The restoration and preservation of metallic

archaeological objects made of ferrous materials

requires the elimination of the chlorinated
components contained in the corrosion products.
Otherwise, after excavation of the artefact,
corrosion will continue, sometimes at an
accelerated rate. Different treatments may be
applied for that purpose : electrolytic or alkaline
sulphite baths, cold hydrogen plasma. This paper
describes the hydrogen plasma treatment reactor
in use at the Archaeological Museum of Val dOise.
Results of plasma treatments on artefacts are
presented, together with optical measurements
made at the reactor during the treatments.
I INTRODUCTION
Excavation of an artefact starts a critical phase of its life, as
the equilibrium between this artefact and its burying envi-
ronment, which has been established for years, is then sud-
denly broken.
Actually, when buried, the objects are submitted to corro-
sion, which results in the formation of both internal and
external corrosion layers. Internal corrosion layers confine
around the subsisting metallic core, and are mainly made of
Fe
3
O
4
magnetite (1), on ferrous artefacts. External layers
mainly consist in iron oxides and hydroxides such as
-FeOOH, -FeOOH or -Fe
2
O
3
combined with other mine-
ral products coming from the soil, among which chlorides,
leading to the formation of -FeOOH, for example, which
contains chloride anions in its chemical structure.
After the artefact has been excavated, chlorinated products
decompose into chlorides which promote corrosion again. For
example, -FeOOH becomes -FeOOH, and chloride anions
contained in -FeOOH can then initiate new corrosion phase,
named active corrosion. This active corrosion can dramati-
cally affect the artefact, up to complete destruction.
Conservation and restoration of metallic artefacts aim to
eliminate external corrosion layers, in order to reach the
original surface, and also to prevent new corrosion phases
in order to save the object for the future. This implies the eli-
mination of chlorides contained in the corrosion layers.
Mainly two methods may be used in order to eliminate the
chlorides :
Chemical treatment in alkaline sulphite baths : the object is
immersed in a NaOH-Na
2
SO
3
bath at 50C. SO
3
2-
anions
lead to the chemical reduction of the corrosion layers and
the extraction of the chlorides. The main disadvantage of
this method, the most widely used for conservation and res-
toration of ferrous artefacts, is the duration of the treatment,
which can last over a few months. Moreover, baths have to
be regenerated when saturated in chlorides, which repre-
sents quite a heavy maintenance.
Plasma treatment under a high chemically reducing atmos-
phere by using hydrogen. The use of a low pressure hydro-
gen plasma in order to reduce oxides on corroded objects
was first presented in 1979 (1), and this method was first
developed for ferrous artefacts in the eighties at Zrich
University by S. Veprek et al. (2).
In this article, after a brief report about the principle of this
treatment, we will present the plasma reactor used at the
Archaeological Museum of Val dOise for this kind of treat-
ment. We will report the results of this treatment for some
ferrous objects, and how this treatment helped.
In order to try to understand the mechanisms of this treat-
ment, and also to control it as precisely as possible to pre-
vent any degradation of the objects, optical diagnostics by
emission spectroscopy were also conducted in the system
measurement device, and results will be presented.
As a conclusion, extensions of this plasma treatment to
either other nonferrous metallic artefacts or for industrial
goals such as fine cleaning or surface reductions will be dis-
cussed.
La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001 809
Plasma treatment of artefacts
C. Normand-Chave*, P. Leprince**, F. Dussre***
* Materia Systmes, Ormes
** Laboratoire de Physique des Gaz et des Plasmas,
Universit Paris-Sud, Orsay
*** Muse Archologique Dpartemental du Val dOise,
Guiry-en-Vexin
Manuscrit reu le 20 avril 2001, bon publier le 1er septembre 2001.
La Revue de Mtallurgie 2001.
810 La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001
La restauration et la conservation des objets archolo-
giques mtalliques ferreux passe par llimination des
produits chlors contenus dans les produits de corro-
sion, partir desquels la corrosion continue se dve-
lopper, parfois de manire acclre aprs excavation
de lobjet. Pour ce faire, diverses mthodes peuvent tre
utilises : les bains de sulfite ou lectrolytiques, ou les
traitements par plasma froid dhydrogne. Les premiers,
les plus couramment utiliss actuellement, ncessitent
plusieurs mois de traitement et la mise en place dune
maintenance parfois lourde. Les seconds, outre le
gain de temps quils permettent (traitements allant de
quelques heures quelques jours), permettent la mise
en vidence et la conservation de certains dcors fra-
giles sur les objets.
Cet article prsente le racteur de traitement par plasma
froid dhydrogne dont sest quip le Muse Archo-
logique Dpartemental du Val dOise, ainsi que des
rsultats de traitements dobjets et les analyses optiques
ralises sur le racteur durant les traitements.
Dot dune enceinte ractionnelle de 0,45 m de dia-
mtre et de 1,5 m de longueur (volume de 240 l environ),
ce racteur permet la cration dun plasma majoritaire-
ment compos dhydrogne (80 90 % typiquement)
au moyen dun gnrateur RadioFrquence (27,12 MHz),
des pressions pouvant varier de quelques 10
-1

