An introduction to the history of

metals conservation

The Metals Conservation Summer Institute May 27- June 7, 2006, Worcester, MA, USA
Valentin Boissonnas, HEAA Arc, La Chaux-de-Fonds, Switzerland
An introduction to the history of metals
conservation
 An introduction to the history of metals
conservation

1. Traditional techniques and materials

 An introduction to the history of metals
conservation

1. Traditional techniques and materials

2. The first conservation research centres
 An introduction to the history of metals
conservation

1. Traditional techniques and materials

2. The first conservation research centres
3. Chronological survey of concepts and techniques
 An introduction to the history of metals
conservation

1. Traditional techniques and materials

2. The first conservation research centres
3. Chronological survey of concepts and techniques
• Corrosion, patina, original surface
 An introduction to the history of metals
conservation

1. Traditional techniques and materials

2. The first conservation research centres
3. Chronological survey of concepts and techniques
• Corrosion, patina, original surface
• Conservation treatments of bronzes
 An introduction to the history of metals
conservation

1. Traditional techniques and materials

2. The first conservation research centres
3. Chronological survey of concepts and techniques
• Corrosion, patina, original surface
• Conservation treatments of bronzes
• Conservation treatments of iron
 Traditional techniques and materials

Traditional products and techniques used on metal artefacts aimed

at maintaining their function and preventing their deterioration
 Traditional techniques and materials

Traditional products and techniques used on metal artefacts aimed

at maintaining their function and preventing their deterioration

• Mechanical treatments: Riveting, soldering, polishing

• Chemical treatments: dissolution of corrosion products (vinegar,

lemon juice, oxalic acid, etc.)

• Protective coatings: prevention of atmospheric corrosion after

cleaning (paints, lacquers, resins, metallic coatings)
Traditional techniques and materials
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins

• Pliny, AD 75:
Iron can be protected from rust by means of cerussa (lead oxide), gypsum and vegetable
pitch. Bronze can be coated with turpentine and pitch.
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins

• Pliny, AD 75:
Iron can be protected from rust by means of cerussa (lead oxide), gypsum and vegetable
pitch. Bronze can be coated with turpentine and pitch.

• Theophilius, 12th century:

To protect iron, boil it in linseed oil and pitch
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins

• Pliny, AD 75:
Iron can be protected from rust by means of cerussa (lead oxide), gypsum and vegetable
pitch. Bronze can be coated with turpentine and pitch.

• Theophilius, 12th century:

To protect iron, boil it in linseed oil and pitch

• Cellini, 17th century:

First description of mechanical cleaning of archaeological bronzes with small chisels and
hammers
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins

• Pliny, AD 75:
Iron can be protected from rust by means of cerussa (lead oxide), gypsum and vegetable
pitch. Bronze can be coated with turpentine and pitch.

• Theophilius, 12th century:

To protect iron, boil it in linseed oil and pitch

• Cellini, 17th century:

First description of mechanical cleaning of archaeological bronzes with small chisels and
hammers

• Traditional recipe for knights armour, 1616:

Pour olive oil in a heavy mortar, stir it well with a pestle until it warms itself, put white lead
into it and rub it again until it becomes black. Pour a little oil of tartar into it and with Neat’s
foot oil or old fat make a salve. Smear armour with the salve.
 Traditional techniques and materials
• 1000 BC:
Egyptians use excellent varnishes, heated combinations of oils and natural resins

• Pliny, AD 75:
Iron can be protected from rust by means of cerussa (lead oxide), gypsum and vegetable
pitch. Bronze can be coated with turpentine and pitch.

• Theophilius, 12th century:

To protect iron, boil it in linseed oil and pitch

• Cellini, 17th century:

First description of mechanical cleaning of archaeological bronzes with small chisels and
hammers

• Traditional recipe for knights armour, 1616:

Pour olive oil in a heavy mortar, stir it well with a pestle until it warms itself, put white lead
into it and rub it again until it becomes black. Pour a little oil of tartar into it and with Neat’s
foot oil or old fat make a salve. Smear armour with the salve.

• Far East:
Lacquers are used well before the Christian area, mainly made from Rhus vernicifera
 The first major conservation research centres

Königliches Museum Berlin

inaugurated in 1888.

Otto Olhausen (1840-1922)

establishes the first scientific
conservation lab and hires
Friedrich Rathgen (1862-
1942) as assistant.
Rathgen soon becomes head
of the research department
and will stay there for 40 years
doing pioneering work.

