Each
part is a “crystal grain” and is in contact with the other grains through an interface,
that is called a “grain boundary”. The grain boundaries are very important for
determining the characteristics of the metal. They are the grain growth front during
annealing and also interact with the slip bands of plastic deformation. Moreover the
grain boundaries are sites of high chemical reactivity and in the case of corrosion,
grain boundaries are corroded first.

Basic metallurgical concepts

When an external stress is applied to a solid metal, the crystal grain deform by slipping along
specific planes of the crystal lattice or with the formation of geminates. The effective stress on
the lattice planes is always a shear stress. There is experimental evidence that a decohesion
of the lattice planes caused by stress perpendicular to the lattice plane never occurs.
There are three rules describing the slip planes in a single crystal:

• Slip usually takes place in the direction where the atoms are more densely packed
• Slip usually takes place in densely packed planes
• When many slip systems (planes and directions) are possible, slip occurs along the
system subjected to the stronger shear stress.

Slip is not the only process by which a crystal may deform plastically, an alternative one,
called twinning, is commonly observed. When twinning occurs, a part of the stressed
crystal lattice becomes a mirror image of the other part. The contribution of twinning to
plastic deformation is usually negligible, but can have an important indirect effect on the
global amount of deformation, because it can originate favourable conditions in the lattice
for a new slip process.

As far as the type of crystal lattice is concerned, suffice it to say here that face centred
cubic metals, like gold and copper, have a large number of slip systems (12, produced by
4 planes, each with 3 directions) that makes them ready for plastic deformation.
Calculation of the shear stress needed for pushing a whole crystal plane past the other
gives a yield stress of about 15 GPa, while experiment gives maximum values of yield
stress of about 1MPa. This enormous difference is due to the fact that the slip process
does not consist of the rigid motion of atomic planes relative to one another, but it starts
from a lattice imperfection and then spreads along a plane. For temperatures far below the
melting point and relatively low stress, dislocations are the most commonly occurring
defect. The properties of dislocations, their ability to multiply under stress, the mutual
interaction between dislocations and the interaction with other types of defects are
responsible of the largest part of mechanical properties of metals (cold working, yielding,
elongation, creep) (Figure 3).
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 Figure 3 - Sketch of dislocations movement: a) edge dislocation, b) screw dislocation

Dislocations in a crystal are line defects, i.e. unidimensional defects and can be considered
as the boundary (a few atomic spacing thick) between the part of the crystal lattice that has
been subjected to slip because of the applied stress and the part that did not slip.
The displacement of a dislocation line can take place in the slip plane or perpendicularly to
the slip plane. In the first case we have an edge dislocation, in the second case we have a
screw dislocation. In real crystals usually a combination of both dislocation types is present.

We will now discuss the plastic deformation processes most commonly used for
metal working, that are used also in the field of jewellery production.

• Rolling is the operation where a piece of malleable metal (cold or hot) is submitted
to a gradual plastic deformation by passing between two cylindrical or grooved
rolls. The rolls can be made of steel or nodular cast iron and rotate in opposite
direction. The amount of reduction for each pass is selected as a function of the
number of rolling passes through a set of roll pairs (rolling train) (Figure 4).

Figure 4 - Sketch of the rolling process

• Wire drawing is the operation where a gradual cold reduction of section and a
simultaneous elongation of a metal piece are obtained by passing it through a
tapered hole (die plate) under the action of an external force. Wire drawing is
started with an annealed and pickled wire rod (coils of a cold rolled semifinished
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 product, with smooth surface). The cross section of the wire rod is reduced by
means of a set of passes through the die plate. In this case too the drawing
operation depends on the number of dies used and on the characteristics of the
dies (Figure 5).

Figure 5 - Sketch of the wire drawing process

• Die striking: die struck products are obtained by applying a load on a metal
piece that is pressed into an impression in a die. The impression corresponds to
the shape that should be given to the piece. The final shape can be obtained in
one or more steps. Usually the load is applied with a press (pressure action) or a
drop hammer (strike action).
• Extrusion: the metal piece is forced by compression through a tapered hole having
the size and the shape of the cross section of the desired product, or through the
annular space between the die and the plug.
• Blanking and punching: a piece of sheet is cut with two contoured cutting tools
(the punch and the die) to obtain a cut piece having the contour of the cutting
tools (Figure 6).

Figure 6 - Sketch of the blanking process

• Bending: it enables to obtain pieces with a geometry that must be developable

on a plane.
• Deep drawing: it enables to obtain hollow shapes with a press, starting from flat
sheets.