quelques mbar (0,5 mbar typiquement), et pour des

puissances de lordre de 1000 1500 W.
Dans ces conditions, la dure moyenne de traitement
dun objet varie gnralement de 2 10 h, et la temp-
rature de cet objet reste stable, infrieure 300C pen-
dant la dure du traitement.
Les atomes dhydrogne crs dans ce plasma peuvent
alors, dune part, rduire certains oxydes des couches
externes de corrosion, rendant ainsi la surface de lobjet
corrod pulvrulente et friable (et facilitant donc un net-
toyage mcanique ultrieur), et, dautre part, rduire les
produits chlors contenus dans les couches de corro-
sion active internes (ces produits, rduits, disparaissent
sous forme gazeuse, stoppant et stabilisant ainsi la cor-
rosion).
En cas de mise en uvre ultrieure dun traitement par
bain de sulfite afin dliminer les dernires traces de pro-
duits de corrosion chlors, la dure de ce traitement est
rduite quelques jours seulement.
Les traitements raliss sur un certain nombre dobjets
ont permis de mettre en vidence la facilit plus grande
de nettoyage mcanique au cours de la restauration,
ainsi que la prservation de certains dtails de dcor
fragiles.
Afin de mieux comprendre les mcanismes intervenant
lors de ces traitements par plasma, un dispositif dana-
lyse optique a t mis en place sur le racteur de traite-
ment du Muse Archologique Dpartemental du Val
dOise : il est constitu dun spectromtre optique cou-
pl une fibre optique, les longueurs donde analyses
allant de 200 900 nm.
Il est principalement noter que lon observe une mis-
sion notable, au cours des traitements, dans la rgion
des 310 nm, correspondant lmission de radicaux
-OH, et pouvant tre attribue la formation dhy-
droxydes au cours de la rduction de certains oxydes,
ainsi que, dans une certaine mesure, un dgazage
complmentaire durant le traitement.
Des analyses complmentaires, en cours sur des objets
plus chargs en produits chlors que les prouvettes
analyses dans un premier temps, devraient permettre
la mise en vidence dmissions caractristiques lies
la rduction des produits chlors au cours du traitement.
Traitement dobjets archologiques
par plasma avant restauration
C. Normand-Chave*, P. Leprince**, F. Dussre***
* Materia Systmes, Ormes
** Laboratoire de Physique des Gaz et des Plasmas,
Universit Paris-Sud, Orsay
*** Muse Archologique Dpartemental du Val dOise,
Guiry-en-Vexin
EXPERIMENTAL PROCEDURE
Principle of the plasma treatment
Low pressure plasmas, created by means of DC, radio fre-
quency, or microwave discharge, are partially ionized (ioni-
zation rate between 10
-8
and 10
-4
depending on the way the
plasma is created), and contain electrons, ions and electri-
cally neutral species such as atoms, radicals or excited
molecules, which can be highly chemically active.
For example, low pressure plasmas created in air or oxygen
contain oxygen atoms which can enhance surface modifi-
cations such as improvement of plastics wettability. Such
plasmas are already used for industrial purposes : plastic
treatment before sticking, painting, metallizing, printing (3).
In hydrogen plasmas, hydrogen atoms are created : their
concentration may reach 80 % depending on operating
conditions (4). These atoms will play a key-role for the chemi-
cal reduction of the corrosion products.
The plasma reactor at the Archaeological
Museum of Val dOise
The system is presented figure 1 and the vacuum chamber
and control panels are shown figure 2.
The vacuum chamber, made of glass, is 1.5 m in length and
0.45 m in diameter (volume 240 l). The objects to be trea-
ted are put on a quartz plate of 1.5 m in length.
The pumping device consists in a rotary pump of 80 m
3
/h,
associated with a dust filter, in order to prevent severe
damage of the pump due to potential abrasive dust coming
from the artefact. Hydrogen, argon, nitrogen and methane
are introduced into the vacuum chamber for the treatment ;
their flow are controlled by means of flow meters.
The plasma is created at 27.12 MHz by means of a
2.8 kW Sairem generator, and the power is coupled to
the gas by means of copper electrodes outside of the
vacuum chamber. The impedance adapter is motori-
zed, in order to get easy use of the reactor. The gene-
rator is water-cooled.
Two pressure gauges allow precise control of the pres-
sure before (outgassing) and during the treatment. A
thermocouple has also been added in order to control
the temperature of the object during the treatment. In
fact, this parameter has to be carefully controlled, and
operating conditions have to be adjusted to avoid
important temperature increase of the artefact, in order
to prevent degradation due to metallurgical phase
transformations which may occur with increased tem-
perature.
In order to prevent exhaust of toxic products, gases at
the exhaust of the pump are cracked in a furnace
before coming out at atmospheric pressure.
The whole system is associated with an hydrogen
detector and a general control panel, in order to allow
completely safe operation.
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La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001 811