‘Die Konservierung von

Alterthumsfunden’ (1898)
The first major conservation research centres

National Museum of Denmark

in Copehagen (1855)
Gustav Rosenberg (1878-
1941), heads the conservation
department.

‘Antiquités en fer et en
bronze. Leur transformation et
leur conservation’ (1917)

Works mainly with electrolytic

reduction techniques to stabilize
bronze and iron finds.
 The first major conservation research centres

The British Museum London

1920 the conservation research
department is opened by Dr.
Alexander Scott after many
objects were damaged because
of bad storage conditions during
the 1st World War.
‘The Cleaning and Restoration
of Museum Exhibits’ (first
report 1921, second 1923, third
1926)
 The first major conservation research centres

The British Museum London

1926 Harold Plenderleith is appointed
conservation-scientist and heads the
conservation & research department.

‘The Conservation of antiquities and

works of art’ (1956, 1971)
Robert Organ, a physicist, joins the
research lab in 1951 where he works for
14 years before heading for the Royal
Ontario Museum and later for the
Smithsonian Institution in Washington.
 The first major conservation research centres

Columbia University
Professor Colin Fink and his
assistant Charles Eldridge
are working at Columbia
University in the electro-
chemical department. They
publish in 1925 a manual on
the conservation of bronze
antiquities.

The Metropolitan Museum

of Art installs its first
conservation laboratories at
Columbia University following
the example of the British
Museum.
 The first major conservation research centres

Rutherford Gettens, chemist and

metallurgist, works at the Freer
Gallery of Art in Washington on the
technology of Chinese bronzes.

Fogg Art Museum in Harward

publishes ‘Technical Studies in
the Field of the Fine Arts’.

After the war museums scientists

will found in 1950 the International
Institute for Conservation (IIC).

‘Studies in Conservation’ first

appears in 1952
 The first major conservation research centres

France-Lanord (1915-1993)
A founding member of the Laboratoire
d’Archéologie des métaux de Nancy
in France.

Helps developing major concepts such

as the integrity of the object and the
location of the ‘primitive surface’ or
‘skin’.
1850-1900 Digging up problems

Schliemann

Milkau

Schliemann

Rathgen
1850-1900 Digging up problems
 1850-1900 Digging up problems
‘During the 1860's it was possible to "excavate" as many as sixty-six grave
barrows from an Iron Age graveyard in Ringerike, Norway, in ten days, amassing
thousands of iron objects in need of treatment once removed from the soil
(Hansen 2001).’
 1850-1900 Digging up problems

Corrosion:
Corrosion First interpretations are
rather confused. Some call only nicely
preserved green surfaces Edelrost or
Patina (Krause, Vanino / Seitter),
others accept a variety of colours, as
long as the surface is uniform and
smooth (Hausding).

Various attempts are made to

chemically describe the variations in
colour from green to blue to red with
the burial context and the composition
of the artefacts.

Boissonnas
 1850-1900 Digging up problems

Corrosion:
Corrosion Many bronzes are excavated from peat bogs and
preserve a metallic surface. Others, from lake dwellings, just have
calcareous deposits. The acceptance of metallic surfaces and the
application of stripping techniques might well have been influenced
by those early finds from Northern Europe.
 1850-1900 Digging up problems

Active Corrosion on copper alloys is first described

by Mond and Cuboni (1893) and then by Frazer and
Nicols in 1898. Bacteria discovered on such items
lead to the suspicion that they are responsible for this
‘bronze disease’.

Contaminated objects
are systematically
sterilized at 120-150°C.

Ellis & Hermanis

Boissonnas

Boissonnas
 1850-1900 Digging up problems

Cleaning of copper alloys :

The total removal of corrosion

products is considered
important by certain to regain
the aesthetically pleasing
metallic shine of the metal
(Bibra 1869).

Others are less convinced, as

many objects are first stripped
and then patinated to satisfy an Van Langh

esthetical look (Petrie 1888).

 1850-1900 Digging up problems

Mechanical Cleaning of copper alloys :

All traditional mechanical methods were in use, such

as wire brushes, abrasive papers, grinding tools,
hammers, heating and quenching. Fragments were
regularly soft soldered as no adhesives existed that
had the necessary strength to
hold load bearing metal pieces.

Animal glue (fish bladder) was

mostly used for smaller parts,
drilling and doweling were
standard operations.