In other sectors of metallurgy there is a distinction between hot working and cold working.
Hot working is defined as an operation that is carried out at a temperature higher than
June 2005 221
recrystallisation temperature, i.e. at a temperature where a heavily cold worked metal
reaches the microstructure of the annealed material within one hour. Such temperature is
typical for each metal and usually ranges from one third to half of the absolute melting
temperature. This empirical rule is generally in accord with the more exact differential
thermal analysis, which enables to measure the amount of energy that is stored in the cold
worked material as mechanical energy and is released as heat during annealing.
Some working operations, like die striking or forging, are usually performed at a relatively
high temperature. In other cases like deep drawing, blanking and bending, cold working
is commonly used. Rolling, extrusion and wire drawing can be carried out both hot or cold
(depending on material type and on the designed use). In some rolling processes there is
a first stage of hot rolling, followed by some passes of cold rolling to obtain a partially cold
worked structure. In this way the mechanical characteristics of the rolled product can be
brought at a specific desired level. In the field of jewellery production only cold working is
used and the above distinction does not apply.

Each method of cold working submits the material to specific plastic deformations
that are reflected in the microstructure transformations of the metal. This is the tight
link connecting macroscopic parameters like ductility, malleability and hardness with
alloy composition. The metallurgical transformations and heat treatments, along with
the specific alloy composition, will determine alloy microstructure. In its turn, alloy
microstructure will indicate the further working operations that could be carried out
on a piece, avoiding defect formation.

Principal methods for determining the physical and

mechanical characteristics of a carat gold alloy

1. Tensile test: The tensile strength of a material is usually evaluated with this kind of
destructive test. A sample with suitable elongated shape is clamped at both ends
and is submitted to an increasing tensile load in a machine that records both

Figure 7 - Comparison between two different stress-strain curves

- Curve 1 - Alloy with low proof stress, with a wide range of plastic deformation, that
is suitable for processing with strong deformation.
- Curve 2 - Alloy with high proof stress, and wide range of elastic deformation,
that typical of high strength alloys.
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 tensile stress and tensile strain. This is one of the simplest and most important
tests in the field of metallurgy for the characterisation and acceptance of a material,
because in a short time it gives information on proof stress, ultimate tensile
strength and some other properties of a metallic material (Figures 7 and 8).

Figure 8 - Equipment for tensile testing, carried out on a 1 mm dia. rope

Some considerations can be made on the curves of Figure 7. Curve 1 shows a low
proof stress and is typical for a material with relatively good workability, with a wide
deformation range before rupture. This material will tolerate a fair number of working
operations before becoming too work hardened. Such curve is typical for annealed
alloys. The second curve shows a more steep, linear slope, indicating a markedly
elastic behaviour, with high proof stress. Such curve is typical for high strength
alloys, suitable for the production of springs.

2. Hardness test: Hardness can be considered as an index of the resistance of a

material to plastic deformation. It gives also approximate information on wear and
scratch resistance. The tests used in metallurgical practice are based on the
resistance of the material to the penetration of an indenter with a specified shape.
This indenter is perpendicularly pressed onto a face of the sample with a
predefined load. Then the size of the impression left by the indenter is measured.
The Vickers hardness test is the most commonly used hardness test in the field
of jewellery production. In this case a square pyramid indenter is used that can
give reliable results with a very wide range of hardness values. It is possible to
test very soft materials (5 HV) up to very hard ones (1500 HV) (Figure 9).

Figure 9 - Impression of the Vickers microindenter on the surface of a sample

June 2005 223
3. Differential Thermal Analysis (DTA): This method enables to record the
temperature difference between a reference sample and the sample under study
as a function of time and temperature. The two samples are submitted to identical
heating and cooling cycles in a suitable furnace. The recorded temperature
difference reveals phenomena occurring in the sample under study which imply
heat absorption or release and enables to measure such parameters as melting
enthalpy, liquidus and solidus temperatures and also solid state transformations,
like phase changes or recovery and recrystallisation of work hardened samples.
Modern instruments are also equipped with thermogravimetric analysis that
enables to monitor the mass of the sample when submitted to temperature
changes, to investigate phenomena like the evaporation or the oxidation of high
vapour pressure or reactive elements (Figure 10).

Figure 10 - Plot of a DTA analysis on an alloy sample.

The solidus and liquidus temperatures of the alloy can be seen.
The measurement of the highlighted area enables to evaluate melting enthalpy.

4. Evaluation of grain size: This evaluation is carried out on the images of the
metallographic observations. After selecting a representative samples, pictures are
taken with a known magnification. Then the two main diagonals are measured for
a number of grains sufficient for a statistical analysis (a minimum of ten) (Figure
11). Alternatively, an evaluation of grain size and shape can be obtained by
comparing the image of the sample with a set of standard charts (ASTM Standard).