Figure 1 Schematic of plasma reactor.
Figure 1 Schma de principe du racteur
de traitement par plasma.
Figure 2 Plasma reactor. Vacuum chamber
and control panels.
Figure 2 Racteur plasma : vue densemble.
I RESULTS AND DISCUSSION
Treatment of ferrous artefacts
Typical operating conditions are : pressure 0.5 mbar, plasma
containing either 90 % H
2
, 8 % N
2
and 2 % Ar, or 80 % H
2
,
20 % Ar, radio frequency power between 1000 and 1500 W,
treatment time approximately 2 to 10 h.
Under these conditions, temperature of an object remains
stable under 300C during the treatment.
Figure 3 (5) shows a Merovingian damascened buckle
after plasma treatment. Reduced corrosion products after
the treatment are shown, with the restored original damas-
cened surface.
Figure 4 (5) shows other Merovingian objects after plasma
treatment. The plasma treatment here helped to reveal
some decorative details that had not never been seen pre-
viously (fig. 5).
Figure 6 also shows claps on which some textile pieces have
been preserved after the plasma treatment.
From these few examples, it appears that the main advan-
tages of the plasma treatment for ferrous artefacts are :
corrosion products become dusty and friable, allowing
easier work for the restorer and preservation of some
decorative details that are damaged when using other
methods ;
traitement plasma
812 La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001
Figure 4 Other Merovingian objects after plasma treatment
and restoration.
Figure 4 Fibules mrovingiennes aprs traitement
par plasma et restauration.
Figure 3 Merovigian damascened buckle after plasma treatment
and partially restored.
Figure 3 Boucle mrovingienne damasquine aprs traitement
par plasma et restauration partielle.
Figure 5 Detail of figure 4.
Figure 5 Dtail de la figure 4.
Figure 6 Claps with textile pieces after plasma treatment
and restoration.
Figure 6 Boucle daumnire ayant conserv
des traces de textile, aprs traitement par plasma et
diffrents stades de restauration.
plasma treatment lasts over a few hours against a few
months for sulphite bath treatments ;
after plasma treatment, artefacts also are submitted to
sulphite bath treatment, in order to eliminate residual
chloride traces. In this case, the sulphite bath treatment
only lasts a few days or weeks, and is easier to conduct.
For all these reasons, plasma treatment is a very promising
method for the treatment of artefacts before restoration and
conservation.
At the moment, most of the experiments conducted at the
Archaeological Museum of Val dOise concern ferrous arte-
facts, but other scientists over Europe and Egypt are also
working with plasma devices on nonferrous artefacts, such
as copper, copper alloys, silver, tin (4). They point out that
plasma treatment is also suitable for these materials, under
appropriate operating conditions.
These preliminary studies at the Archaeological Museum of
Val dOise and by other scientists in Europe have demonstra-
ted the feasibility and interest of plasma treatment.
A purpose now is to optimize this way of treatment, and to
determine whether it is possible to set real-time control
of it. For this purpose, the plasma reactor at Archaeological
Museum of Val dOise has been equipped with optical dia-
gnostics.
Emission spectroscopy
As the plasma naturally emits some light, emission spectro-
scopy is widely used to identify plasma species, to measure
them, and to control industrial plasma processes.
The experimental setup for spectroscopic analysis is pre-
sented figure 7.
An optic fibre is placed 0.5 cm away from the vacuum cham-
ber, so that the light emitted by the plasma around the object
during the treatment can be analysed. The signal is trans-
mitted by the optic fibre to a Jobin Yvon-Sofie spectrometer,
which is able to accumulate spectra in order to minimize
the noise and get the most precise information possible.
Spectra are recorded between 200 and 900 nm, but as the
vacuum chamber is made of glass, transmission of wave-
lengths between 200 and 300 nm is very poor.
Figure 8 shows the spectrum of a gas mixture containing
hydrogen, nitrogen and argon, without any artefact in the
plasma.
Characteristic spectral bands of molecular excited nitrogen
appear in the range of 300-430 nm, and between 550 and
800 nm. Characteristic emission lines of hydrogen are also
seen at 486.3 and 65.5 nm.
traitement plasma
La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001 813
Figure 7 Experimental setup for spectroscopic analysis.
Figure 7 Dispositif exprimental pour la ralisation
des analyses spectroscopiques.
Figure 8 Spectrum between 200 and 900 nm of a plasma
in a mixture of H
2
-N
2
-Ar. No artefact within the plasma.
Figure 8 Spectre entre 200 et 900 nm dun plasma
dans un mlange de H
2
-N
2
-Ar.
Figure 9 Spectrum between 200 and 900 nm of a plasma
created in a H
2
-Ar mixture. No artefact within the plasma.
Figure 9 Spectre entre 200 et 900 nm dun plasma plac
dans un mlange de H
2
-Ar.
(
6
5
6
,
2
7

