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Advanced Plasma Treatment for Cleaning and Protecting

Precious Metal Artefacts
Sabrina Grassini1, Emma Angelini1, Riccardo d’Agostino2, Fabio Palumbo3, Gabriel M. Ingo4
1
Dipartimento di Scienza dei Materiali ed Ingegneria Chimica, Politecnico di Torino, Italy
2
Dipartimento di Chimica, Università di Bari, Italy
3
Istituto per le Metodologie Inorganiche e dei Plasmi, IMIP-CNR, Bari, Italy
4
Istituto per lo Studio dei Materiali Nanostrutturati, ISMN-CNR, Roma, Italy

Dipartimento di Scienza dei Materiali ed Ingegneria Chimica, Politecnico di Torino

Corso Duca degli Abruzzi 24, 10129 Torino, Italy
Phone: +390110904642
Fax: +390110904699
e-mail: sabrina.grassini@polito.it

Low pressure plasmas can be successfully carried out to develop a reversible procedure for cleaning and pro-
tecting precious metal artefacts. In this study, cold plasma treatments were applied on Ag-based alloys with
microchemical and microstructural features similar to ancient artefacts, buried for six months in the archaeo-
logical site of Tharros (Sardinia, Italy). Dry etching in H2 plasma allows to completely remove the patina with-
out affecting the bulk properties, while SiOx thin films, deposited in a glow discharge fed with TEOS, Ar and
O2, exhibit good corrosion protection.

Keywords: low pressure plasma, protective coatings, dry etching, metallic artefacts, corrosion
1. INTRODUCTION
One of the main problems for the preservation of
metallic archaeological objects excavated and stored in mu-
seum is their long-term conservation. Not only is corrosion
is a never-ending problem, conservator-restorers (C-R)
must also clean the artefact from dirt to reveal its shape and
hidden decorations, as well as stabilize it. C-Rs must choose
the correct strategy to slow down surface degradation phe-
nomena so as to avoid further damages.
Conservation must use protection methods which are
reversible as well as respecting the integrity of the objects,
such as the aesthetic appearance.
Low pressure plasmas (the so-called cold plasma) ex-
hibit the following major advantages, which suit perfectly
their application in the field of metals conservation:
— dry processes easily performed at room temperature in
order to preserve the metallurgical features;
— application can be made directly on the exterior or the
interior of complex shapes of objects;
— plasma etching can be controllable and selective at
nanoscale and the surface ion bombardement can be
carefully controlled in order to avoid any damage;
— plasma deposition can produce very thin coatings with
customizable structure having a minimal effect on the
appearance of the surface, along with very good corro-
sion protection.
Cold plasmas fed with organosilicon compounds ob-
tain one of the most investigated classes of PECVD trans-
parent thin films [1]. Among them, SiCxHyOz pinhole free
thin films have been successfully employed for the corrosion
protection of different metals. Moreover, plasma deposition
can be preceded by surface treatments with inert or reactive
gases, which play a fundamental role in enhancing the adhe-
sion of the coating to the underlying substrate [2, 3].
The aim of this study, carried out under the framework
of PROMET project (financially supported by the Euro-
pean Commission, VI FP, INCOMED contract no 509126)
is to develop a non-destructive and reversible procedure for
cleaning and protecting precious archaeological objects,
mainly Cu and Ag-based alloys, in low pressure plasma.
Silver objects are usually alloyed with copper, and even
if there is 50/50 Cu/Ag, the appearance of the metal is still
white. When silver is tarnished, the removal of tarnishing
film requires the use of Table 1 – Experimental conditions
of Plasma Treatments

Table 1 – Experimental conditions of Plasma Treatments

Step Feed composition Pressure Power Treatment time Thickness
(sccm) (mbar) (W) (min) (Ìm)
Etching of the patina H2: 20 1.3.10-2 50 20-60 -
TEOS: 2
SiOx deposition O2: 45 1.33 250 90 0.6-1.5
Ar: 22
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S. Grassini et al.