Figure 11 - Optical micrograph with measurement of

the diagonals to evaluate grain size
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Technology and processes for jewellery production

Common production stages

In the field of jewellery production, semifinished products like plate or wire are the
starting material for manufacturing jewellery by plastic deformation. Here we will
briefly describe the production techniques for such semifinished products. Crucible
type, casting temperature, amount of cast metal, mould size and cooling rate are the
most important parameters for both continuous casting and ingot casting.

Continuous casting. The furnaces for continuous casting enable to cast plates of any
thickness and size and rods with 3 to 12 mm diameter. The most evident advantages
of continuous casting are a better process control and a higher productivity.
Additional advantages come from a better quality of the cast metal, which is more
homogeneous and does not show shrinkage porosity or pipes (Figure 12).

1: Molten metal
2: Crucible
3: Induction Heating
4: Casting die
5: Water cooling
6: Cast bar
7: Pulling device

Figure 12 - Sketch of continuous casting of gold alloys

Ingot casting. Plates with size and thickness similar to continuously cast plates can
be obtained by mould casting (but in limited amount). Also bars with round or square
cross section can be produced. The cast material is sent to rolling or wire drawing.
Only a part of the cast material goes to further processing, because it is necessary
to remove segregated or oxidised zones.
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The cast plates are sent to the rolling mill for thickness reduction. The width is not
appreciably increased, but the thickness is reduced of 40 to 80% of the starting
thickness. The most common thickness reduction is 70%, but each alloy requires a
different amount of rolling reduction. Therefore a plate with 10 mm starting thickness
will be rolled to 3 mm thickness.

In the case of wire drawing, the starting rod has usually 8 mm diameter and, with 70%
area reduction, is brought to 4.4 mm diameter by passing through a set of drawing
dies with a reduction of .2 to .5 mm per pass.
After each set of reduction passes the material should be annealed. In the field of gold
alloys, annealing is carried out at 650-680°C for an average time of 25-35 min (as a
function of thickness) with rapid cooling, (with the exception of nickel white gold in
some cases). There are three different ways for performing the annealing treatment.

Annealing in a batch furnace. When possible, this is the best choice, because it
allows an accurate control of temperature, time, atmosphere and cooling rate.
However the limited size of the furnace chamber makes its use difficult in the case of
bulky materials (it is not possible to bend plates or rods more than 2.5 mm thick).

Annealing in a belt furnace. It is rapid, a reducing atmosphere can be used and it is

suitable also for long sections, but belt speed is the only adjustable parameter. But there
is frequently the disadvantage of a low cooling rate, that can cause undesirable effects
with age hardening alloys. Moreover higher annealing temperatures should be used,
because of the short stay of the material in the heating chamber. The belt furnaces are
widely used for annealing plates for stampato and tubes for hollow jewellery.

Torch annealing. This method can be used only by very skilled goldsmiths. Anyway
the control of annealing parameters is insufficient.

The sequence of deformation and annealing stages is repeated until the thickness (or
diameter) more suitable for further processing is obtained. It is preferred to carry out the
last reduction step with the strongest admissible reduction. This goal can be achieved
with a suitable planning of the preceding reduction stages. This schedule enables to
obtain the best performances whether a work hardened material (for blanking, cladding)
or a last annealing operation are required.

Examples of production processes commonly used for jewellery manufacturing are

given in the following paragraphs.

Production of hollow tube

The starting material could be an 18 ct gold annealed plate 0.6 mm thick and a tube
with 12 mm diameter is produced by TIG welding. The thickness of the tube is sized
by mandrel drawing on a 10 mm diameter casehardened steel bar. The steel bar is
removed after sizing and is substituted with a tombac core with slightly smaller
226 Jewelry Technology Forum
diameter (9.7 mm) to make coupling possible. After some drawing steps (to 9.5 mm),
cladding is performed in a belt furnace between 730 and 780 °C with a speed of 60
to 70 cm/minute. Further drawing and annealing steps are then performed until the
required final diameter is obtained. Subsequently the tube is shaped, coiled, sawed,
hollowed, soldered, age hardened and finished, with mechanized finishing and finally
hand finishing.
For 14 ct alloys the procedure is the same but thickness is different (Figure 13).

Figure 13 - Earrings produced with the hollow tube technique

Required characteristics: The yellow golds require hardening by heat treatment. They
should have fine grain size and good ductility. Moreover hardness of cold worked
material should not be too high, because before annealing the tube is wound on a coiler
and this could cause the formation of micro-cracks hardly visible to the naked eye.
For red golds the highest level of grain refining should be reached, to prevent and
control excessive grain growth and precipitation phenomena in processes that do not
allow fast cooling after annealing or soldering.
The use of low nickel white golds improves ductility, even if fine grain size and good
malleability are still needed.
For both yellow and white golds it is preferable to add alloying elements preventing
oxide formation during melting or TIG welding.

