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Niello Manning - Chris

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Niello for the Modern Jeweler

Christopher M. Manning
Owner
Silver Hand Studios
Ottawa, Ontario, Canada

Introduction
Niello was an important alloy used by metalsmiths from ancient times until the
end of the Renaissance. The low-temperature metal sulfide was commonly used
as a high-contrast, fusion inlay alloy. The color permeates the alloy and ranges
from dark grey to deep black. It is an excellent choice when making high-wear
items where patinas and other surface treatments will wear. It was regularly fused
into bronze, iron, silver and gold.
My first introduction to niello came from Cellini’s Treatise on Goldsmithing and
Sculpture.1 Since first experimenting with niello six years ago, it has become an
important material in my art.
Niello was an important alloy in Renaissance Italy and commanded the first
chapter in Cellini’s Treatise. While the Renaissance was the pinnacle of niello
production, its use in decorative metalwork spans from the ancient Egyptians
and Romans up to modern-day Russian and Thai jewelers. The Fuller Brooch,
located in the British Museum, is one of the finest surviving examples of niello
work (Figure 1).

Manning

Figure 1 Late 9th century Anglo-Saxon brooch made of silver and niello

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In my 2017 Santa Fe Symposium® paper, “Niello: An Introduction to an Ancient
Material for the Modern Jeweler,”2 I explored some of the most common historical
recipes for making niello. While many of the traditional recipes have withstood the
test of time, there are significant toxicity and contamination issues associated with
their use. Most traditional recipes include lead to lower the melting temperature
of the alloy. This paper explores practical substitutes for lead-bearing niello in
order to reduce the health risks for artisans as well as consumers.

Traditional Niello
Various forms of niello have been used in decorative metalwork for thousands of
years. Early recipes used silver and copper alloys and were applied primarily to
bronze. The early lead-free alloys are difficult to work with. They were primarily
silver and copper, which require high melting temperatures for application. The
high temperatures can cause the sulfides to break down and can also come close
to the melting temperature of the metal into which the niello is being inlaid. By the
early Middle Ages, lead was added to the silver/copper alloy to lower the melting
temperature. Niello’s use on bronze decreased, while its use on silver, gold and
iron increased. A number of early niello recipes have survived, including recipes
by Pliny the Elder, Benvenuto Cellini and Theophilus. Despite tin being a well-
known metal earlier than lead-based niello, there is no evidence that tin was used
as an alternative to lead.
While niello recipes have varied dramatically in their proportions, the principle
ingredients have not changed. Unfortunately, the lead content in traditional niello
makes it dangerous for both the artist and the consumer. Modern consumer
protection laws in many countries prohibit lead in jewelry, which makes
traditional niello recipes inappropriate for this purpose. Lead also presents a
significant long-term health hazard to artisans who prepare and use niello, and it
is also a contamination hazard in the shop. A modern alloy of niello is needed for
it to be used safely in the modern shop.

Materials Used in Niello


Manning

Traditionally, there are four elements used in making niello: silver, copper,
lead and sulfur. Increasing the silver content raises the value of the niello,
lowers the melting temperature by a small amount, and lightens the color.
Increasing the copper content raises the melting temperature and makes the niello
blacker. Increasing the lead content significantly lowers the melting temperature.
Introducing sulfur to the molten alloy converts it into a metal sulfide, causing it
to turn black.
Reducing the melting temperature of niello is crucial. Without reducing the
melting temperature of a silver/copper-only alloy, it becomes challenging to
apply and the sulfides begin to break down.
In an attempt to find a replacement for lead, I examined other elements
surrounding it on the periodic table for their suitability. The primary criteria for

Niello for the Modern Jeweler


346
selection were these three: low melting temperature, boiling temperature above
the melting temperature of the silver/copper alloy and low toxicity.

Gallium
Gallium (Ga) is number 31 on the periodic table. It appears between zinc and
germanium, aluminum and indium. It has a melting temperature of 30ºC (86ºF),
and a boiling temperature of 2400ºC (4352ºF). Gallium is non-toxic. It is liquid near
room temperature, which can make it difficult to measure and handle. Gallium
is relatively easy to obtain and has a higher cost relative to the other alternative
metals.

Indium
Indium (In) is number 49 on the periodic table. It appears between cadmium
and tin, gallium and thallium. It has a melting temperature of 156ºC (313ºF) and
a boiling temperature of 2072ºC (3762ºF). Indium is mildly toxic if injected into
the blood stream. It is not absorbed through the skin and is not well absorbed
by ingestion or inhalation. It is a very ductile metal, which makes it very easy to
work with in the shop. It can be easily cut with a knife or scissors. Indium is easy
to obtain and has a higher cost relative to the other alternative metals.

