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 aime Traditional products and techniques used on metal artefacts aimed d
at maintaining their function and preventing their deterioration at maintaining their function and preventing their deterioration
Traditional techniques and materials
Traditional products and techniques used on metal artefacts aime Traditional products and techniques used on metal artefacts aimed d
at maintaining their function and preventing their deterioration 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 Neats
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 Neats
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
Knigliches 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.
Antiquits 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
dArchologie des mtaux 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
Schliemann
Milkau
Rathgen
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
1850-1900 Digging up problems
Boissonnas
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.
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 Active Corrosion on on copper alloys 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 120-150C.
Ellis & Hermanis
Boissonnas
Boissonnas
1850-1900 Digging up problems
Cleaning of Cleaning of copper alloys 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
esthetical look (Petrie 1888).
Van Langh
1850-1900 Digging up problems
Mechanical Cleaning of Mechanical Cleaning of copper alloys 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 Electrochemical cleaning of copper alloys 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 Electrochemical cleaning of copper 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 Protective coatings for copper 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 Cleaning & stabilization methods for 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
Mallowan Brittner
Brittner Williams
1900-1920 Towards a better understanding
Corrosion & mechanical cleaning of copper alloys Corrosion & mechanical cleaning of copper 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
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.
Mechanical cleaning of copper alloys Mechanical cleaning of copper alloys:
Born
1900-1920 Towards a better understanding
Active Corrosion Active Corrosion on copper alloys 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 Stabilization of
copper alloys 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 Stabilization of iron 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
o
C,
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
Carter
British Museum
Schorsch
British Museum
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 Cleaning copper 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 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 Protective coatings
come from the automobile and aircraft industry.
Cellulose acetates and Perspex are replacing
traditional natural waxes.
B
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1920-1950 New concepts and old recipes
Stabilizing iron Stabilizing 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 Stabilizing 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 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 surface that represents the
object when abandoned object when abandoned. Bertholon (2000)
defines the original surface more precisely
as limitos limitos, , that can be located with the help
of markers markers.
Boissonnas
1950-Today
Electrolytic treatments of copper alloys Electrolytic treatments of copper alloys:
Boissonnas
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.
1950-Today
Electrolytic treatments of copper alloys Electrolytic treatments of copper alloys:
In the 70ies France-Lanord proposes electrolytic reduction with electrolytic reduction with
low current low current. Increases removal of chlorides without stripping
corrosion products. EDF pushes technique further for treating
marine bronzes under cathodic cathodic protection protection in sodium
sesquicarbonate.
This treatment has been adapted as standard treatment for marine
bronzes. The measurement of the corrosion potential corrosion potential of the object
with a reference electrode 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 Electrolytic treatments of lead and silver 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 2
nd
World War, mineralized silver
is also converted into metallic particles
by electrolytic reduction.
ArcAntique
1950-Today
Chemical cleaning of copper alloys Chemical cleaning of copper 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.
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.
B
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1950-Today
Stabilization of copper alloys Stabilization of copper 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 Protective coatings for copper alloys:
New protective coatings appeared after the
2
nd
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 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 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 850C.
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 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 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 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
ArcAntique
1950-Today
Stabilization of iron 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 akaganite.
Boissonnas
1950-Today
Adhesives & protective coatings for iron Adhesives & protective coatings for iron
After 2
nd
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 Preventive conservation of metals
1950-Today
Preventive conservation of metals Preventive conservation of metals
Dessicants and barrier films:
Silica gel, ESCAL foils
Wallert
1950-Today
Preventive conservation of metals Preventive conservation of metals
Dessicants and barrier films:
Silica gel, ESCAL foils
Oxygen scavengers:
Ageless, RP System
B
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Wallert
1950-Today
Preventive conservation of metals 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 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
Selwyn
Boissonnas
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
Deal with an ever increasing
mass of previously conserved
and freshly excavated objects
B
o
i
s
s
o
n
n
a
s
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
facilitate access to education
and training in conservation
B
o
i
s
s
o
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n
a
s
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