chemicals, abrasives, or electrochemical reduction to re- Microscopy (FEG-SEM Supra40, Zeiss, Microscope
move the silver sulphide. The restored surface still has high equipped with a EDAX 9900, Energy Dispersion Microprobe).
susceptibility to re-tarnish, when re-exposed to an environ- The protective effectiveness of the SiOx film was as-
ment with sulphur containing materials. In this case, the sessed by means of Electrochemical Impedance Spec-
silver objects have to be cleaned frequently, and each time troscopy (EIS). Electrochemical impedance measure-
the tarnish is removed so is some silver [4, 5]. The best way ments were performed in aerated 0.1M NaCl solution at
to avoid frequent cleaning is to protect the silver objects in the laboratory temperature of 25±1oC, using a frequency
a controlled environment, if possible. However, it may be response analyzer EIS300 (Gamry Instruments). Imped-
impossible for curators to maintain such a microclimate ance spectra were recorded at the open circuit potential af-
free of sulphur, and for this reason, some conservators pre- ter 1h of exposure to the aggressive environment, by apply-
fer to coat silver objects for their protection against tar- ing a sinusoidal signal of 10mV amplitude in the frequency
nishing. However, lacquering or waxing is not recommend- range 100 kHz–10 mHz with five points per decade.
ed for silver, because of the difficulties in obtaining an even
coating, so that if there is uneven coating when the object 3. RESULTS AND DISCUSSION
tarnishes again, the end result may be worse than if no
coating is applied at all. For this reason, the suitability of 3.1 Characterisation of the Silver Alloys
PECVD transparent thin films for protecting such objects The silver reference alloys were characterised by het-
made of cultural property need to be investigated further. erogeneous microchemical structure, chemical composi-
tion and metallurgical features similar to those of the an-
2. EXPERIMENT cient alloys.
The SEM-EDS results (Fig.1) disclose the presence of
The experimental apparatus used for this study is a ca- small copper islands scattered in the silver alloys and the
pacitively coupled parallel plate reactor with an asymmet- occurrence of a phase separation i.e., discontinuous pre-
ric electrodes configuration. It consists of a vacuum cham- cipitation typical of the copper-silver alloys used in antiqui-
ber made of stainless steel, a powered electrode connected ty. It is well known that this phenomenon, as well as the
to a RF power supply (13.56 MHz) through an impedance presence of Pb along grain boundaries, could be related to
matching unit and a ground electrode. Gas and organosili- the age-embrittlement of ancient silver based artefacts.
con vapour flow rates are controlled by mass-flow and
vapour source controllers, respectively, while a turbomole- 3.2 Plasma Etching of the Patina
All Ag-alloy specimens buried in the archaeological site
cular pump backed by a rotary pump, a throttle valve, and a
of Tharros had on both sides, a uniform dark brown patina
pressure gauge allow to keep the pressure fixed at the se-
on its surface. Soil traces (carbonates, etc.) are present in the
lected value.
white areas. The results of the chemical and microstructural
Plasma treatments have been applied on two silver/
characterisation of the surface confirm that the artificial
copper reference alloys with microchemical and mi-
patinas are similar to the archaeological ones because the
crostructural features similar to ancient artefacts. Their
main corrosion products detected are chloroargyrite (AgCl)
chemical compositions are as following:
and paratacamite ((Cu,Zn)2(OH)3Cl) as observed on silver
— Alloy A: Ag 97.0, Cu 1.5, Pb 1.5 (wt%)
archaeological artefacts (Fig. 2).
— Alloy B: Ag 96.5, Cu 3.5 (wt%).
In order to evaluate the possible application of the
plasma treatment on real artefacts, the reference alloy
specimens were buried at the archaeological site of Thar-
ros (Sardinia, Italy) for a period of 6 months. For acceler-
ating the corrosion degradation 5wt% of NaCl has been
added to the soil. This addition is justified considering the
role played by chlorides on the degradation of silver alloys
during burial.
After 6 months, the aged specimens were gently
cleaned in ultrasonic bath using iso-propylic alcohol for 15
minutes to remove all the traces of soil.
Dry etching of the patina has been performed in low
pressure hydrogen plasma, while protective SiOx thin films
have been deposited in plasma fed with tetraethoxysilane
(TEOS), Ar and O2 (see Table 1).
The chemical and morphological characterisation of the
patina, before and after the H2 glow discharge, was per- Figure 1 - Back scattered electrons images that show the
formed by means of X-Ray diffraction (Philips X-Pert pow- metallurgical features of the reference alloy B (a) and of a
der diffractometer) and Field Emission Scanning Electron Roman Republican silver coin (b)
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Advanced Plasma Treatment for Cleaning and Protecting Precious Metal Artefacts
Figure 2 – XRD spectra recorded on the reference alloy A,
before (black spectrum) and after the H2 plasma treatment
(red spectrum)
During burial the silver alloys specimens were subject-
ed to the main degradation phenomena found on ancient
silver artefacts:
— silver corrosion with formation of patina mainly made
up of chloroargyrite
— the copper degradation commonly called “bronze dis-
ease”, since copper exists in the copper rich phases of
the silver alloy matrix.
Figure 3 – SE and BSE images of the patina of the alloy A
(a); EDS maps of: Ag (b), Cu (c), Cl (d) and O (e)
The back scattered electron images of the patina and
EDS data show high concentration of Cu in small, circle-
129
shaped area of the surface, that appear black in the BSE im-
age; while high Ag concentration is detected in the white ar-
eas (Fig. 3). A glow discharge in a low pressure hydrogen
plasma produces H atoms as well as ions. Though not stud-
ied in detail yet, it can be assumed that hydrogen atoms di-
rectly react with the patina and remove the dangerous cop-
per chlorides by the formation of volatile HCl. However the
role of the impinging ions cannot be ruled out: very likely the
reactivity of the surface is enhanced by the striking ions. Fur-
thermore, the glow discharge reduces silver ions (Ag+) back
to silver (Ag0). These two effects of the H2 discharge are
confirmed by the XRD and EDS analyses: the peaks of
chloroargyrite disappear in the XRD spectrum (Fig. 2),
Figure 4 – SE and BSE images of the surface of the alloy A
after H2 discharge (a); EDS maps of: Ag (b), Cu (c), Cl (d)
and O (e)
while the EDS maps show evidence of a noticeable reduc-
tion of the chloride concentration on the surface treated in
H2 plasma (Fig. 4). Consequently, the surface was convert-
ed again into bright metallic silver without affecting the
bulk properties (Fig. 5).
Depending on the treatment time, the H2 plasma was
able to significantly reduce the thickness of the corrosion
layer. Fig. 6, the thickness of the patina grown during burial
on the silver reference alloy B is about 13.4 Ìm. After a
plasma treatment of 30 min, it is reduced to about 6.4 Ìm.
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S. Grassini et al.