Tin
Tin (Sn) is number 50 on the periodic table. It appears between indium and
antimony, germanium and lead. It has a melting temperature of 232ºC (450ºF) and
a boiling temperature of 2602ºC (4716ºF). Tin does not represent a health risk. It
is very ductile and when purchased as sheet, it is easy to cut with scissors. Tin is
very easy to obtain and is relatively inexpensive.

Lead
Lead (Pb) is number 82 on the periodic table. It appears between thallium and
bismuth, tin and flerovium. It has a melting temperature of 327ºC (621ºF) and a
boiling temperature of 1749ºC (3180ºF). Lead does represent a long-term health
risk. The primary risk of exposure is through inhalation and ingestion. Exposure
is gradual and symptoms are often not obvious until a significant build-up occurs.
Manning

Because of the dangers of lead exposure, a replacement is needed.

Bismuth
Bismuth (Bi) is number 83 on the periodic table. It appears between lead and
polonium, antimony and moscovium. It has a melting temperature of 271ºC
(520ºF) and a boiling temperature of 1564ºC (2847ºF). Bismuth has low toxicity and
because it shares many physical properties with lead, it has become a common
replacement for lead. Bismuth is used in some cosmetics and medicine, and it
does not present a significant risk for use in the studio. It is often found in a crystal
form and is very brittle. It is easiest to smash into smaller pieces when measuring.
Bismuth is easy to obtain and relatively inexpensive.

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Experiments and Results
During the experiments with leaded niello recipes for last year’s Santa Fe
Symposium® paper,2 I found that the “Modern French” recipe gave the best
results. It provided the best combination of black color, melting temperature and
flow. The recipe, Ag:Cu:Pb 3:7:5, provided a starting point for experimenting
with the new metals. I prepared and tested 20-gram samples of each for melting
temperature, color and ease of application. I cast the silver sample disks, then
sanded to 600-grit prior to applying the niello. I sanded the gallium-, indium- and
bismuth-based samples to 400-grit, and I sanded and polished the lead- and tin-
based samples as I would for a finished piece.
I quickly discounted the gallium-based niello as a possible replacement (top right
in Figure 2). Despite repeated applications of sulfur to the molten alloy, it would
not turn black. It appears as though the gallium resists turning into a sulfide. The
resultant alloy is slightly more grey than silver, but not enough to provide a useful
contrast to the silver. I did not conduct any further experiments with gallium.

Figure 2 Experimental results of making niello with (clockwise from top left) tin,
Manning

gallium, indium, bismuth and lead (center) as the third element in the recipe. The
bismuth sample is from the first experiment. All others are from the second.

The three remaining alloys (indium, bismuth and tin) had very high melting
temperatures. All were high enough to be unviable as niello. The indium-based
alloy had a melting temperature above 650ºC (1202ºF). The bismuth and tin-based
alloys had melting temperatures above 530ºC (986ºF). Based on past experience
with niello, I find that temperatures above 430ºC (806ºF) during application are
problematic. Above that temperature, the sulfides begin to break down in lead-
based niello, and the silver will usually precipitate out. The precipitated silver
forms small crystals that look like snowflakes and, in more extreme examples,

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348
large areas turn silver. The bismuth- and tin-based alloys held up to the higher
temperatures during a single application; however, there were flow issues during
application. Since multiple applications are often required, the chance of damage
on subsequent applications is high. The indium-based niello required enough
heat to cause the sulfides to begin breaking down during the first application.
During the next set of experiments, I changed the initial approach for the recipe.
In order to start with as low a temperature as possible, I created a near-eutectic
silver/copper alloy with a ratio of Ag:Cu 7:3. Adding five parts of the third metal
allowed for dramatic reductions in temperature compared to the initial recipes.
based on the Modern French recipe.
The tin-based recipe flowed at roughly 230ºC (446ºF). Once flowing, it filled both
large areas and small details nicely. The color after application is a good dark
grey. The tin-based sample is top left in Figure 2. A common problem with this
formula is the precipitation of silver from the alloy. The effect is exaggerated
by the photograph and is not visible at arms’ length. When compared to the
lead-based niello, this recipe is not as dark, primarily due to the silver crystals
that formed on the surface. Without a direct comparison, it would be difficult to
distinguish this niello from many lead-based ones.
The bismuth-based recipe flowed at roughly 200ºC (392ºF). This recipe is the
closest to the lead-based niello with regard to flow and fill qualities. The alloy
does not have a consistent color after application (bottom left in Figure 2) and the
surface shows evidence of damage from over-heating. It appears as though the
silver is precipitating out in larger amounts than from the tin-based alloy. The
black areas are a bit darker than the tin-based alloy.
The indium-based niello requires a higher temperature than the other recipes,
roughly 350ºC (662ºF), to begin melting. It does not flow well until heated over
500ºC (932ºF). As a result, there is a risk of sulfides breaking down with this
recipe. In addition to the high temperature required, the alloy is not consistent
in color. Large areas are affected by silver precipitating from the alloy (in Figure
2 the indium-based sample is bottom right). Due to the melting temperature
being higher than is safe for the sulfides, I don’t believe it is worth experimenting
further with an indium-based recipe.
Manning