“Aggraffatura” (hollow chain) (7). The “aggraffatura” is an evolution of the cladding

process, is easily performed for all caratages and enables to obtain also very
complex shapes. Probably it is the most widely used process for producing bi-
metallic wire (gold/copper, gold/tombac, gold/iron). The core material must be
selected as a function of the caratage of the gold alloy, that causes a different
resistance to the emptying process after jewellery manufacture.
Copper is used as core material for 18 ct or higher caratage alloys, because it shows
June 2005 227
the maximum mechanical similarity and weldability and a very good adhesion to gold
alloy after cladding. After shaping and soldering, the copper core can be removed by
dissolution in a diluted nitric acid solution for 7 to 12 hours, depending on the shape
and thickness of the pieces. A so long dissolution time is acceptable thanks to the
very good resistance of high caratage alloys to chemical dissolution.
Tombac (90% Cu, 10% Zn) is the most widely used core material for 14 ct gold
(Figure 14). Tombac characteristics are similar to copper, but resistance to nitric acid
is lower. Therefore the time required for core dissolution is about 25% shorter. So the
exposure time of the precious alloy to the acid solution is also shorter, because the
chemical resistance of the gold alloy decreases markedly with decreasing caratage.
Core dissolution with nitric acid is not possible for 9 ct alloys, so the only choice is a
low carbon iron core, and dissolution is carried out with hydrochloric acid. In this way,
fineness homogeneity is guaranteed, because hydrochloric acid removes iron
completely and has little effect on the gold alloy, even in the case of low caratage alloys.
However the mechanical characteristics of iron and interface diffusion of iron with
gold are completely different from copper and tombac and a specific processing
technique is required. Iron can also be used for the production of 14 and 18 ct hollow
jewellery, to achieve the maximum guarantee on fineness.

Figure 14 - (a) Cross section of the tombac core before the “aggraffatura”.
(b) Cross section of the gold alloy plate “aggraffata” to the tombac core.
A gold solder wire can be seen in the centre of the tombac core.

For producing hollow chain a gold plate is “aggraffato”(linked) to the core that has
been previously milled to make the grooves for fastening the gold plate. The
“aggraffatura” is machine made, with a speed of 25-30 cm/min, depending on core
type. The bi-metallic material is annealed at about 680-700°C. The core material
greatly affects the diffusion process at the interface between the two metals. Iron does
not show particular affinity with gold, therefore it does not form a strong bond and can
freely slip during subsequent processing. On the contrary, after diffusion copper and
tombac cores give a true bimetallic body with well defined mechanical properties.
Further drawing and annealing steps are required to obtain the required diameter wire.
The wire is then used for the different operations needed for chain production (chain
shaping, soldering, hammering, diamond cutting, attachment of optional pieces, etc.).
The core is then dissolved out with a suitable acid. Subsequent steps are deoxidising
and possibly a hardening heat treatment before finishing (Figure 15).
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 Figure 15 - Bracelet made with the hollow chain technique

Required characteristics: No specific characteristics of the alloys are required for this
production technique, but only fine grain, ductility and resistance to dissolution by
acid solutions. In the case of 14 ct alloys, a high liquidus temperature is preferred for
furnace soldering, to have a sufficient melting temperature difference between the
solder and the gold alloy tube. In the case of “aggraffatura” usually the solder wire is
placed near the centre or near the surface of the core wire.

Cladding. The plate is rolled to 3.5 mm thickness without annealing and is then
joined with a copper or tombac plate. The joining process includes a high
temperature diffusion step (800-860°C for about 140 min) and a subsequent pressing
operation under a load of 350 tons, immediately after pulling the plates out of the
furnace. The material is cooled a couple of minutes after pressing. In the pressing
operation a further diffusion takes place at the gold-tombac interface and an inter-
metallic bond is formed, and “cladding” is obtained. The subsequent rolling process
is carried out with the usual reduction and annealing steps, as already said.
When a suitable thickness has been reached, strips are cut and are closed with a
suitable device; a filling copper core is also inserted.
Then a further rolling cycle is performed, as in the “aggraffato” process. The only
difference is that with cladding gold and tombac form a single body that can be
submitted to all types of deformation.
The cladding process usually causes the formation of an appreciable amount of
scrap, that must be refined, so this process is less commonly used.

Required characteristics: an alloy suitable for cladding should show a wide melting
range, to be able to retain some strength when in the pasty state. This characteristic
prevents the occurrence of some problems as the melting of the gold plate during the
June 2005 229
heat treatment and the subsequent pressing operation. So a uniform thickness and
an optimum cladding are guaranteed.
Fine grain size is required because of the many mechanical working steps with long
high temperature treatment. Moreover fine grain gives a better resistance of the alloy
during core dissolution.
The alloy should also be protected from high temperature oxidation (particularly in
the cladding operation) by means of the addition of deoxidisers.
This technique enables to obtain very good results even with alloys with above
average hardness.