Boissonnas
 1850-1900 Digging up problems

Electrochemical cleaning of copper alloys :

Finkener (1886) advocates electrolytic reduction in potassium

cyanide (Cyankalium) baths and stripping by hydrogen evolution
before thorough washing. Removal of all accessible core material!
After brushing with wire brush objects are coated with nitrocellulose
lacquer in order to ‘give back a metallic look’.

Rathgen
 1850-1900 Digging up problems

Electrochemical cleaning of copper alloys:

alloys

Axel Krefting (1883), suggests to remove all

corrosion layers, preventing further rusting.
Bronzes are stripped for 24h by immersion in
sodium hydroxide with zinc granules without
external electrical source.

Other obscure methods exist at the time, such as

dipping coins in liquid lead (Pb), followed by
quenching in cold water and leaving over night in
milk. Is supposed to give a beautiful olive
coloured patina.

Rathgen
 1850-1900 Digging up problems

Protective coatings for copper alloys:

alloys

Protective coatings are already used to protect,

consolidate, but also to improve the look of
bronzes. Mostly linseed oil, bees wax or
shellac.

The invention of cellulose nitrate coatings

(Celluloid or Zapon lacquers) is considered a
major step in improving surface coatings and is
immediately adopted by many conservators.

Paraffin wax will replace bees wax and

improve long term protection.
Ashmolean Museum Oxford
 1850-1900 Digging up problems

Cleaning & stabilization methods for iron:

iron

Peter Petersen (pre 1870): boiling in linseed oil and coating with
hot beeswax (later replaced with Copal varnish).

Axel Krefting (1883): electrolytic stripping techniques. Coating

with paraffin wax. Other coatings such as stearin, shellac, linseed
oil are frequently used.

Boissonnas
1900-1920 Towards a better understanding

Brittner Mallowan

Williams Brittner
 1900-1920 Towards a better understanding

Corrosion & mechanical cleaning of copper alloys:

alloys
1905 Corrosion that contains detail is defined by Rathgen as a
noble patina.
1917 Rosenberg is the first to talk of an original surface and
how it can be replaced by corrosion products. He also suggests
that it is possible to find it by mechanical means.

Rathgen
 1900-1920 Towards a better understanding

Mechanical cleaning of copper alloys:

alloys

An interesting method is
described by Springer
who coats bronzes with
hot and liquid animal
glue. While drying it
shrinks and pulls off
mostly external corrosion
products.

Born
 1900-1920 Towards a better understanding

Active Corrosion on copper alloys :

The debate about what influences the corrosion of copper

alloys continues. Sometimes even chlorides are attributed to
the good preservation of bronze surfaces!

It is Rathgen (1889), Krefting (1892) and then Petrie (1904)

who suggest that chlorides are the reason for actively corroding
bronzes. From then onwards chlorides are acknowledged by
most to be the source of active corrosion.

Conservation treatments now aim at removing chlorides

from objects in order to stabilize them. This has priority
over the growing concept of preserved information within
corrosion products.
 1900-1920 Towards a better understanding

Stabilization of
copper alloys :

Rosenberg advocates
a localized stabilization
method by using
aluminium foil and an
Agar Agar / Glycerol
electrolyte to electro-
chemically reduce
copper chlorides into
stable cuprite or
tenorite.

Rathgen
 1900-1920 Towards a better understanding

Stabilization of iron :

1904 William Flinders Petrie uses on-site washing of iron in

water, oven drying, waxing.

1905 Rathgen & Finkener propose boiling iron in molten

potassium cyanide.

1917 Rosenberg suggests heating iron up to 800 oC,

quenching in potassium carbonate. Subsequent boiling in
frequent changes of distilled water until no more chlorides.
Boiling in paraffin or microcrystalline wax.

Other impregnation methods use water glass, natural rubber,

dammar resin, linseed oil, and animal fats.
1920-1950 New concepts and old recipes

British Museum Carter

British Museum
Schorsch
 1920-1950 New concepts and old recipes

Corrosion:
Corrosion
Total removal of corrosion products is being seriously questioned
by Rathgen in his reedited book (1924) and Scott (1926), who now
considers a corroded surface far more important than a shiny
surface of bare metal.
With the introduction of the Rosenberg method there is an
alternative to stripping actively corroding bronzes.

However, the loss of such

surfaces observed with
some treatments is still
accepted in order to
stabilize objects.