For comparison, a fifth sample was made using the Modern French lead-based
recipe (center sample in Figure 2). This niello flowed comfortably at 175ºC (347ºF).
It is very easy to apply and flows well. It is a nice black color and, due to the low
melting temperature, overheating (and the associated damage to the sulfides or
silver precipitation) is unlikely.

Safety
The recipes presented in this paper were selected with the intention of reducing
the long-term health risks to the artist using them. While the elimination of
lead from the alloy has removed the most significant health risk, there are still
important steps required to work safely with niello.

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During the preparation of niello, all normal precautions should be taken while
working with torches, high heat and molten metal. The most important safety
consideration compared to normal alloying procedures is the sulfur dioxide
produced from burning sulfur in air. Sulfur dioxide readily reacts with the
moisture in mucous membranes and forms sulfurous acid, a severe irritant. Mild
exposure will result in airway restriction, coughing, sneezing and eye irritation.
Higher exposure will result in bronchospasms, resulting in an obstructed airway
and severe eye irritation.
Sulfur dioxide is heavier than air and will pool in low-lying areas of the shop.
Good ventilation is important while preparing niello. If adequate ventilation
is not possible in the studio, preparation outside is encouraged. Along with
adequate ventilation, a full-face respirator should be worn during preparation.
For information on how to build an effective fume hood for preparing niello, see
Whit Slemmons' excellent article/tutorial entitled, "Studio Ventilation Tutorial."3
Care should also be taken when filing, sanding and polishing niello. Dust can
present a health risk regardless of the toxicity of the metals. The dust and particles
from niello can also contaminate other work. Pitting can occur during high-
temperature operations such as soldering with pieces contaminated by niello
particles. Care should be taken to avoid cross contamination with other work.

Preparation
All recipes are prepared essentially the same way, requiring similar equipment
and precautions. The silver and copper are first alloyed together. The third metal
is added and allowed to mix. The molten alloy is then poured into the sulfur. At
that point the niello can be cast into a rod for easy use.
Below is a list of the tools and materials required to perform the above experiments.

• Full mask respirator • Scale


• P100 filter for respirator • Torch
• Two crucibles • Steel angle iron
• Graphite stir rod • Mortar and pestle
Manning

• Fume hood • Wire mold


• Sulfur • Borax
• Copper • Steel spoon
• Silver • Ingot mold
• Tin, galium, indium or • Steel bowl with water
bismuth

A good fume hood is an absolute requirement for making niello in a shop. The
hood must exhaust out of the room, and care must be taken when selecting where
the exhaust exits the structure. Be sure to test the draw of your fume hood before
you start burning sulfur because the fumes from this process will contain large

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350
amounts of sulfur dioxide. Niello can also be made outdoors, as long as there
is a reasonable breeze to carry away the fumes (be sure to prepare away from
bystanders who are unaware and/or unprotected).
No matter where it is made, everyone in the studio or area must wear an
appropriate full-face respirator. A half-face respirator is inadequate for this
work as it will not protect the eyes from the sulfur dioxide. The respirator must
fit properly and should be fitted with a P100 cartridge. If you are unsure about
the respirator or cartridge you currently have, consult with a reputable safety
equipment supply house. They will be able to provide you with the correct
products to protect against lead and sulfur dioxide.
Wear clothes you are willing to discard. The smell of burning sulfur is invasive,
and you should be willing to throw out the clothes you are wearing. Be aware
of the dust created when filing, sanding, and polishing niello, as it can also
contaminate clothing. The dust can cause issues with other work in the shop.

Manning

Figure 3 The raw materials required for this experiment

The sulfur must be in a powdered form. It is unnecessary to use chemically


pure sulfur. Garden centers are a good source of sulfur, which is sold as a slug
deterrent and is typically 92% pure. Despite some historical sources that discuss
specific quantities of sulfur, it is difficult to recommend an exact amount. The goal
is to saturate the alloy with sulfur. More sulfur is better, and with experience you
will get a sense of how much to work with at a time.