Stamping. Stamping is carried out on .09 to .3 mm thick annealed sheet and it

essentially is a kind of deep drawing. The sheet must not tear during stamping. If
there is a risk of tearing, stamping must be carried out in many steps, and the stroke
of the punch should be increased step by step. The sheet piece should be annealed
after each step and then placed again in the die. The lubricants used to facilitate
slipping of the sheet on the die surface should be removed after the desired shape
has been obtained. Subsequently, the stamped piece can be soldered to other
components, if necessary, to obtain the end product. For example, if the stamped
piece should be soldered to a flat sheet, a solder flush sheet (i.e. a solder covered
carat gold sheet) could be used. The pieces to be joined are positioned and are put
in a furnace. Final trimming and surface finishing are carried out on the soldered
pieces, Figure 16.

Figure 16 - Pendants produced through stamping and soldering

Required characteristics: Carat gold alloys suitable for stamping should have a lower
than average proof stress, high deformability and controlled grain size. Usually these
alloys are not hardened by heat treatment, unless very low thickness is reached (lower
than 0.12 mm). In this case a hardening heat treatment is required that is carried out
after soldering.

Blanking. Usually a carat gold sheet is cut into strips, and the number of obtainable
items per unit length is optimised. Then the blanks are cut with a punch and a die
plate. If blanking is correctly performed, the blanks are ready for further use:
assembling and furnace soldering. Tooling plays a fundamental role in this process.
The design of punch and die plate, blanking speed, and the punch to metal thickness
ratio should be carefully considered, Figure 17.
230 Jewelry Technology Forum
 Figure 17 - Components produced by blanking

Required characteristics: Hardness is an important parameter for blanking. Relatively

harder materials give better results, because bending of the sheet by the punch is
lower, the blanks do not tend to stack up in the die plate and the cut edge is more
regular. The optimum hardness is about 250 HV for a 14 ct white gold.

Machine made chain (5, 8). A large variety of chain shapes and sizes can be machine
made. A carat gold wire is fed to the machine which cuts and bends it to form the links
which are also linked together.
All operations giving the links the desired shape (flattering, winding, hammering) can
then be carried out. After degreasing, the chain is soldered, to join the link ends. A
solder powder is put on the joints and talc powder is used for separating link from link.
Soldering is carried out in a furnace.
Hammering, diamond cutting, cutting to length, soldering of end rings, finishing and
possibly gold or rhodium plating follow, Figure 18.

Figure 18 -Machine made solid chain

Required characteristics: Usual workability characteristics are required, in addition to

solderability and corrosion resistance, in the case of low caratage alloys. Usually a
hardening heat treatment is not required if solid material is used.
June 2005 231
Hand working. Also in this case wire or plate are the starting material. These are
chiselled, modelled, carved or hammered, according to handicraft experience and
tradition. The only requirement is a good workability of the alloy.

Enamelling. Enamelling is a technique for surface decoration that uses powders of

low melting vitreous oxides that are applied by hand and subsequently fired in a
furnace at 750°C. The main requirement for this technique is to use zinc-free gold
alloys, because zinc hinders the adhesion of the vitreous oxides to the surface of the
metal. Experience shows that the thermal expansion coefficient of gold alloys is
usually compatible with the thermal expansion of the enamels, so there is little risk of
enamel spalling when the pieces cool after firing.

Elastic alloys. Also in the case of jewellery there are parts which are submitted to
stronger mechanical stress as, for example, clasps and catches of necklaces and
bracelets. A quite strong gold alloy with a wide elastic range is required for this use.
The suitable gold alloy should be heat treatable, to obtain a microstructure
compatible with high stress in the elastic range, and should have fine grain size and
controlled impurity content, Figure 19.

Figure 19 - Clasps and catches are examples of findings requiring high strength

Specific requirements for different production

technologies

An outline of the specific requirements for different types of mechanical working is

shown in the Tables 1 and 2.
Mechanical, thermal, micro-structural and chemical characteristics of the suitable
alloys are indicated for each processing technique.

232 Jewelry Technology Forum

 Table 1 - Required mechanical characteristics of the alloys
Hardness
Ultimate
Proof Elongation Age
tensile Plastic range Work
stress to rupture After hardening
strength of the material hardening
YS E% annealing ability
UTS ability

Medium Medium Very

Tube High Medium High Low
to low to low important

Hollow chain - Medium

High Low High High Low Important
“Aggraffato” to low

Acceptable
even if Very
Cladding High Medium Medium Medium Medium
medium important
to high

Medium Medium High - High Medium Not very

Stampato High Low
to high to low drawability to low important

Used as
Medium Not very
Blanking Low High Low Low work
to high important
hardened

Machine Medium Medium Not very

Low Medium to high High Low
made chain to high to low used

Not very
Hand working High Low High Medium Low Low
used

Medium Medium to Very

Elastic alloys High High Low Low
to low low important

The data on workability and mechanical properties as ultimate tensile stress, proof
stress and elongation to rupture have been obtained from the tensile test curve. This
set of data can give an evaluation of the amount of cold plastic deformation the
material can tolerate during processing.