Plenderleith
 1920-1950 New concepts and old recipes

Cleaning copper alloys:

alloys

Vigorous chemical cleaning methods are

still used such as electrochemical
cleaning, boiling in sodium phosphate,
Alkaline Rochelle salt and citric and
sulphuric acid.

Plenderleith

Born
 1920-1950 New concepts and old recipes

Stabilizing copper alloys

Scott (1921) suggests long immersion in sodium
sesquicarbonate, sometimes combined with
Alkaline Rochelle salt.

Nichols (British Museum 1924) uses localized

stabilization treatments such as silver nitrate
(later modified to silver oxide, then zinc powder).

Protective coatings
come from the automobile and aircraft industry.
Cellulose acetates and Perspex are replacing
traditional natural waxes.

Boissonnas
 1920-1950 New concepts and old recipes

Stabilizing iron:
iron

Scott (1921) suggests to use long soaking in sodium

sesquicarbonate. Dammar varnish as surface protection.

In 1933 he tries natural

rubber in solution and
advocates the use of
chlorinated rubber to
consolidate fragile
metals.
Soon abandoned, as
unstable and most
irreversible.

Boissonnas
 1920-1950 New concepts and old recipes

Stabilizing iron:
iron

For both bronzes and iron

finds the use of controlled
storage in sealed cases with
buffering materials (silica gel)
are beginning to be used after
Rathgens 1924 publication.
The use of nitrogen filled
storage containers are first
used for finds of the Sutton
Hoo treasure in 1946.

Rathgen
1950-Today
 1950-Today

Corrosion:
Corrosion

Increasing awareness of corrosion

crusts and the concept of original
surface.
surface For France-Lanord and
Eichhorn preservation of original
surface has priority over stabilization.

Organ

But only in 1990ies the original surface is

defined as the surface that represents the
object when abandoned.
abandoned Bertholon (2000)
defines the original surface more precisely
as limitos, that can be located with the help
of markers.
markers
Boissonnas
 1950-Today

Electrolytic treatments of copper alloys:

alloys

1956 Plenderleith still

recommends the use of
electrolytic reduction in
sodium hydroxide.

Most unfortunately this

harsh method is still
used today on some
excavations and in labs
that lack trained
personnel. Boissonnas
 1950-Today

Electrolytic treatments of copper alloys:

alloys

In the 70ies France-Lanord proposes electrolytic reduction with

low current.
current Increases removal of chlorides without stripping
corrosion products. EDF pushes technique further for treating
marine bronzes under cathodic protection in sodium
sesquicarbonate.
This treatment has been adapted as standard treatment for marine
bronzes. The measurement of the corrosion potential of the object
with a reference electrode allows a precise and controlled
reduction of only un-
wanted corrosion
products (chlorides).

Pennec
 1950-Today

Electrolytic treatments of lead and silver alloys:

alloys

Consolidative reduction of very

corroded lead also uses a low current,
preventing hydrogen bubbling and
reducing acidifies corrosion products to
metallic lead.
In the 90ies potentiostatic reduction
helps refining this technique.

After 2nd World War, mineralized silver

is also converted into metallic particles
by electrolytic reduction.

Arc’Antique
 1950-Today

Chemical cleaning of copper alloys:

alloys

Various complexing agents and

acids were used, such as Alcaline
Rochelle salt, Calgon, ammonium
hydroxide, EDTA, sodium hydro-
xide, citric acid, formic acid and
sulfuric acid.

Boissonnas
All these products can etch copper alloys and if not properly
used. Most research went into improving these existing
recipes and changing to less aggressive chemicals.

Sodium tripolyphosphate (replaced Calgon), EDTA, alcaline

dithionite (for chlorinated marine bronzes), sodium dithiolate (for
copper sulfates), formic acid.
 1950-Today

Stabilization of copper alloys:

alloys

1967 Madsen introduces Benzotriazole (BTA), a corrosion

inhibitor developed for the copper industry.
Widely adopted by the conservation community. The most recent
studies use it in combination with another corrosion inhibitor,
AMT.

Madsen
 1950-Today

Protective coatings for copper alloys:

alloys
New protective coatings appeared after the
2nd World War such as Frigilene and
Ercalene (nitrocellulose lacquers).
Bedacryl (butyral methacrylate) and
soluble nylon both proved insoluble after a
while.

All these polymers were were replaced by

acrylic resins such as Paraloid (in US
Arcyloid) as well as combined with
stabilizing agents (Incralac).