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The silver should be pure or contain nothing except copper. If it is an alloy such
as sterling or coin silver with a known amount of copper, take into account the
copper content when weighing all the metals. The silver should be cut into small
pieces or used in grain form to help it melt rapidly.
The copper should be pure. Unused copper plumbing tube is a reasonable source.
Even though it often contains a very small amount of deoxidizer, I have found
that it does not affect the quality of the niello produced. However, do not use
pipe taken from an existing plumbing installation as it may be contaminated with
solder. Electrical wire can also be used; however, removing the insulation can be
tedious. As with the silver, it should be cut into small pieces or used in grain form.
Pure tin can be purchased in several forms. Sheet tin is the easiest to use—a 1-mm
thick sheet can be cut easily with scissors.
Preparation is important. Before starting, lay out everything you need so it is
easily at hand. Weigh all metals and keep them separate. Making 20 grams of
niello at a time is reasonable. Disposable paper cups are useful to keep each of the
metals sorted.
Prepare the two crucibles by coating them in borax and firing them. The crucible
used for alloying the metals should be pre-heated before adding any metals. The
crucible with the sulfur should not be pre-heated. Fill the sulfur crucible with a
spoonful of sulfur.
The steel angle iron should be a few feet long and tilted at a slight angle. You will
be pouring the molten niello into it and making a long rod of niello. It should be
readily accessible and stable while handling the torch and the crucible of molten
niello. Prepare the angle iron by coating it with a thin layer of oil and burning it
off to create a layer of soot. There is no need to heat the angle iron prior to pouring
the rod.
Once everything is laid out and ready, begin by melting the silver with a reducing
flame. When the silver is liquid, slowly add the copper. Stir the alloy as necessary
to ensure that everything has melted and mixed. When the silver/copper alloy is
liquid, slowly add the third metal. It is important to ensure that the third metal
has melted and successfully alloyed with the existing metal before pouring it
into the sulfur. Roll the molten metal in the crucible to ensure it is all molten and
Manning

consistent. Temperature is important from this point on, as high temperatures can
damage the sulfides you will create in the next step. Overheating the niello can
also cause the silver to precipitate from the alloy.
When you are satisfied the alloy has mixed, pour it into the crucible with the
sulfur. Stir the mixture and add heat occasionally until all of the sulfur has been
absorbed or burned off. Apply short bursts of heat from the torch to keep the
niello molten. While allowing the sulfur to burn off, there may be a small amount
of cinder on the molten niello. Do not heat the mixture to the point where the
cinder is absorbed into the niello. Instead, remove the cinder with the graphite
rod. Once the sulfur is absorbed or burned off, slowly pour it into the angle iron
to form a long, irregular rod. The rod should be consistent in color throughout
and should be brittle. If there is a silver core in the rod, you have overheated the

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352
niello or did not add enough sulfur. It is impossible for the niello to absorb too
much sulfur. Melt the rod and pour it into another crucible of sulfur. Pour a new
rod in the angle iron and check it for consistency.
When you are satisfied with the niello, make it into either rods or powder. If you
want to use niello as a powder, melt it and pour it into a bowl of water. Remove
the niello from the water, then grind it in a mortar and pestle. Once ground, it
should not be stored for long periods of time. A simple wire mold works well for
making niello rods for either immediate or later use. Be careful not to overheat the
niello when casting into rods or ingots.

Application
Using niello in a piece needs some planning and requires preparation similar to
using enamel. All soldering operations must be complete before applying niello.
At soldering temperatures, the niello will flow again and the high temperature
will cause damage to the sulfides. Niello will also cause significant pitting in silver
and gold at soldering temperatures. Even extra easy solder requires too high a
temperature for use with niello that has already been applied to a piece. Laser or
fusion welding is required to repair a piece after the niello has been applied. All
stone setting should wait until after the niello has been applied and finished.
A basic finish should be completed prior to application. I recommend finishing
with at least 400-grit sandpaper before. It is best if the area where niello is being
applied is flat, or convex, and is easily accessible with files and sanding sticks.
All forming should be complete before applying the niello. Do not apply to a flat
piece of metal and then try to form it.

Manning

Figure 4 Sample disks cast in Argentium® silver


and prepared with sandpaper up to 400-grit

Niello is opaque once it is more than 0.05 mm thick. It can be applied into deep or
shallow pockets or engravings. Be cautious about using very shallow depressions,
as it is easy to damage the surrounding piece when sanding and possibly destroy
the pattern in the process. I recommend making depressions 0.5 mm deep.