Moreover an evaluation is given of work hardening ability and of the hardness in the
annealed state. Also an indication of the possibility of a hardening heat treatment is
given. In the case of stamping a hardening heat treatment is required only if the
thickness of the piece is lower than 0.12 mm. In the case of machine made chain a
hardening heat treatment is required only for some special design (snake or super-
flex chain) or when very thin wire is used.

A low rate of work hardening enables to make a larger number of reduction passes
before annealing is required. This increases productivity.

Processing techniques involving very strong reductions of section, like “aggraffato” and
tube production, need alloys with the best deformability and ductility, to prevent the
occurrence of problems like cracks and defects. A reduced plasticity range is preferable
for processing techniques requiring more rigid alloys, as is the case of blanking.
June 2005 233
 Table 2 - Required metallurgical characteristics of the alloys
Characteristics
T° T° Melting
Grain size Corrosion resistance of the solder
Liquidus Solidus range
Melting range T° Solidus
Tube Very fine Very important Medium Medium Medium Medium Medium
Hollow chain -
Fine Very important High High Narrow Wide Low
“Aggraffato”
Cladding Very fine Very important High Low Wide Wide Low

Important for low

Stampato Fine High Low Wide Wide Low
caratage alloys
Important for low
Blanking Medium High Low Wide Wide Low
caratage alloys
Machine Important for low Medium Medium
Medium Narrow Narrow Medium
made chain caratage alloys to high to high

Hand working Medium Not very important Medium Medium Medium Medium Medium
Medium Medium
Elastic alloys Fine Important Narrow Narrow Medium
to high to high

Table 2 highlights some more characteristics, like melting range. These

characteristics affect the behaviour of the alloy at high temperature. For example, in
the case of cladding a wide melting range helps to keep some strength of the alloy
when it is kept under pressure at high temperature. Also solderability and the correct
matching between the alloy and the solder are very important. It should be
emphasized that the thickness of the pieces to be soldered is very important for the
correct selection of the solder. Very low temperature melting solders are needed for
very thin materials, to avoid deformation of the pieces during furnace soldering.
Grain size is another important parameter for the processes where heavy deformation
is required, but it is less important when thicker materials are used, as for solid chain
machine making. Corrosion resistance is very important for all processing techniques
requiring chemical dissolution of the core metal. Moreover corrosion resistance
should be guaranteed during the lifetime of jewellery pieces. Low caratage alloys are
more problematic under this aspect than higher caratage alloys (18 ct or higher),
where higher fineness guarantees excellent resistance to corrosion.

Statistical analysis

An analysis of the data contained in our database on gold alloys as a function of alloy
composition and related effects on alloy properties has been the subsequent step for the
definition of the most important parameters for each type of mechanical working.
A multivariated statistical analysis has been carried out (the Modde software from
Umetrics has been used, Figure 20) on 150 characterised alloys, which have been
subdivided into six different classes, according to the different caratage (9, 14 and 18 ct)
and colour (white or yellow). All alloys from red to yellow-green have been included in
the “yellow” class. Palladium white golds have been excluded from white alloys.
Normalising coefficients were used for the concentration of the different alloying
elements, to allow a comparison of the effects of the addition of different amounts of
234 Jewelry Technology Forum
different alloying element. The effect of the addition of specific alloying elements on the
following parameters has been analysed:

• Colour coordinates (CIELAB a, b, L). The CIELAB colour coordinates are

referred to the CIELAB colour space, that enables us to evaluate the colour of an
alloy (with a well defined surface finishing) with a three-dimensional vector, whose
components are:
• a: positive a colour tends to red; negative a colour tends to green;
• b: positive b colour tends to yellow; negative b colour tends to blue;
• L: brightness.
• Solidus and liquidus temperatures, with indication of the (melting range).
• Tensile properties. Ultimate tensile strength (UTS), proof stress (YS) and percent
elongation to rupture (E%) have been taken into account. In addition the ratios L1
and L2 have been considered, where:
• L1 = (UTS - YS)/E gives an evaluation of the range of plastic behaviour of the
alloy, compared to elongation to rupture, (For example, for the same value of
UTS-YS, a more ductile alloy shows higher elongation, and a lower value of L1).
• L2 = (UTS-YS)/UTS , gives an evaluation of the range of plastic behaviour of
the alloy, compared to the ultimate tensile stress. (For example, for the same
value UTS-YS, the material with lower UTS shows better workability, and a
higher value of L2.
• Hardness. Hardness has been considered in the following conditions:
• HVac: as cast hardness;
• HV70%: hardness after 70% cold drawing reduction of section;
• HVann: hardness after annealing at 650°C for 30 min and fast cooling;
• HVhard: hardness after hardening heat treatment at the most convenient
temperature for two hours.
• Grain size. The used evaluation of grain size is the average of the measurement
of two diagonals of ten grains, obtained from the micrograph of a cross section of
as cast samples.