m
m
)
(
6
5
6
,
2
7

m
m
)
RF generator
Plasma reactor Spectrometer Photomultiplier
Acquisition
system
Computer
Optic
fiber
G
a
s

i
n
e
r
t
To pumping divice
and furnance
Figure 9 shows the spectrum of the hydrogen-argon mixture
without any artefact. Actually, nitrogen mainly acts as a pas-
sivating agent for the surface. As artefacts after plasma
treatment are restored, the passivation layer is mechani-
cally eliminated by the restoration. So some experiments
were conducted without any addition of nitrogen in the gas
mixture. Yet, considering the limit pressure of the system,
some nitrogen always remains trapped on the chamber
walls, which explains the emission of NH, and the existence
of some bands between 300 and 430 nm which may be attri-
buted to excited N
2
.
Figure 10 presents recorded spectra at various times during
the plasma treatment of an artefact. It has to be noticed that
an intense emission appears at the beginning of the treat-
ment, in the region of 310 nm, which may be attributed to
-OH bonds. This emission might be due either to the out-
gassing of-OH radicals (water vapour, for example) from the
object during the treatment, or to the chemical reduction of
hydroxides into oxides. This has to be confirmed by further
experiments.
The main expectations related to spectroscopy concern the
existence of characteristic emission of chlorinated products
during the treatment. Unfortunately, it was not possible to
identify any one.
Yet, it has to be noticed that quantitative analysis on cur-
rently treated objects by the Archaeological Museum of Val
dOise indicate that chlorine concentrations in these arte-
facts is very low, which may explain the lack of optical detec-
tion of these species. This has to be confirmed by plasma
treatments on artificially highly chlorinated samples. This
work is in progress.
traitement plasma
814 La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001
Figure 10 Evolution of the plasma spectrum during plasma treatment of artefacts.
Figure 10 volution du spectre du plasma durant le traitement par plasma des objets.
a) b)
c)
d)
e) f)
I CONCLUSION
Plasma treatment of artefacts seems to be a promising
method for preparing objects to be restored and conserved,
shorter than classical sulphite bath treatment, leading to
easier work for the restorer, and less aggressive than other
methods, as it helps in the preservation of some ornamental
details which had previously never been observed.
Yet, this method still has to be investigated, for example in
order to treat nonferrous objects, or, for ferrous objects, to
get a precise control of the object temperature, preventing
metallurgical modifications of the structure.
Precise knowledge of the mechanisms of the treatment and
the way to control it also have to be investigated.
As the principle of this method is a chemical reduction of
products under plasma conditions, this technique may be
used for fine cleaning of other non-archaeological objects :
preliminary experiments have been conducted in a laboratory
device, which prove the feasibility of the method.
As it also has been proved with the plasma reactor at the
Archaeological Museum of Val dOise that this kind of plasma
is stable, repetitive, easy to start, and that the starting and
coupling may easily be achieved with automatic coupling sys-
tems, industrial use of this method might be considered.
Acknowledgements
The authors wish to thank the Archaeological Museum of Val
dOise for its help and photographs.
references
(1) DANIELS (V.D.), PASCOE (M.W.), HOLLAND (L.) Studies
in Conservation, 24 (1979), p. 85-92.
(2) VEPREK (S.), ELMER (J.T.), ECKMANN (C.), JURCIK-
RAJMAN (M.) J. of the Electrochemical Society, 134(10)
(1987), p. 2398-2405.
(3) NORMAND-CHAVE (C.) Le Vide : Les couches minces.
273 (1994), p. 333-340.
(4) ROUSSEAU (A.), GRANIER (A.), GOUSSET (G.), LEPRINCE
(P.) J. of Physics D, Applied Physics, 27 (1994), p. 1412.
(5) Archaeological Museum of Val dOise la recherche du
mtal perdu, Errance, ed. (1999), p. 135-155.
traitement plasma
La Revue de Mtallurgie-CIT/Science et Gnie des Matriaux Septembre 2001 815