May 2018 353


If a flux is required to protect the base piece, use a mixture of alcohol and boric
acid. Apply the mixture to the work before applying the niello. Heat the piece until
the flux has become liquid. The work is now hotter than the melting temperature
of the niello. It can be fed by rod through the flux, displacing it. Depending on
the size of the piece, it may be necessary to apply heat to the piece to keep it hot
enough to melt the niello. Avoid applying heat directly to the niello.
If flux is not required to protect the base piece, apply heat to the base piece and
allow it to melt the niello. Once again, avoid applying heat directly to the niello.
If using niello as a powder, apply it as you would enamel. Over-pack the area to
be filled with powdered niello. The piece can either be torch fired or heated in a
kiln. Follow the same steps as above when torch firing. If using a kiln to fire the
piece, pre-heat the kiln to 700ºC (1292ºF) and use a trivet to support the work. The
temperature of the kiln is high enough to damage the niello, so closely monitor the
niello to observe when it has melted and remove it once it has flowed. Be careful
when removing it as the niello is molten and can be spilled from the depression.
The niello may stay liquid for a few minutes. Place the piece on a flat surface to
prevent the niello from under filling one side and overfilling another side of the
piece.
Regardless of application method, always overfill the area with niello. There is
often damage to the top surface of niello, and overfilling will ensure it can be
filed and made level with the surrounding surface (Figure 5). If necessary, use a
solder pick to pull niello into all areas of the pattern and prevent air pockets. In
particular, pay attention to corners and areas of fine detail.
Manning

Figure 5 Sample Argentium® silver disks after the initial application of niello

When filed flat, a second application may be necessary to fill air pockets or areas
without enough niello to reach the same level as the base piece. Slowly heat the
piece and watch for the existing niello to melt. Use a solder pick to draw the niello
into any air pockets and apply a small amount of fresh niello to overfill the area.
Niello for the Modern Jeweler
354
With practice, most pieces can be filled in one or two applications. Be cautious
when reheating the piece. It is easy to become impatient and damage the niello
with too much heat.
Once applied, niello can be drilled, allowing mechanical fastening of stone
settings or other parts. I also commonly use Loctite® to secure parts together
where appropriate. Low- and medium-temperature Loctite will provide a semi-
permanent bond and can be released with heat below the temperature at which
niello will melt.

Finishing
Because niello is a metal alloy, many of the standard finishing techniques used in
jewelry will apply to pieces with niello. Files and sanding sticks should be used
to complete most of the finishing. Dedicated tools should be used for finishing.
All files, sanding sticks and polishing buffs will be contaminated with the low-
temperature niello. If they are used on another piece in the future and high
temperature is applied during soldering, pitting can occur from the fine niello
particles.
As much finishing as possible should be completed with progressively finer
sanding sticks. The niello is very soft compared to the surrounding gold or
silver. Avoid aggressive polishing to prevent undercutting the niello. Use
buffing compounds that are appropriate for the metal of the base piece. The most
aggressive buffing compounds should be avoided; instead, prepare the surface as
best as possible for final buffing using sanding sticks. After finishing, the niello
and base silver should be level, and then polished (Figure 6).

Manning

Figure 6 Taj Mahal pen by author in Argentium® silver and niello

May 2018 355


Conclusion
The purpose of these experiments was to explore alternatives to traditional lead-
bearing niello. Some of the alternatives are viable but they are certainly not perfect
replacements for historical recipes.
Tin is the most promising replacement for lead. It is not a perfect replacement,
primarily because it does not lower the melting temperature of the alloy as much
as lead. However, the results show that it is worthwhile to use a lead-free niello
as a replacement to traditional alloys.

Acknowledgements
I wish to thank Steven Strang and Rich Loen for their continued support and
friendship. They both help drive my curiosity and push me to become better at
what I do. Thanks to Jon Edwards for helping me share my thoughts on being
a maker, and asking me questions to help me understand what I do. Finally,
I would like to thank Eddie Bell and the Santa Fe Symposium® staff for their
interest in my work and for inviting me to present this paper.

References
1. C.R. Ashbee (translator), The Treatises of Benvenuto Cellini on Goldsmithing and
Sculpture (New York: Dover, 1964).
2. Christopher M Manning, “Niello: An Introduction to an Ancient Material
for the Modern Jeweler,” The Santa Fe Symposium on Jewelry Manufacturing
Technology 2017, ed. E. Bell et al. (Albuquerque: Met-Chem Research, Inc.,
2017).
3. Whit Slemmons, "Studio Ventilation Tutorial"; http://www.andreaguarino.
com/read-me/.
Manning

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