Figure 20 - Graphical representation of the multivariated analysis carried out with

Modde from Umetrics on 14 ct yellow alloys.
The effect on the different parameters is shown for each alloying element
June 2005 235
The data shown in the Tables 3 and 4 use the following codes:
“+++”: strong increase “-”: low decrease
“++”: medium increase “--”: medium decrease
“+”: low increase “---”: strong decrease
Hollow cells
Hollow cells denote
denote no
no appreciable
appreciable effect.
effect.

Table 3 - White gold alloys

cf Ag Cu Ni Zn Ir Ru Si
CIELAB a 9 - +++ - --
14 ++ - --
18 -- + + -
CIELAB b 9 ++ --- +
14 ++ ---
18 ++ --
CIELAB L 9 ++ -- +
14 + --
18 n.r.
Liq. Temp. 9 --- +++ -
14 -- ++ -
18 - ++ - ++
Sol. Temp. 9 -- +++ ---
14 --- + ++ -
18 -- ++ -- ++
Range 9 +++ --
14 + -- ++ --
18 ++ ++ -
UTS 9 - ++ ++
14 - ++ - + ++
18 --- + ++ + +
YS 9 - + - ++
14 ++ -
18 -- + ++ +
E% 9 - ++ ---
14 n.r.
18 - + - ++ -
HV ac 9 ++ - --- ++
14 + - ++ --
18 + -- + ++
Hv 70% 9 n.r.
14 -- ++ - ++ ++
18 +++ - + --- ++
Hv ann 9 - -- + ++
14 ++ -- --
18 -- + +
HV hard. 9 -- ++ - +++
14 ++ --
18 ++ - + -- ++
L1 9 +++ - +
14 - +++ - --
18 - ++ +
L2 9 + ---
14 -- + -
18 -- + - ++
Grain 9 -- --- +
14 -- -- ++
18 -- -- +++

Comments: copper causes a clear shift of the colour towards red and yellow, opposed
to nickel which has a marked effect on the b coordinate. Copper and nickel show a
strong effect on the increase of melting temperature, opposed to the effect to silver.
Zinc, like silver, increases the melting range by decreasing the solidus temperature. As
far as mechanical properties are considered, the hardening effect of silver and ruthenium
236 Jewelry Technology Forum
in the as cast material has been evidenced along with the stiffening effect of silicon. Also
the addition of nickel causes an increase of hardness, particularly in 14 ct alloys.
Zinc additions lower the hardness in the as cast and in the annealed material, and
increases UTS and YS. The most important increase of UTS and YS after heat treatment
is given by a combination of silicon and copper.
Silver increases hardness and YS, particularly in high caratage alloys. For low caratage
alloys, L1 shows the toughening effect of nickel and L2 the embrittling effect of silicon.
Moreover it can be seen that iridium and ruthenium cause some more interesting effects
in addition to grain refining. Silicon affects the UTS and causes a coarsening of the grain
size. Table 4 shows the results of the analysis on yellow gold alloys: only yellow alloys for
mechanical working have been considered.