On outdoor bronzes microcrystalline waxes

are still used today.
J. Scott
 1950-Today

Cleaning of iron

The introduction and adaptation

of air abrasive cleaning with
various abrasive powders
(aluminium oxide, sodium
bicarbonate, walnut shells etc.)
improved cleaning techniques
tremendously.

X-ray radiography and

tomography greatly improved
assessing and cleaning of
corroded iron.
Boissonnas
 1950-Today

Stabilization of iron
1964 Hydrogen reduction is
first used for the conservation of
iron finds from the Vasa. These
heat treatment involves
temperatures of up to 850°C.

Pearson

Successful for stabilization of

cast iron artefacts, but much
metallurgical information is
destroyed.
Replaced by controlled electro-
lytic reduction techniques.
Pearson
 1950-Today

Stabilization of iron
Hydrogen gas plasma emerges in the 80ies as the ideal
treatment for large amounts of artefacts. The created hydrogen
plasma is highly reactive and reduces iron oxides.

Proved not effective

enough to reduce all
chlorides.
Today it is still used
in some labs as a
pre-treatment before
desalination and
mechanical cleaning.

Boissonnas
 1950-Today

Stabilization of iron

1984 EDF sets up a research

programme advocating electrolytic
techniques.
Cast and wrought iron is treated,
but also non-conducting materials
such as leather, wood, paper or
porcelain.

1987 The Titanic is discovered and

1800 items are conserved at EDF
using innovative electrolytic
techniques.
Lacoudre
 1950-Today

Stabilization of iron

Electrolytic techniques have greatly

improved and the use of reference
electrodes has given us safe tools to
work with. They are currently also
used in situ to monitor and stabilize
submerged iron artefacts.

Lacoudre

Arc’Antique
 1950-Today

Stabilization of iron

A new desalination method using

alcaline sulfite baths was
introduced in the late 70ies and has
been widely adapted for chloride
contaminated archaeological iron.

This method breaks down insoluble

chloride containing products, such
as akaganéite.

Boissonnas
 1950-Today

Adhesives & protective coatings for iron

After 2nd World War, epoxy resins are widely used in
conservation of all materials due to their strength and durability.
They replace traditional soldering methods that often
damaged the patina and were highly irreversible. However,
epoxy resins once cured, cannot be dissolved.

Much iron was consolidated and glued with epoxies such as

Araldite. Today we struggle with such objects that have not
undergone desalination, as they continue to break up, but
cannot be retreated.

Lacquers are still in use, mostly acrylic polymers such as

Paraloid (Acryloid) for indoor iron artefacts. Outdoors epoxy
resins or polyurethane resins are used for their durability.
 1950-Today

Preventive conservation of metals

 1950-Today

Preventive conservation of metals

Dessicants and barrier films:

Silica gel, ESCAL foils

Wallert
 1950-Today

Preventive conservation of metals

Dessicants and barrier films:

Silica gel, ESCAL foils

Oxygen scavengers:
Ageless, RP System

Boissonnas
Wallert
 1950-Today

Preventive conservation of metals

Dessicants and barrier films:

Silica gel, ESCAL foils

Oxygen scavengers:
Ageless, RP System

Pollution scavengers:
Activated charcoal, impregnated
textiles,

Wallert
 1950-Today

Preventive conservation of metals

Dessicants and barrier films:

Silica gel, ESCAL foils

Oxygen scavengers:
Ageless, RP System

Pollution scavengers:
Activated charcoal, impregnated
textiles,

Pollutant identification:
Oddy test, Beilstein test, ….. Boissonnas
Tomorrow?
 Tomorrow?

• Achieve better understanding

of corrosion mechanisms

Boissonnas

Selwyn
 Tomorrow?

• Achieve better understanding

of corrosion mechanisms

• Achieve better understanding

of current treatments, develop
new and safer methods

Boissonnas
 Tomorrow?

• Achieve better understanding

of corrosion mechanisms

• Achieve better understanding

of current treatments, develop
new and safer methods

Boissonnas
• Deal with an ever increasing
mass of previously conserved
and freshly excavated objects
 Tomorrow?

• Achieve better understanding

of corrosion mechanisms

• Achieve better understanding

of current treatments, develop
new and safer methods

• Deal with an ever increasing

mass of previously conserved
and freshly excavated objects

• Improve standards and

Boissonnas
facilitate access to education
and training in conservation
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