The SiOx film was deposited in the experimental condi-

tions optimised for silver substrates in a previous study.
Here, the high barrier properties against sulphide, oxygen
and water vapour can be achieved by depositing the film at
high input power in oxygen rich plasma [6].
The SiOx coating is really effective in the protection of
the silver surface against aggressive environments as estab-
lished by the impedance measurements.
Figure 5 – Aged alloy A, before and after the H2 plasma
treatment

The plasma cleaning treatment restored the original

surface of the object and it is important to underline that
the H2 discharge can be performed also for cleaning gilded
artefacts without damaging surface decorations. In this
case the experimental parameters must be optimised by re-
ducing the discharge input power, and consequently reduc-
ing the surface ion bombardment.

3.3 Plasma deposition of the protective layer

The high versatility of plasma processes allow to per-
form, after the cleaning treatment, a deposition of a thin
protective coating without exposing the object to atmos-
pheric contaminants. Figure 7 – Bode plots recorded on silver alloy B before and
after the deposition of the SiOx film

Figure 7 shows the Bode plots recorded on the silver al-

loy B before and after the deposition of the protective SiOx
layer. Notwithstanding the low thickness (about 0.9 Ìm) of
the deposited coating, a noticeable inhibiting action to-
ward the corrosion process occurring on the metal surface
was observed, as underlined by the increase of the value of
the low frequency complex impedance |Z| that may be esti-
mated from the plateau region on the Bode plot in the fre-
quency range 0.001-0.01 Hz.
The utilization of the Bode plot has the advantage to
avoid the complex and time-consuming data fitting pro-
cedures normally used to define the system’s equivalent
electric circuit for fitting the impedance spectra. The
value of |Z| indicates the extent of the electrolytic con-
duction paths at the metal/coating interface: high |Z|
values are indicative of a good protective effectiveness
of the coating [7].
The increase in the value of the impedance modulus
(|Z|) can be correlated to the barrier effect of the SiOx film
against the aggressive environment and also to its high con-
formability to the surface, even if it is already coated by a
thin layer of corrosion products. The SiOx film smoothes
the cavities present in the patina, avoiding the penetration
of the corrosive agent through the corrosion layer till the
metal surface.
The high degree of adaptability to any surface rough-
ness is another key factor to meet the requirements of cu-
rators involved in the conservation of archaeological sil-
Figure 6 – SEM images of the patina of alloy B (a) before ver artefacts characterised by very complex decorations.
(13,4 Ìm thick) and (b) after (6.4 Ìm thick) the H2 plasma The advantage of the EIS technique over other labora-
discharge tory techniques for the assessment of the corrosion behav-
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Advanced Plasma Treatment for Cleaning and Protecting Precious Metal Artefacts
iour of coated systems is the possibility of using very small
amplitude signals (10 mV) without significantly disturbing
the properties being measured.
This approach can be applied by curators and C-Rs not
skilled in electrochemistry; as a matter of fact C-Rs can
easily obtain an indication of the protective effectiveness of
the coatings without affecting the conservation state of the
artefact.
9. CONCLUSIONS
The conservation of Cultural Heritage requires a mul-
tidisciplinary approach in order to develop tailored conser-
vation strategies for cleaning and protecting precious
works of art of archaeological and historical interest.
The preliminary results, discussed in this paper, show
the feasibility of the application of low pressure plasma
treatments in the conservation of movable ancient silver
artefacts.
Further investigations should be considered in order to
optimise the cleaning procedure as a function of the chem-
ical composition of the patina and to optimise the deposi-
tion of plasma coatings as a function of the samples surface
condition.
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