Table 4 - Yellow gold alloys

ct Ag Cu Zn Co Ir Sn Si Ge
CIELAB a 9 ++ -- +
14 - ++ --- +
18 --- +++ -- ---
CIELAB b 9 - +++ - -
14 + --- ++ -
18 +++ --- + - +++
CIELAB L 9 + -- + +
14 + -- +++ -
18 + -- ++ + +
Temp. Liq 9 -- ++ -
14 --- +++ -- +
18 --- ++ +++
Temp. Sol 9 -- ++
14 --- +++ --
18 --- + ++ --
Range 9 ++ - +
14 ++ -- +
18 - + + ++ +++
Rm 9 ++ -- ++ +
14 + -- +++ -- +
18 - + - ++ + - -
Rp 9 +++ -- +++ ++
14 + -- +++ - +
18 -- ++ + - --
A% 9 -- +++ --- --
14 ++ --- ++ --
18 ++ --- -- --
HV ac 9 +++ - -- -
14 ++ - -- +
18 -- ++ - --
Hv 70% 9 + -- --
14 + - + -- +
18 -- ++ - + --
Hv ann 9 ++ -- +++ +
14 + -- +++ - ++
18 -- ++ - - --
HV hard. 9 +++ - - +
14 +++ - -- + ++ +
18 --- +++ -- ---
L1 9 + -- +++ ++
14 -- ++ +++ - +
18 -- +++ ++ ++ ++
L2 9 --- + ++ -- -
14 --- + ++ -- -
18 ++ -- ++ + ++
Grain 9 -- -- ++ +
14 -- + + --- +++ -
18 -- + ++
June 2005 237
Comments: The colour of the alloys is mainly affected by elements like zinc, copper
and, particularly for high caratage alloys, silver. Copper increases melting
temperature in low caratage alloys and it is the most important alloying element for
obtaining a good age hardening effect in high caratage alloys.
Silver tends to widen the melting range and to increase alloy strength (not the
elongation). It has a strong effect on age hardening of low caratage alloys. Copper
and silver show a contrasting effect on hardness in 18 ct alloys.
Zinc lowers hardness, tensile strength and proof stress, but increases elongation to
rupture.
The effect of cobalt (not present in white golds) on mechanical properties is to increase
tensile strength and proof stress and to decrease elongation to rupture. In the case of
hardness, the most evident effect is an hardness increase of the annealed alloys.
Tin increases ductility of 14 ct golds (increased elongation to rupture). In 18 ct alloys
tin widens the melting range and decreases elongation and proof stress.
Germanium lowers solidus temperature (it widens the melting range) of 18 ct golds,
while silicon increases grain size and proof stress, and decreases elongation and
hardness after 70% cold reduction in low and medium caratage alloys.
Iridium acts as a grain refiner in alloys of all caratages.

Overview of technical specifications for the alloys for

the different processing techniques

In this final part of our work we will define the numerical values of the ranges for the best
mechanical, thermal and plastic characteristics for each production process. These
data have been obtained from the multivariated analysis and from our records on alloy
characterisation. The results obtained for 14 ct yellow golds are shown in table 5.

Notes on measurement units: Ultimate tensile strength (UTS) and proof stress (YS) are
given as MPa (N/mm2). Hardness values are given as Vickers hardness number (HV).
Grain size is given in µm (10-6 m). Temperatures are given as centigrade degrees.

Table 5 - Mechanical characteristics required for different uses.

14 ct yellow gold alloys
14 ct L1 L2 HV HV HV Grain Liq. Sol. Melt.
UTS YS E%
Yellow Hard. Ann. Aged size Temp. Temp. Range
Tube > 530 300-400 High High 22-30 < 270 160-180 > 230 < 50 840-870 810-830 35-45
Hollow
450-500 220-250 High High > 36 < 250 < 150 > 200 < 200 890-930 850-900 25-40
chain
Cladding 450-500 240-280 Medium Medium 30-40 < 280 < 165 > 220 < 100 870-910 800-830 > 50
Not very
Stampato 400-450 210-240 High High > 42 > 260 < 140 < 200 870-900 810-840 > 45
important
Blanking
Not very
Blanking < 430 > 300 Low Low < 28 > 260 of work < 300 870-900 810-840 > 45
important
hardened
Machine Medium Medium 230- Not very
420-490 < 240 > 42 < 140 < 300 870-920 840-890 25-40
chain to high to high 260 used
Elastic
> 500 > 370 Low Low < 26 < 270 < 180 > 230 < 100 870-920 840-890 25-40
alloys
238 Jewelry Technology Forum
Conclusions

In this study a survey has been performed on the possibility of finding a clear
connection between processing needs and optimum composition of an alloy.
Another aim of this work is to find if and how precise parameter values could be
defined for a mechanical working process (obviously the most important process
parameters should be identified previously), to make process results consistently
optimised, thanks to the definition of the most suitable alloys. The selection of the
most suitable alloy enables the producer to reduce the number of process parameter
he must select. In the same time alloy performance can be optimised for each
specific process, thanks to the consistent behaviour of the material.
Another specific aim was to evaluate how much professional experience in alloy
selection could be assisted by the data obtainable from laboratory alloy characterisation.
Statistical analyses carried out on the basis of our records of characterisation data gave
generally reliable information, in agreement with practical experience. It has been found
that it is necessary to characterise a medium to high number of alloys (about twenty at
least, with different colour and fineness) for having reliable data. For this reason a study
of this type can also be considered as a control to be periodically repeated, because
new data are entered in the characterisation database. A deep knowledge of production
processes and of the composition of used alloys have still fundamental importance for
the interpretation and critical evaluation of the data.
A road has been traced. Now we can begin to consider precise parameters for the
selection and optimisation of an alloy for a specific production process. This is a first step
to substitute objective and comparable data for “sometimes objective impressions”.

References

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Spring 2002.
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5. AA.VV., Precious metals: Science and technology International Precious Metals Institute, 1991.
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June 2005 239